Bd. 40 (1986) H. 2 Organic Acid Pulping of Wood, Part II.

99

Holzforschung
40(1986)99-108

Organic Acid Pulping of Wood

Part II. Acetic Acid Pulping of Aspen
By Raymond A. Young and James L. Davis
Department of Forestry, University of Wisconsin, Madison, Wisconsin USA
and
Eva-Barbara Wiesmann
Department of Wood Technology-Wood Chemistry, University of Hamburg, Hamburg, West Germany

Keywords Organic Acid Pulping of Wood. Part H. Acetic Acid Pulping of Aspen
Acetic acid
Pulping Summary
Delignification Aspen chips were cooked in aqueous acetic acid (50—87.5%) for up to two hours at temperatures in the
Water absorbency ränge of 160-185PC. Good delignification was achieved (Kappa numbers 10-40) with pulp yields of
Aspen 50—60%. Although satisfactory lignin removal could be realized with äs low äs 50% acetic acid, the de-
Populus tremuloides Michx. lignification selectivity was improved at higher concentrations. A useful guideline for Optimum choice of
the acetic acid concentration in the liquor is a Hildebrand solubility parameter of approximately 11.0.
An acetone wash may be necessary to remove reprecipitated lignin after the cook. The pulps showed
satisfactory to good water absorbency.

Schlüsselwörter
(Sachgebiete)
Essigsäure-Aufschluß
Delignifizierung
Wasseraufnahmeeigenschaften
Amerikanische Zitterpappel
Holzaufschluß mit organischen Säuren. Teil II. Aufschluß von Aspenholz
Zusammenfassung
Es wurde ein Essigsäureaufschluß mit Aspenholz untersucht. Die Hackschnitzel wurden bei Temperatu-
ren zwischen 160—185 °C mit einer wäßrigen Essigsäurelösung (50—87,5%) aufgeschlossen. Eine aus-
reichende Delignifizierung konnte schon mit einer 50%igen Essigsäure erzielt werden, jedoch fand eine
erheblich selektivere Delignifizierung bei Einsatz einer höher konzentrierten Essigsäurelösung statt.
Wieder ausgefallenes Lignin kann durch eine Acetonwäsche entfernt werden. Die Zellstoffe erreichten
befriedigende bis gut Wasserabsorptionseigenschaften.

Introduction quality, chemical losses and recovery, and environ-

The pulp and paper industry must undergo changes in
the next few decades due to increased shortages of
capital, energy, chemicals, wood fiber and water. The
established pulping processes, the sulfite and kraft
process, show limited flexibility regarding modifica-
tions to meet the requirements of future situations.
For these reasons alternate pulping methods are con-
tinually under investigation.
During the past 20 years, a variety of non-conven-
tional solvent pulping methods have been explored.
Solvents such äs glycols (Nelson 1977), amines
(Ogiyama et al. 1973), ketones (DeHass and Lang
1974), dimethylsulfoxide (Nahum and Pellegrini
1970), dioxane (Engel and Wedekind 1933), phenol
(Schweers 1974), nitric acid (Ba et al. 1980), and
aliphatic alcohols (Kleinert 1974, Diebold et al. 1978,
Hansen and April 1982, Paszner and Chang 1981),
have been evaluated äs pulping media. Poor pulp
mental problems have plagued the further develop-
ment of most of these processes.
Aqueous ethanol pulping has been recently promoted
for delignification of hardwoods (Myerly et al. 1981).
However, catalysts such äs mineral acids (HC1),
(Young and Achmadi 1983), Lewis acids (A12C13),
(Sarkanen 1980) or magnesium chloride (Paszner and
Chang 1981), are necessary to pulp softwoods. Pulp
strength is generally comparable to sulfite pulps. Al-
though the aqueous ethanol organosolv process has
reached the pilot plant stage (Lora and Aziz 1984),
energy requirements for ethanol recovery and the
need for total byproduct utilization may limit further
development.
Less attention has been paid to the use of organic
acids äs pulping agents. This series of papers will
explore the use of organic acids äs pulping agents for
wood (Young et al. 1985).

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 R.A. Young, J.L. Davis and E.-B. Wiesmann
100
Use of Organic Acids in Pulping and Bleaching
Several investigators have used a small quantity of acetic acid äs an
additive to improve the delignification rate or the carbohydrate re-
tention in chemical or semichemical pulping processes.
Lyubavskaya (1974) added up to 15% acetic acid to an aqueous sol-
ution of sodium sulfite in a semichemical process. The rate of delig-
nification and the rate of carbohydrate dissolution both increased,
but the selectivity for lignin did not change significantly.
Sakakibara et al. (1983) observed an increase in selectivity for lig-
nin dissolution, äs well äs improvements in the burst factor and
folding endurance, when they added acetic acid to cooking liquor
composed primarily of cresols and water. Spruce chips were pulped
for 1.5 hours at 180°C with a L/W ratio of 7/1. With liquor contain-
ing 49% cresols, 49% water, and 2% acetic acid, pulp with a Klason
lignin content of 7.3% was obtained at a yield of 50.8%. With 65%
cresols, 28% water, and 7% acetic acid, the lignin content feil to
5.6% and the yield rose to 58.2%. Both pulps were superior to cor-
responding pulps produced without the addition of acetic acid.
Buchholtz and Jordan (1982) described a pulping process in which
hardwood or softwood chips were boiled in an 80% formic acid sol-
ution containing a catalyst (not identified). Hardwood chips were
reportedly pulped to a Kappa number 60—65 (i.e. lignin content of
9-10%) in 45 minutes with a yield of 59%.
Mbachu and Manley (1981) studied the effects of acetic and formic
acids on the protection of carbohydrates during ozone bleaching.
Unbleached kraft pulp that had been soaked in a solution of 45%
acetic acid (pH = 2) or 45% formic acid (pH = 2) before bleaching
exhibited a higher bleached pulp viscosity than pulp that had been
presoaked in water (pH = 5 or 6) or in a sulfuric acid solution (pH
= 2). All pulps were ozone bleached to the same lignin content.
This improvement in selectivity for lignin removal during bleaching
was attributed by Mbachu and Manley to decreased accessibility of
the cellulose to the ozone. The degree of cellulose swelling was
thought to be lower in the organic acid Solutions than in a sulfuric
acid solution of the same pH.
Kamishima et al. (1982) reported that a variety of organic acids
exhibited this carbohydrate protection phenomenon during ozone
bleaching of kraft pulp. Oxalic, propionic, butyric, valeric, and ace-
tic acids provided significantly higher bleached pulp viscosities than
did unsaturated or aromatic adids, when pulps were presoaked in
the acid and then bleached to approximately the same lignin con-
tent.
Acetic Acid Pulping
It has been known for a long time that acetic acid acts
äs a solvent for lignin (Schuerch 1952). However,
there are few published investigations on the use of
acetic acid for pulp production. Wiltshire (1944)
boiled wood chips in glacial acetic acid at atmospheric
pressure and was able, by the addition of a small
amount of sulfuric acid, to produce satisfactory pulp.
Under these conditions, Wiltshire could not obtain a
pulp unless sulfuric acid (1% by weight)was added äs
a catalyst. As the sulfuric acid Charge was increased
from 1% to 6%, the screened pulp yield rose to a
maximum value of approximately 52% and the shive
yield declined to about 6%. If the sulfuric acid Charge
exceeded 3%, the pulp became "darker and more
'parchmentized', of decreasing bulk and increasing
hardness." .
Water content in excess of 5% of the cooking liquor
was reported to reduce the rate of delignification; ex-
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Holzforschung
tended cooking times were required. Wiltshire (1944)
estimated that the Optimum value for chip moisture
content lay in the ränge 12-15%.
The replacement of up to 2.5% of the acetic acid by
acetic anhydride lowered the burst factor and in-
creased the bulk factor of the reSuIting pulp, com-
pared to pulp produced with only acetic acid and sul-
furic acid. These differences were attributed to acety-
lation of the cellulose. A reduction in screened pulp
yield and an increase in shive yield were observed
when the acetic anhydride concentration was in-
creased from 0.5% to 1.5% of the cooking liquor.
Herdle et al. (1964) also conducted pulping experi-
ments using strong acid catalysts in acetic acid media.
Their work focused on the production of dissolving
pulp for conVersion to cellulose acetate, but some of
their results have a wider significance. In a series of
experiments at 110°C under atmosperhic pressure for
3 hours, a 0.5% HC1 solution was more effective (pulp
yield = 51%, lignin content = 7.1%) than a 0.5%
H2SO4 solution (pulp yield = 55%, lignin content =
22%). For these experiments the water content of the
cooking liquor was controlled at 2.2%, including the
moisture present in the air dried western hemlock
chips.
Additional experiments were performed in sealed di-
gesters at temperatures ranging from 112° to 160°C.
In these experiments the water content of the solution
was 5%, and the H2SO4 content was lowered to 0.2%.
The yield and pentosan content declined steadilywith
increasing temperature, but a minimum value for lig-
nin content was achieved at approximately 140 °C.
The effect of the water content in the liquor on the
pulp and the pulping reaction was also studied. The
cooking procedure included a one hour heatup in the
150 °C oil bath and four hours at the steady state tem-
perature. Minimum values for pulp yield, lignin con-
tent, and pentosan content. were obtained with
10-14% water in the liquor. These findings confirm,
in more detail, the observations of Wiltshire, and ex-
tend the ränge of applicability to higher temperatures.
Koval and Slavik (1963) obtained a pulp by refluxing
wood chips at 70 °C for 3-6 hours in mixtures of acetic
acid <60-80%), acetone (10-30%), and concen-
trated hydrochloric acid (10%). A L/W rato of 5:1
proved to be satisfactory. The yield of pulp ranged
from 49% to 54%, and the total recovery (i.e. pulp
plus soluble fraction) exceeded 92% of the original
wood material.
DeHaas and Lang (1971) were able to eliminate the
need for a strong acid catalyst by increasing the tem-
perature at which the pulping was carried out. They
obtained pulp from hardwood and softwood chips (or
sawdust) by using a solution of 85-96% acetic acid
and a L/W ratio between 2/1 and 8/1 at a temperature
»r
Bd. 40 (1986) H. 2
in the ränge 150-205 °C, in order to limit the Op-
timum cooking time to 2-5 hours. They asserted that
water content in excess of 15% (of the cooking liquor)
reduced the pulp yield äs a result of polysaccharide
hydrolysis, slowed the delignification process, and
caused precipitation of the lignin addition, they em-
phasized the need to use äs a pulp washing solvent
"fresh acetic acid, (or some) other solvent or solvent
mixture which does not tend to reprecipitate" the lig-
nin. In this paper acetic acid pulping of aspen is
further explored.
Experimental
Three sets of experiments were carried out to evaluate the effects
of selected reaction variables on the acetic acid pulping of aspen
(Populus tremuloides), These three sets will be referred to äs the
"small scale", "intermediate scale", and "large scale" laboratory
experiments. The pulping liquor in each experiment consisted only
of acetic acid (HAc) and water. Unless specified otherwise, the
concentration of acetic acid in the liquor is expressed in percent by
volume.
For the small scale experiments, 10—12 grams of matchstick size
aspen Chips (moisture content = 17%) were charged into a 100 ml.
stainless steel digester. Cold pulping liquor was added to the diges-
ter, and the sealed digester was placed into a temperature-control-
led oil bath for the specified reaction time. Approximately 20 mi-
nutes were necessary before the contents of a small digester
reached the final reaction temperature. The heatup time is not in-
cluded in the reaction time listed for the small scale experiments.
The post-treatment procedure will be described below. The pulp
yield was determined by drying the pulp in vacuo at 60 °C overnight,
and was reported äs grams of oven dry pulp per gram of oven dry
wood. The lignin content of the pulp was measured by the Kappa
number (according to Tappi Useful Method 246 and Tappi Stan-
dard T236).
For the intermediate scale experiments, 60 grams of aspen chips
(approximately 2 cm X 5 cm x 0.5 cm) were charged into a l liter
stainless steel reactor. Cold pulping liquor was added, and a 30 mi-
nute period of presoaking at ambient temperature was included be-
fore the sealed reactor was placed in the temperature-controlled oil
bath for the specified reaction time. Approximately l hour was
needed before the contents of the l liter reactor reached a steady
state temperature. The heatup time is included in the reaction time
listed for intermediate scale experiments. The cooked chips were
washed with an acetic acid-water solution of the same composition
äs the cooking liquor, then fiberized in a blender, and washed fi-
nally with acetone. In addition to the pulp yield and Kappa
number, a Klason lignin determination (Effland 1977) was made
for each batch of pulp. Residual lignin content and percent delig-
nification were computed äs follows:
residual lignin = Klason lignin x pulp yield
residual lignin
delignification = 100% —·—-
lignin content in wood
Content of the five primary sugars (Glucose, xylose, mannose,
galactose, and arabinose) in the pulp was determined by acid hy-
drolysis and high performance liquid chromatography (Pettersen et
al. 1984).
The large scale trials were carried out in a 7 liter rotating (3.5 rpm)
digester. Approximately 340 grams of aspen chips (11.5% moisture
content) were used in each trial. The digester was preheated with
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Organic Acid Pulping of Wood, Part II. 101
steam to a temperature of 120 °C. The chips and liquor were then
charged into the warm digester, and a heatup time of only 30 mi-
nutes was needed to reach a reaction temperature of 175°C. The
reaction time for the large scale experiments does not include any
heatup time.
The intrinsic viscosity [ ] of selected pulps was measured using the
method of Jayme and Neuschaffer (1957). The weight average de-
gree of polymerization (DPw) was calculated by means of the
Staudinger equation, äs follows:
[ ] = 0.0184 x DPw°76
The dewatering ability of a pulp was measured in degrees Schop-
per-Riegler and converted to Canadian Standard Freeness. The re-
maining physical property tests were conducted according to Tappi
Standard methods, äs follows: tensile strength (Tappi 494), burst
strength (Tappi 403), double folding endurance (Tappi 423), tear
strength (Tappi 414), and density (Tappi 410, 411).
To measure the water absorbency a sample of fluffed, air dry pulp
was packed to a density of 0.1 gr./ml. into a vertical cylinder with
a partially open bottom surface. The cylinder was placed into a con-
tainer of distilled water, allowed to remain partially submerged for
30 seconds, and then removed. The water absorbed by the pulp was
measured by the weight gain. The cylinder was again partially sub-
merged in distilled water, this time for 30 minutes, and weighed a
second time. The absorbency of the pulp was reported äs grams of
water per gram of pulp.
Results and Discussion
The initial objective of this project was to produce a
highly absorbent pulp of low Kappa number, using a
low acetic acid concentration, a short cooking time,
and a moderate reaction temperature. With these in-
itial goals in mind, a number of independentvariables
were adjusted. The independent variables included
reaction time, acetic acid concentration, liquor-to-
wood ratio, maximum reaction temperature, and pulp
washing procedure. The effects of the variables on
pulp yield (%), lignin content (Kappa number), ab-
sorbency (grams of water per gram of pulp), and
strength properties were determined. The present dis-
cussion will focus primarily on pulp yield, Kappa
number, and delignification.
Effect of Reaction Time and Pulp Post-Treatment —
Small Scale
The effect of both cooking time in 50% acetic acid at
175 °C and the pulp washing procedure on the extent
of delignification for small scale experiments is shown
in Figure 1. It is immediately obvious from the consis-
tently high Kappa numers at all reaction times (upper
curve) that a substantial amount of the lignin remains
adsorbed on the pulp at the end of the cook even with
an extensive water wash. This lignin adsorption
phenomenon was promoted by the post-treatment
procedure which involved cooling of the small scale
digesters in a cold water bath before removal of the
pulp and spent liquor.
The dramatic effect of a subsequent acetone washing
of these same pulps is shown by the difference be-
tween the upper and lower curves (Figure 1); the re-
 Holzforschung
102 R.A. Young, J.L. Davis and E.-B. Wiesmann

duction in Kappa number averaged 112 units. At the
same time the pulp yield declined by 10-20% (based
on oven dry wood). A two-stage washing procedure
(first acetic acid/water, then acetone) was incorpo-
rated for all additional small scale trials.
200 1
160
120
«a
S:
3 60
1 4
ReacHon Time (hrs)
\
Fig. 1. Effect of cooking time in 50% acetic acid (175°C) on delig-
nification of aspen chips. The upper curve is for water washed pulp
and the lower curve for acetone washed pulp.
As shown in Figure l, increasing the reaction time
from l to 4 hours resulted in only a slight decrease in
Kappa number; pulp yield showed the same general
trend. However, cooking times greater than four
hours caused an increase in both the Kappa number
and yield. It is probable that the lignin irreversibly
reprecipitates onto the pulp at longer reaction times;
that is, a lignin precipitate is formed on the fiber dur-
ing prolonged cooking, and this precipitate is not
acetone extractable. Acetylation of the cellulose and
lignin is also remotely possible under the reaction
conditions.
Based on these and subsequent experiments, it ap-
pears that with an acetic acid concentration of 50% or
greater the majority of the delignification takes place
during the first hour of cooking. At lower acetic acid
concentrations a reaction time greater than one hour
may be beneficial.
Effect of Acetic Acid Concentration and Liquor
to Wood Ratio - Small Scale _
The effect of the acetic acid concentration and liquor-
to-wood ratio on delignification for small scale
batches reacted for one hour in thef 175°C oil bath is
shown in Table 1. A concentration of 25% acetic acid
is insufficient for suitable delignification (minimum
Kappa No. 59). However, at a concentration of 50%
(or above) the aqueous acetic acid delignifies the
wood very well; a Kappa number äs low äs 22 is attain-
able with a liquor-to-wood ratio of 4:l.
Further, although less dramatic, improvements were
achieved at 75% acetic acid concentration. A Kappa
number of about 14 was obtained at the lower liquor-
to-wood ratios with 75% acetic acid. At four hours
reaction time the delignification was further improved
with both 50% and 75% acetic acid; Kappa numbers
of 14 and 7 were obtained, respectively (Table 1).
The acetic acid concentration also affects pulp yield
5
(Table 2) but not to the same extent that it influences
delignification. It appears that there is better selec-
tively for delignification at a higher acetic acid con-
centration. This conclusion is in agreement with that
of previous investigators (DeHaas and Lang 1971).
There is a small but significant increase in yield when
the acetic acid concentration in the cook is raised from
50% to 75% (Table 2). This increase may be due to
enhanced carbohydrate protection resulting from a
lower water content in the liquor or possibly some
acetylation of the pulp. With the acetic acid concen-
tration fixed at a value of 50% or greater, the pulp
yield increased äs the liquor-to-wood ratio decreased.
Similar reasoning to that just described for acetic acid
concentration effects would also be pertinent to the
effect of the liquor-to-wood ratio. There appears to
be no delignification advantage with high liquor-to-
wood ratios for acetic acid pulping. This is in contrast
to the Situation with aqueous ethanol pulping where
high liquor-to-wood ratios are generally necessary to
achieve good delignification (Young and Achmadi
1983, Sarkanen 1980). ,
A 3-factorial experiment was conducted with the data
in Table l to obtain systematic Information on the in-

Table 1. Delignification (Kappa Numbers) at Various Reaction Conditions for Acetic Acid Pulping of Aspen

Acetic Acid Concentration Acetic Acid Concentration Acetic Acid Concentration

25% 50% 75%
Liquid/Wood Ratio 4:1 6:1 8:1 10:1 4:1 6:1 8:1 10:1 4:1 6:1 8:1 10:1

Reaction Time (hrs)

l 59.8 83.5 98.3 122.2 22.1 23.4 30.4 22.5 14.7 13.6 14.1 23.3
2 71.4 77.4 87.2 119.0 23.4 16.3 23.7 28.3 15.7 8.6 11.0 18.2
3 69.1 75.0 89.0 122.2 21.5 22.4 17.5 23.8 12.6 9.8 11.5 23.3
4 59.4 70.0 86.6 109.5 14.0 23.9 15.0 22.2 16.2 7.6 6.8 13.3

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Bd. 40 (1986) H. 2 Organic Acid Pulping of Wood, Part II. 103

Table 2. Yield at Various Reaction Conditions for Acetic Acid Pulping of Aspen

Acetic Acid Concentration Acetic Acid Concentration Acetic Acid Concentration

25% 50% 75%
Liquid/Wood Ratio 4:1 6:1 8:1 10:1 4:1 6:1 8:1 10:1 4:1 6:1 8:1 10:1

Reaction Time (hrs)

1 54.1 52.9 55.7 57.6 52.9 49.3 48.6 48.6 58.6 51.3 53.3 51.4
2 55.4 52.8 54.4 54.2 51.9 49.0 48.7 48.7 54.8 50.8 51.8 53.4
3 57.0 52.7 54.6 55.0 51.8 51.2 47.6 47.7 55.0 50.1 54.0 52.4
4 56.5 52.0 54.2 52.3 51.9 52.5 47.8 48.6 55.7 50.7 51.9 52.2

teraction between the different variables. Based on an several pertinent acetic acid concentrations was deter-
analysis of variance, no significant effects could be mined in intermediate scale experiments (Figure 2;
found for the interactions between acetic acid concen- Table 3). The pulp yield declined with time for each
tration and time nor between the liquor-to-wood ratio level of acetic acid Concentration (Table 3); the high-
and time. However, the interaction between acetic est yield at each cooking time was obtained with the
acid Concentration and liquor-to-wood ratio was highest level of acetic acid Concentration (87.5%).
found to be highly significant. This result suggests that With 50 or 75% acetic acid the minimum Kappa
the acetic acid content (i.e. grams of acetic acid per ιοο
gram of oven dry wood) and the water content (i.e. 90
grams of water per gram of oven dry wood) would 60
represent significant independent variables in a study 7Ο
of pulping kinetics. The reaction time was evaluated υ 60
between l and 4 hours and was not found to be signif- Λ

icant; however, it is expected that time up to one hour Ο

α.
50
α
would be highly significant for delignification. 40

3Ο

Effect of Reaction Time and Acetic Acid 20 -

Concentration — Intermediate Scale 10 -

Using the improved pulp washing sequence (hot ace-

tic acid/water, then cold acetone) and the low liquor- 50% HAc
Reoction Time (hrs)
75% HAc o 87.5% HAc
to-wood ratio (4:1)
^ ' established
. in the small scale -.
Fig. -2. cEffect
« ^ of *· acid
f acetic -A Concentration
* *· and A cooking
\,· *·time onAde-
tnals, the effect of reaction time m a 175°C bath for lignification of aspen chips.
Table 3. Acetic Acid Pulping of Aspen-Intermediate Laboratory Scale

Acetic Acid Pulping (Aspen) per 100 gr. D wood

Trial Bath L/W Liquor Time Max. Overall Pulp Kappa Delignifica- Resid. Resid. Resid. Resid.
Temp. Concen. Temp. Rec'y. Yield number tion Lignin Xylose Glucose Mannose
(O^^*\
^^ r
/ O/ \
\ /O J (%) (%) (g1"·) (gr.) (gr.) (gr.)

64 175°C 4.0 50% Ihr 103.1 71.7 82 58.5 8.68 10.5 50.9 2.18
60 4.0 1.5 hr 101.9 59.1 48 79.0 4.38 6.15 48.5 1.51
75 3.9 2hr 96.7 56.2 36 83.4 3.46 5.37 49.0 1.18
70 3.9 3hr 88.9 52.3 33 87.5 2.62 4.03 48.4 0.94
51 4.0 4hr 87.2 52.3 34 86.5 2.82 4.13 50.8 0.84

57 175°C 4.0 75% Ihr 160 103.8 64.7 60 76.8 4.88 8.61 46.5 2.25
59 3.9 1.5 hr 164 100.8 58.1 32 88.0 2.50 7.09 46.5 2.02
58 3.9 2hr 165 94.2 55.4 20 93.4 1.37 5.87 45.3 1.80
84 4.0 3hr 165 89.5 52.5 11 95.4 0.97 5.09 47.4 1.70
49 4.0 4hr 165 90.2 53.2 14 92.3 1.60 4.95 41.7 1.97

67 175°C 4.0 87.5% Ihr 103.1 . 70.2 60 67.4 6.81 11.3 46.6 2.27
74 4.0 1.5 hr 101.2 63.2 37 82.2 3.59 8.91 50.2 2.17
71 3.9 2hr 97.6 58.7 24 89.9 2.12 7.51 47.4 1.94
72 4.0 3hr 93.5 55.6 14 94.4 1.18 6.72 49.9 1.66
73 3.9 4hr 91.5 55.0 11 96.2 0.79 5.61 49.0 1.39

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 Holzforschung
104 R.A. Young, J.L. Davis and E.-B. Wiesmann

number (Figure 2) and maximum degree of delignifi- minimum Kappa number and the highest degree of
cation (Table 3) were obtained after 3 hours of cook- delignification were achieved at the lowest reaction
ing. Cooking beyond this point resulted in excessive temperature when 75% acetic acid was used.
lignin condensation, which led to a rise in the Kappa 100

number and a decline in the degree of delignification. 90 -

With 87.5% acetic acid, delignification and Kappa 80 -
number improved steadily with time up to a cooking
70 -
time of 4 hours. Longer cooking times were not
evaluated. The use of 75% acetic acid allowed more »sp 60 -

rapid delignification to take place and permitted the v 50 -

α
delignification to proceed to a greater extent than was Q.
40 -

possible with 50% acetic acid. A further increase in 30 -

acid concentration from 75% to 87.5% offered no sig- 20 -

nificant advantage in delignification rate at this reac- 10 -

tion temperature. Ο —τ— —l—

20 40 60 ΘΟ
Koppo Number
Effect of Acetic Acid Concentration and Maximum 50% HAc 75% HAc o 87.5% HAc

Reaction Temperature — Intermediate Scale
Table 4 contains the results from a series of inter-
mediate scale experiments performed by reacting the
aspen chips for l hour with a specified maximum reac-
tion temperature (160,170, or 183 °C) and a specified
acetic acid concentration (50, 75, or 87.5%). A
liquor-to-wood ratio of 4:1 and the improved washing
procedure (described above) were employed for all
trials in this section. The pulp yield and Kappa
number both declined and the percent delignification
steadily increased s the reaction temperature was
raised. It is clear that through proper choice of the
acetic acid concentration and the reaction tempera-
ture, a pulp with a Kappa number between 9 and 40
may be obtained after only one hour of cooking, in-
cluding the heatup time. Among several possible
combinations (of acetic acid concentration and reac-
tion temperature) the pulp yield for a desired Kappa
number was maximized at high acid concentration
and low reaction temperature. However, the
Fig. 3. Selectivity plots of percent pulp yield versus Kappa number
for pulping of aspen chips at several acetic acid concentrations.
Selectivity
The specificity for the dissolution of lignin is shown
most clearly in a plot of pulp yield against Kappa
number (Figure 3). Data points from trials with vari-
ous temperatures and various reaction times using a
fixed acetic acid concentration lie along a single line.
Thus, it is primarily the acid concentration that deter-
mines the Selectivity of the process for removing lig-
nin. Figure 3 indicates the major improvement in
Selectivity was obtained by increasing the acetic acid
concentration from 50% to 75%. The improvement
in yield became greater s the target Kappa number
declined. Additional improvement was realized by in-
creasing the acid concentration from 75% to 87.5%.
It should be noted that the Selectivity curves may not
be extrapolated in the direction of lower Kappa num-

Table 4. Intermediate Scale Laboratory Acetic Acid Pulping of Aspen-Temperature and Concentration Effects

Acetic Acid Pulping (Aspen) perlOOgr.ODwood

Trial Bath L/W Liquor Time Max. Overall Pulp Kappa Delignifica- Resid. . Resid. Resid. Resid.
Temp. Concen- Temp. Rec'y. Yield number tion Lignin Xylose Glucose Mannose
tration (°C) (%) (%) (%) (gr.) (grO (gr.) (gr.)

64 175°C 4.0 50% Ihr 103.1 71.7 82 58.5 8.68 10.5 50.9 2.18
57 4.0 75% Ihr 160 103.8 64.7 60 76.8 4.88 8.61 46.5 2.25
67 4.0 87.5% Ihr 103.1 70.2 60 67.4 6.81 11.03 46.6 2.27

63 187°C 3.9 50% Ihr 98.3 54.3 40 . 86.2 2.89 4.90 47.2 1.33
65 3.9 75% Ihr 170 92.1 52.8 10 96.2 0.79 4.99 46.9 1.30
68 4.0 87.5% Ihr 101.2 62.9 40 85.5 3.03 8.24 48.9 2.23

62 200°C 3.9 50% Ihr 91.9 50.9 30 89.8 2.13 3.79 44.6 0.92
66 3.9 75% Ihr 183 89.2 51.3 9 96.5 0.73 4.32 46.4 1.11
69 4.0 87.5% Ihr 93.3 55.1 10 96.2 0.79 5.79 45.8 1.77

aspen wood 20.9 20.2 48.4 2.8

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Bd. 40 (1986) H. 2 Organic Acid Pulping of Wood, Part II. 105

bers. The increase in lignin condensation rate with
time, limits the minimum obtainable Kappa number
to a fixed value, which is dependent upon the acetic
acid concentration (cf. Figure 3).
The yield improvement (for a given Kappa number)
obtained by increasing the acetic acid concentration
translated primarily into improved retention of the
hemicellulose fraction during pulping. Figure 4 dis-
plays the relationship between the residual xylose
content (i.e. grams of xylose remaining in the pulp per
100 grams of oven dry wood) and the residual lignin
content (i.e. grams of lignin remaining in the pulp per
100 grams of oven dry wood). For a given amount of
residual lignin in the pulp, the use of 75%, rather than
50%, acetic acid led to the retention in the product
pulp of an additional 2—3 grams of xylose (per 100
grams of oven dry wood). Less than one additional
gram of xylose (per 100 grams of oven dry wood) was
retained when the acetic acid concentration was
further increased from 75 to 87.5%.
14
13 -
12 -
11 -
10 -
9 -
8-
o
O 7 -
6-
5-
4 -
3-
2-
1 -
were made on a larger scale. The results obtained
from the large scale rotating digester are shown in
Table 5. It is obvious for these trials that only a one-
half hour reaction time was necessary to produce pulp
with a very low Kappa number. The liquor circulation
and agitation caused by the rotating digester en-
hanced the delignification rate, compared with the
previous experiments.
The properties of the acetic acid pulps from aspen are
shown in Tables 6 and 7 and Figure 5. Reference sul-
fite and kraft pulps were included for comparison, al-
though the Kappa number of the sulfite pulp was
higher than the acetic acid pulp. The pulps were gen-
erally delignified to low Kappa number to improve
absorbency characteristics, which was the primary
goal of this initial investigation.
As shown in Figure 5, the beating resistance of the
acetic acid pulps is similar to that of the reference Sul-
fite pulp. The unbeaten acetic acid pulp reaches a
freeness level äs low äs 250 with 10 minutes beating
time. The reference kraft pulp shows a much higher
beating resistance.
Although pulp strength was not the primary goal, the
strength results are shown in Table 6. At a freeness of
450—475, the acetic acid pulp has lower strength than
800
70O

O 2 10 12
Lianin Content
O 50% HAc 75% HAc 87.5% HAc

Fig. 4. Percent xylose versus lignin content of pulp from aspen

chips cooked at several acetic acid concentrations. Dashed line
represents a 1:1 relationship.

12 14
Large Scale Laboratory Trials Beotino Time, min
Kroft o HAc(4:1) HAc(6:1)
To validate the results obtained with intermediate Fig. 5. Beating curves for two acetic acid pulps cooked at two
scale laboratory experiments and to obtain larger liquor-to-wood ratios (4:1 and 6:1) compared to reference kraft and
quantities of pulp for paper testing, pulping trials sulfite pulps.

Table 5. Large Scale Laboratory Acetic Acid Pulping of Aspen

Acetic Acid Reaction Temperature, Liquor-to- Kappa Intrinsic Degree of Yield, «%

Concentration, Time, Min. °C Wood Ratio Number Viscosity, Polymerization
% cm3/g (Weight Average) Fiber Shive Total

40 30 175 4:1 13.0 595 2049 44.0 0.3 44.3

50 30 175 4:1 14.8 667 2327 46.6 0.8 47.4
50 30 175 6:1 12.8 680 2394 46.6 1.7 49.3
50 30 175 8:1 11.3 693 2451 47.3 0.3 47.5
50 60 175 4:1 9.2 443 1360 22.5 ...
22.5
50 120 175 4:1 burned cook L_
«.

50 ,30 160 4:1 38.8 —

770 — —
2813 50.6 6.4 57.0
50 30 150 4:1 47.9 777 2850 48.2 13.3
_ 61.5
75 30 175 4:1 8.7 791 2917 ^_
—

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 R.A. Young, J.L. Davis and E.-B. Wiesmann Holzforschung
106

Table 6. Strength Properties of Acetic Acid and Conventional Pulps

Kappa Tensile Burst Fold Tear Density

Pulp Freeness
Number Strength(m) (m2) (double) (cN) (g/cc)
(CSF)
•
Acetic Acid 13
0.71 .
S\ *V<4

650 4220 18.6 6 54.$

475 5220 32.3 102 58.6 0.78
375 6190 34.5 210 50.2 0.81
450 10 7205 34.9 178 ' 77.8 0.74
Kraft
Sulfite 475 30 7780 43.7 549 56.7 0.84

centrations used in this investigation is äs follows:

Table 7. Absorbent Properties of Acetic Acid and Commercial
Pulps
Absorbency*
Pulp 30 second, Rating
Commercial AI 2.73 poor
Commercial A2 , 3.86 good
Acetic Acid \ \
AA1 2.70 poor
AA2 2.85 fair
the reference kraft and sulfite pulps in all categories
except tear where the acetic acid pulp is comparable,
even at a much lower Kappa number. Optimization
for pulp strength will be evaluated in future work.
The pulp absorbency characteristics were determined
by the modified procedure described in the experi-
mental section. A comparison of the absorbency of
the acetic acid pulps with Standard commercial absor-
bent pulps is shown in Table 7. The two commercial
pulps were rated for absorbency äs "good" and
"poor". While the acetic pulp was fair to poor in the
30 second absorbency category, the 30 minute absor-
bency was good.
Overview of Acetic Acid Pulping
The following two-step mechanism is proposed to ex-
plain the above results in acetic acid pulping:
1. Acid catalyzed hydrolysis of lignin (and the car-
bohydrate components).
2. Solvation of lignin fragments by the pulping liquor
(i.e. acetic acid and water).
A high concentration of acetic acid is necessary in the
pulping liquor because the acetic acid is thought to
perform two roles. It is a:
1. Source of the hydronium ions for acceleration of
the acid hydrolysis of lignin.
2. Solvent for the lignin fragments produced by the
hydrolysis reaction.
The pH of aqueous acetic acid Solutions for the con-
25% HAc (pH = 1.7), 50% HAc (pH = 1.2), 75%
HAc (pH = 0.3). Solutions of 25% and 50% acetic
acid fall within the pH ränge (1-2) commonly used
to promote efficient lignin removal in the acid sulfite
30 Minute, Rating pulping process (Sjöström 1981). The sulfite process
is generally regarded äs a three Step process in which
5.69 poor
acid hydrolysis of the lignin is followed by sulfonation
7.62 good of the lignin fragments; the modified fragments
(which have become more hydrophilic by virtue of the
5.48 poor sulfonation) are then solvated by water molecules
9.64 excellent
(Sjöström 1981). Acetic acid is an extremely weak
nucleophile, so acetylation of the lignin is unlikely.
Since the pH in the acetic acid Solutions used in the
present experiments was low enough to accelerate lig-
nin hydrolysis, the solvation of lignin fragments must
hold the key to lignin removal in the acetic acid pulp-
ing process.
Table 8. Values of the Hildebrand Solubility Parameter for Vari-
ous Solvents
Solvent Solubility Parameter ( )
formic acid 12.1
acetic acid 10.1
propionic acid 9.9
methanol 14.5
ethanol 12.7
n. propanol 11.9
acetone 9.9
water 23.4
If lignin is viewed äs a high molecular weight polymer
for which a suitable solvent is to be found, the Hilde-
brand solubility parameter is a useful tool. Schuerch
(1952) tested the ability of more than 30 organic sol-
vents and water to dissolve a variety of lignin prepara-
tions. He concluded that those solvents with a Hilde-
brand solubility parameter ( ) of approximately 11.0
were the solvents best able to dissolve large lignin
fragments. If the value of the solubility parameter for
a solvent lay far from the Optimum value, Schuerch
(1952) asserted that this solvent would only be able to
dissolve small lignin fragments. Since a solvent with a
value of close to 11.0 would be able to dissolve large
lignin fragments, use of a better lignin solvent in the

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Bd. 40 (1986) H. 2
pulping liquor would reduce the degree of lignin de-
gradation necessary in order for the lignin fragments
to become soluble in the cooking liquor. The values
for several organic solvents and water appear in Table
8. The high value of for water (23.4) is consistent
with the observation that lignin is practically insoluble
in water, unless the lignin is chemically modified to
make it hydrophilic. In order for the effective solubil-
ity parameter of an aqueous acetic acid solution to ap-
proach 11 to 12, the concentration of acetic acid
would have to be quite high. In the present discussion
the acetic acid concentration is generally given in per-
cent acetic acid by volume. However, for the consid-
eration of solvation phenomena, the composition of
the solvent by mole, rather than by volume, may be
more appropriate. Solutions of 25%, 50%, 75% and
87.5% acetic acid by volume correspond to Solutions
of 9.5%, 23.9%, 48.6%, and 68.8% acetic acid by
mole.*
On a molar basis Solutionsof 25% and 50% ace-
tic acid (by volume) may be considered to be moder-
ately dilute Solutions of a lignin solvent (acetic acid)
in a lignin precipitant (water). It is therefore not sur-
prising that the former solution is completely unsatis-
factory for use äs pulping liquor (Table 1) and that the
selectivity of the latter solution .for lignin dissolution
is quite poor (Figure 3, 4). Only when the number of
acetic acid molecules present in the pulping liquor is
roughly equal to the number of water molecules does
the selectivity for delignification in the acetic acid
pulping process reach a satisfactory level.
An additional factor in the relationship between
greater specificity for lignin dissolution and higher
acetic acid concentration may be the ability of acetic
acid to prevent the wood substance from swelling.
Apostol and Koslov (1980) reported that the degree
of swelling observed in wood chips that had been im-
pregnated with aqueous acetic acid Solutions de-
creased äs the acetic acid concentration of the solu-
tion increased. However, the work of Schuerch (1952)
showed that acetic acid should be an excellent solvent
(and thus an excellent swelling agent) for lignin prep-
arations. If the results of Schuerch are applicable to
native lignin äs well, then the results obtained by
Apostol and Koslov (1980) suggest that an increase in
the acetic acid concentration reduces the swelling of
primarily the carbohydrate components of wood.
Less swelling of the carbohydrates would mean that
the carbohydrates would be less accessible for hydro-
lysis and dissolution. More of the lignin could be at-
tacked with less degradation of the hemicellulose.
This conclusion is consistent with the increase in pulp
yield, specifically xylose retention, (for a fixed Kappa
number) that was observed in the present study when
the acetic acid concentration was raised from 50% to
75%. In the case pf 87.5% acetic acid, the degree of
swelling may be so limited that even the lignin itself
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Organic Acid Pulping of Wood, Part II. 107
becomes less accessible than it would be in a solution
of 75% acetic acid. This could explain the fact that the
initial delignification rate in 87.5% acetic acid is lower
than the rate in 75% acetic acid (Table 3), even
though the selectivity for lignin dissolution is higher
in 87.5% acetic acid (Figure 4). The need to provide
sufficient hydronium ions to accelerate lignin hydro-
lysis and sufficient acetic acid molecules to solvate the
lignin fragments must be balanced against the need
for sufficient swelling to make the lignin accessible for
rapid chemical attack.
Conclusions
The pulping experiments carried out thus far have
shown convincingly that a pulp with a satisfactory
Kappa number (10—40) may be obtained with an ex-
cellent yield (50—60%) by cooking aspen chips in a
liquor composed entirely of acetic acid and water. A
liquor-to-wood ratio of 4:1 was adequate for this pro-
cess (lower ratios were not evaluated). Delignifica-
tion proceeded most efficiently in small scale experi-
ments, where uniform cooking and a rapid rise to the
final cooking temperature were possible. Even when
a one hour heatup period was adopted, 85—95% de-
lignification was achieved by the end of the heatup
period alone, if the maximum reaction temperature
lay between 170 and 185°C. The maximum degree of
delignification at the lowest reaction temperature was
observed when the cooking liquor contained approxi-
mately 49% acetic acid on a molar basis (i.e. 75% ace-
tic acid by volume). An increase in the acetic acid con-
centration from 49% to approximately 69% on a
molar basis (i.e. from 75% to 87.5% by volume) im-
proved the selectivity of the process for lignin dissolu-
tion and increased the pulp yield for a fixed Kappa
number. However, the delignification rate was lower
in the 69% (by mole) solution, and it was necessary
to increase the reaction temperature or to extend the
reaction time in order to obtain the desired Kappa
number. For every reaction temperature and liquor
composition, there existed an Optimum cooking time,
at which delignification reached a maximum value.
Cooking beyond that point led to further lignin con-
densation and an increase in the pulp Kappa number.
The importance of washing the cooked chips with sol-
utions that are good lignin solvents was demonstrat-
ed. A three step washing procedure (two washes with
fresh cooking liquor and a final wash with acetone)
proved to be very effective for removing the lignin
fragments created during the cooking step.
The initial rate of water absorbence by acetic acid
pulps was marginal, compared with commercial ab-
sorbent pulps. Acetic acid pulps that had been delig-
nified to a low Kappa number showed an excellent
capacity to absorb water over a longer period of time
(e.g. 30 minutes).
 R.A. Young, J.L. Davis and E.-B. Wiesmann
108
Cooking to a low Kappa number (e.g. 13) in order to
improve the absorbency of acetic acid pulps reduced
the strength properties, compared with sulfite pulps
with a more customary Kappa number (e.g. 30). The
strength properties of acetic acid pulps with Kappa
numbers between 15 and 30 will be evaluated in future
work.
Acknowledgements
Appreciation is expressed to Marilyn Effland and other members
of the USDA Forest Products Laboratory for lignin and sugar
analyses. Financial support of the College of Agricultural and Life
Sciences and the Fulbright-Hays Foundation for E.-B.W. is grate-
fully acknowledged.
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•t