ORGANOSOLV-PULPING OF OIL PALM EMPTY BUNCH

USING ACETIC ACID AND ETHANOL

Herri Susanto, Zulfansyah and Firdaus

Department of Chemical Engineering, Institute od Technology Bandung
Jalan Ganesha 10, Bandung-40312, Indonesia
Facsimile: +62-22-2501438; email: herri@bdg.centrin.net.id

Abstract
A comparative study on organosolv-pulping of oil-palm empty bunch has been done
experimentally in a 2 L autoclave. Main process variables were selected based on
literature: 70% acetic acid with addition of a small quantity of HCl (up to 0.2% by mass
to solid raw material) and 50% ethanol with addition of NaOH (up to 9%). Cooking with
acetic acid were carried out at 120 to 160C for 60 to 240 minutes, while cooking with
ethanol were carried out at 150 to 190C for 60 to 140 minutes. Both processes could
produce pulp with lignin contents in the range of 1 to 12% (Kappa number 30 to 100)
expected to be suitable for various types of paper. Acetosolv-pulping could produce pulp
with -cellulose content as high as 93% probably suitable for rayon, while the other
process yielded pulp with -cellulose content only up to 76%.

1. Introduction

Following the growth of crude palm oil (CPO) industries in Indonesia, much
attention should also be paid to manage solid wastes, particullarly on oil-palm empty bunch
6
(OPEB). The annual production of OPEB is estimated at least 3x 10 ton, approximately as

much as CPO production. Unfortunately, utilization of this lignocellulose waste is still

insignificant, although it is collected already in CPO mills and available throughout the year.
Organosolv-process have been proposed by many researchers as an alternative process to
fractionate biomass into its constituents or derivatives: hemicellulose,cellulose and lignin. In
principle, this selective process is simultaneouss hydrolysis of hemicellulose and dissolution of
lignin in an organic solvent, and leaving cellulose in a solid product (see process diagram in
Figure 1). Recently, interests on the use of organosolv-process for pulp production have grown
due to some advantages of this process over the conventional kraft process, such as: no emmision
of sulfur compound, simple process in solvent recovery and potential utilization of by-products
(lignin, fermentable sugars and furfural).
Research on the fractionation of OPEB has been done recently in our laboratory with
emphasis on process development of pulping, as well as recovery of solvent and furfural.
Comparative study on use of acetic acid and ethanol as solvents reported in this paper is the first
part of our research to develop small scale pulp mill with orientation to appropriate technology.
Experimental results pertaining to acetosolv- and ethanosolv-pulping (processes using acetic acid
and ethanol respectively) are presented briefly in this paper, while the detail are presented in
[Zulfansyah, 1998; Firdaus, 1998]. In this beginning of our research, the evaluation of pulping
process is still limited to pulp yield, -cellulose and lignin contents in pulp. Recovery of solvent
and furfural are also discusses shortly at the end of this paper.

2. Theoretical Background
A variety of organic solvents such as alcohol,amines, ketones and acids have been used in
selective fractionation of lignocellulose into its contituents. Actually, first isolation of lignin from
wood (in 1893) was carried out using ethanol. Alcell process developed bu REPAP Canada uses
ethanol as solvent with addition of NaOH, and this process has probably been in a commercial
stage [Petty, 1989]. In acetosolv-pulping, a small amount of strong mineral acid (HCl or H 2SO4)
is usually added as catalyst primarily for hydrolysis of hemicellulose.
Like in many other chemical processes, cooking temperature and time are obviously
important factors in organosolv-pulping. However, care must be taken to avoid lignin
redeposition in a process with extreme temperature and extended cooking time. Redeposition of
lignin during acetosolv-pulping of wood at 190C and prolong time beyond 2 hours was reported
by [Vasquez, et.al., 1994]. While in ethanosolv-process using NaOH as catalyst, redeposition of
lignin was reported as an increase in Kappa number for cooking time beyond 2.5 hours
[Weisheng,et. al., 1988].
Organosolv-process is principally based on the properties of lignin, that dissolves in
organic solvent, but undissolves in water. Thus, concentration of organic solvent will play an
important role in this process. Acetic acid with a concentration as low as 70% can be used as
cooking liquor, usually with addition of a small amount of strong mineral acid (up to 0.5%).
Unfortunately, addition of catalyst may enhance not only the rates of delignification and
hydrolysis of hemicellulose, but also the rates of cellulose degradation and redeposition of lignin.
In ethanosolv-pulping, ethanol with a concentration as low as 50% may be used as
cooking liquor with addition of NaOH up to 12%. This significant amount NaOH obviously
takes part in delignification reaction similar to that in conventional soda and kraft processes.
Thus NaOH should probably be considered as an auxiliary chemical rather than a catalyst. In this
respect, our experiments were directed to reduce the use of NaOH in ethanosolv-pulping.
 organic lignocelullose
solvent, raw
material
water and catalyst

cooking

fresh organic water

solvent solid residue
black liquor
filtration precipitation

washing

filtrat
centrifugation
refining and drying separation process

furfural lignin
pulp fermentable sugar

Figure 1. Diagram of organosolv-fractionation of biomass

(solid lines represent pulping process: dotted line representt recovery of other products)

2. Experiments
Concentration of catalyst, cooking temperature and time have been considered as
important process variables. Ratio of cooking liquor to solid raw material (so called liquor to
solid ratio) and concentration of organic solvent were selected as low as possible to save
chemicals. The two latter variables were studied first in preliminary experiments, and then take
as fixed parameters in main experiments. In acetosolv-pulping, a set of preliminary experiments
was carried out to determine the effect of the concentration of acetic acid (70% and 90%) and
ratio of cooking liquor to solid raw material (8/1 to 14/1) on the pulp quality. In ethanosolv-
pulping, preliminary experiments were carried out primarily to determine the effect of heating up
periode to attain cooking temperature. Main experiments in both acetosolv- and ethanosolv-
pulping were aimed to determine the effect of temperature, catalyst concentration (as percentage
to solid raw material) and cooking time on the quality of pulp.
Oil-palm empty bunch was obtained from a CPO mill in West Java. A pile of raw material
was prepared by cutting OPEB into coarse fibres with a length of about 1 cm. The raw material
was dried under the sun and finally stored in a plastic bag. Its chemical composition was as
follows (in mass fraction and oven dried basis): 40.91% -cellulose, 20.63% , -cellulose and
18.90% lignin. A separate analysis showed that OPEB contained 22.13% hemicellulose (as
pentosan, a source of furfural and fermentable sugars). Prior to every experiment, the raw
material was immersed into water overnight and then washed to remove dirt and pitch. It was
then dried in an 110C oven for 2 hours.
 Experiments were carried out in a 2 L autoclave provided with a temperature controller.
Time to attain cooking temperature was about 30 minutes, and time at cooking temperature was
taken as a process variable. At the end of cooking, the autoclave was immersed into water to
allow fast cooling down. Solid residue was firstly washed with fresh solvent and then with water
(see Figure 1). Finally, suspension of solid residue in water was agitated throughly to loose
micro-fibre (refer as refining-process in pulp mill). Pulp analysis were conducted based on SNI
(Indonesia Standard, mostly adopted from TAPPI standard methods).

Table 1. Cooking conditions and experimental results from acetosolv-pulping

acetic acid concentration 70% liquor to solid ration 12:1

Exp. Temp. NaOH Time Ypulp Clignin C-celullose

No. (C) (%) (min) (%) (%) %
A1 120 0 2.5 61.72 10.16 69.63
A2 120 0.1 1.0 63.50 12.58 70.57
A3 120 0.1 4.0 50.14 5.59 72.30
A4 120 0.2 2.5 54.86 6.42 75.45
A5 140 0 1.0 56.50 5.78 73.24
A6 140 0 4.0 55.69 5.13 67.36
A7 140 0.1 2.5 37.99 1.76 80.19
A8 140 0.1 2.5 36.34 1.43 82.37
A9 140 0.2 1.0 51.74 4.86 83.42
A10 140 0.2 4.0 47.57 3.42 82.28
A11 160 0 2.5 40.34 1.67 76.20
A12 160 0.1 1.0 42.63 2.08 87.81
A13 160 0.1 4.0 36.70 1.37 81.35
A14 160 0.2 2.5 37.03 0.74 93.35

4. Results and Discussion

From our preliminary experiments, we found that acetosolv-process using 70% acetic
acid and liquor to solid ratio od 12:1 yielded a considerable high quality pulp, almost as good as
pulp from cooking with 90% acetic acid. In ethanosolv-pulping, cooking had to be carried out
with a liquor to solid ratio of about 20:1, otherwise solid raw material underwent pyrolysis to
form char at cooking with a lower liquor to solid ratio. These preliminary experiments also
revealed that the extent of delignification during the heating up period (first 30 minutes of
cooking) could be neglected.
Results of main experiments in acetosolv-pulping and ethanosolv-pulping are presented
in Tables 1 and 2 respectively. Pulp yied (Y pulp), lignin content (Clignin) and -cellulose content
(C-cellulose) in these tables are similar to those in equations 1,2 and 3, as well as those in Table 4.

Table 2. Cooking conditions and experimental results from ethanosolv-pulping

ethanol concentration 50%; liquor to solid ratio 20:1
Exp. Temp. NaOH Time Ypulp Clignin C-celullose
No. (C) (%) (min) (%) (%) %
E1 150 3 60 71.5 9.01 53.64
 E2 150 3 140 65.6 8.75 55.86
E3 150 6 100 62.8 8.30 59.32
E4 150 9 60 66.3 7.71 61.23
E5 150 9 140 58.2 7.62 64.17
E6 170 3 100 64.4 7.46 66.31
E7 170 6 60 64.1 7.53 64.57
E8 170 6 100 63.4 7.31 66.71
E9 170 6 100 60.4 7.42 68.69
E10 170 6 100 63.3 7.28 70.24
E11 170 6 100 62.1 7.39 66.76
E12 170 6 140 60.3 7.01 73.97
E13 170 9 100 61.3 6.83 68.49
E14 190 3 60 61.2 6.89 55.52
E15 190 3 140 56.3 5.98 76.49
E16 190 6 100 57.7 6.30 66.51
E17 190 9 100 58.8 6.53 59.14
E18 190 9 140 45.6 3.63 81.38

Based on our experimental results, empirical model (equation 1) have been derived to
represent the effect of cooking temperature, catalyst concentration and cooking time on pulp
yield, lignin and -cellulose contents in pulp. Coefficients in equation 1 (presented in Table 4)
were estimated from experimental data using multi-steps regression, and then coefficients related
to insignificant variables were excluded from equation.
Yi = a + b. X1 + c.X2 + d.X3 + e.X1.X2 + f.X1.X3 + g.X2.X3 + h.X12 + i.X22 + j.X32 (1)
X1,2,3 = dimensionless variables for temperature,catalyst concentration and cooking time (Table 3)
Y1 : Ypulp = pulp yield in percentage to solid raw material (see Tables 1,2 and 4)
Clignin = lignin content in pulp (%-mass, oven dry basis; see Tables 1,2 and 4)
C-cellulose = -cellulose content in pulp (%-mass, oven dry; see Tables 1,2 and 4)

Table 3. Process variables and their dimensionless values (see equation 1)

acetosolv-pulping ethanosolv-pulping
Temperature,C 120 140 160 150 170 190
X1,dimensionless -1 0 1 -1 0 1
catalyst concentration % 0 0.1 0.2 3 6 9
X2, dimensionless -1 0 1 -1 0 1
cooking time, minute 60 150 240 60 100 140
X3, dimensionless -1 0 1 -1 0 1

Table 4. Coefficients for empirical model (see equation 1)

Ypulp Clignin C-cellulose
aceto- ethano aceto- ethano aceto- ethano
coefficients
a 37.165 62.271 1.595 7.141 80.847 68.433
b for X1 (temperature) -9.190 -4.480 -3.609 -1.206 6.399 4.482
c for X2 (catalyst concentration) -2.881 -2.880 -0.915 -0.577 6.063 2.659
d for X3 (cooking temperature) -3.034 -3.590 -1.224 -0.468 -1.469 5.777
e for X1.X2 ns ns ns -ns 2.940 ns
f for X1.X3 ns ns 1.570 0.433 -2.048 4.756
g for X2.X3 ns -1.312 ns ns 1.185 ns
h for X12 3.345 -1.871 1.883 ns ns -5.107
i X22 7.978 ns 1.275 ns -1.866 ns
j for X32 7.733 ns 1.928 ns -2.623 ns
ns = the effect of related variables are insignificant

Kappa number is usually used to represent lignin content in pulp, since its determination
is more practical. Kappa number is also an important factor in the estimation of chemicals
required for bleaching in pulp mills. In this study, Kappa number (KN) and lignin content have
been analyzed together and the following relationships were obtained.
a. Acetosolv-pulping: Clignin = 0.0861 KN (2)
b. Ethanosolv-pulping: Clignin = 0.0985 KN (3)

The two constants in the above equations differ slightly from that in conventional kraft
process of wood (Clignin = 0.15 KN). This difference is probably due to the nature of raw material
and type of process. In our further studies, lignin content in pulp can hopefully be measured from
Kappa number using the above simple relationships.
Pulp from OPEB has been characterized as short to medium fibre [Pratiwi, et.al, 1988];
average length of fibre 1 mm (minimum 0.2 and maximum 2.2 mm), outer diameter of fibre 15.7

m and inner diameter 7.9 m, and flexibility 0.4-0.5. In general, this fibre may be used for

various type of paper with proper addition of long fibre pulp to improve physical properties of
paper. OPEB pulp from soda-anthraquinone process mixed with 20% long fibre pulp has been
successfully used as raw material of printing paper [Guritno, et.al., 1995]. With respect to the
pulp yield and Kappa number based on unbleached pulp, both aceto- and ethanosolv-pulping
yielded pulp suitable for various types of paper (see Table 5). Suitable process condition within
or slightly beyond the range investigated in this study might be estimated using the above
empirical model as discusses in [Zulfansyah, 1998; and Firdaus, 1998].
A high -cellulose content based on bleached pulp is required for pulp for rayon (see
Table 5). In this respect, acetosolv-pulping was apparently very suitable for the production of
pulp for rayon. Pulp with -cellulose content of about 80% could be easily be obtained from
cooking at mild conditions (see Table 1). Since severe conditions might cause lignin
redeposition, further increase in -cellulose content in pulp should be obtained by means of
bleaching.

Table 5. Pulp characteristics related to their downstream products [Kocurek, 1993]

pulp grades pulp yield, Kappa -cellulose notes
% to raw number content in
material pulp, %
low yield pulp 35-49% 14-20 bleachable pulp, for writing and printing paper
medium yield pulp 47-54% 35-50 for top liner of packaging board,printable
 high yield pulp 51-63% 60-110 for bottom liner of packaging board
pulp for rayon 90.5 for cellulose acetate
acetosolv-pulp 40-53% 50-85 93 (max) this study, see Table 1
ethanosolv-pulp 45-72% 30-100 81 (max) this study, see Table 2

On the other hand, ethanosolv-pulping hardly produced pulp with -cellulose content
above 75% (see Table 2). Extending cooking time and elevating temperature might result in
cellulose degradation and also increase lignin content due to redeposition. Moreover, elevating
temperature of cooking would be consequently increase working pressure (e.g. 20 bar at 180C)
beyond a practical condition for an appropriate technology.

5. Further Studies
A key point in developing an economically small scale pulp mill using
organosolv-process lies on the process simplicity to recover organic solvent. An ethanol recovery
up to 70% was achieved in our preliminary experiments by means of a simple distillation.
Furthermore, evaporating ethanol from black liquor would leave water and subsequently resulted
precipitation of formerly dissolved lignin (see process diagram in Figure 2). Thus, recovery of
ethanol and precipitation of lignin took place simultaneously.
Recovery of acetic acid is slightly more difficult than that of ethanol, because black
liquor from acetosolv-pulping is firstly diluted at least 5 times with water to precipitate lignin
(see Figure 2). Moreover the relative volatility of water to acetic acid is close to one, so a straight
run distillation of acetic acid-water will need a great number of equilibrium stages and will
consumes much energy. Butyl acetate was used in elderly acetic acid plant as entrainment to
enhance the withdrawal of water as the top product of azeotropic distillation. But the application
of this method for recovery of acetic acid in acetosolv-process may encounter problems in
further separation of lignin, furfural and acetic acid in the bottom product of the azeotropic
distillation.
Preliminary experiments to isolate furfural were already done using black liquor
obtained in these pulping processes. We found that approximately 25% hemicellulose in OPEB
could be converted into furfural. This selective conversion of hemicellulose into furfural was
relatively low, probably because the process conditions applied in these experiments was too
severe for hydrolysis, so hemicellulose underwent excessive degradation resulting smaller
molecular compounds such as CO2 and H2O.
Separate experiments intended to study the hydrolysis of hemicellulose were conducted
at a low temperature of about 120C (normal boiling point of acetic acid), using 70% acetic acid
and H2SO4 as catalyst (0.5% to solid raw material). At this mild condition, selective conversion
of hemicellulose into furfural was up to 80%. Therefore, if furfural would be taken as valuable
by-products to improve the economic of acetosolv-process, the hydrolysis of hemicellulose
should also be considered in the process optimization.

acetosolv-pulping acetosolv-pulping
150-170C (5 bar) 150-190C (20 atm)

Ethanol
pulp screening pulp screening for reuse
 pulp

water

precipitation of lignin by evaporation of ethanol

means of addition of and simultaneous
water precipitation of lignin

acetic acid
for reuse centrifugation to remove centrifugation to remove
lignin lignin lignin

separation process of low separation process of

conc. acetic acid and relatively high conc.
furfural
furfural in water furfural in water

relatively much waste water small amount of waste water

Figure 2. Comparison of overall acetosolv- and ethanosolv-processes

Besides experimental works, computer simulation on recovery process of acetic acid and
furfural have been carried out using a process simulator, Aspen Plus. Two process configurations
for recovery of acetic acid are being studied (Figure 3), and the results will be presented in
elsewhere [Susanto,1998].

benzene benzene

distillation distillation
Acetic Acetic
acid and acid and
furfural furfural furfural
furfural
in water extraction in water
extraction
of furfural
of furfural

amyl n-butyl
acetate
acetate
extraction
of acetic Azeotropic
distillation distillation waste water
acid

waste water acetic acid for reuse acetic acid for reuse

Figure 3. Proposed configurations for recovery process of acetic acid and furfural
 Another interesting point related to the economic of organosolv-process is the use of
spent organic solvent without purification. Cooking with a sequential use of spent liquor may be
carried out using the principle of counter current extraction. Spent solvent from pulp washing is
used for subsequent cooking, while black liquor is used in following preheating and precooking
of fresh solid raw material. In this case, lignin redeposition must be examined carefully.

6. Conclusions and Recommendations

Fractionation of oil palm empty bunch have been conducted successfully using acetic
acid or ethanol. Both acetosolv-process and ethanosolv-process yielded pulp with Kappa number
in the range of 30 100, suitable for various types of paper.
For production of pulp for rayon with -cellulose content above 90%, acetosolv-pulping
was definitely superior to ethanosolv-process. Thus with respect to pulp-quality we concluded
that acetosolv-pulping was preferable to ethanosolv-process.
A potency to recover furfural as a by-product in acetosolv-process has been shown in our
preliminary experiments. This valuable chemical should be considered in further development to
improve furfural yield in organosolv-process. For this reason, hydrolysis of hemicellulose must
be included in process optimization together with delignification process.
Despite of superiority in pulping, recovery of solvent and furfural in acetosolv-process is
relatively more complex compare to that in ethanosolv-process. Therefore, the downstream
processes must be included in further study for to confirm the selection of acetosolv-pulping.
This study may be done theoretically using computer simulation.

Acknowledgements.
The authors like to thanks our undergraduate student, Rosmanto, Pralampitaning Nugroho and Teddy for
their help in experiments and analysis. Discussion on pulp characteristic with Institute for Research and
Development of Cellulose Industry is gratefully mentioned.

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