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J. appl. Cheni. Biotechnol.

1976, 26, 283-287

Hydrolysis of Pentosans in Bagasse Pith


Charles I. Nee and Wen F. Yee
Taiwan Sugar Research Institute, Tainan, Taiwan
(Paper received 17 June 1975, amendedpaper accepted 29 January 1976)

Work has been conducted on the hydrolysis of pentosans in bagasse pith as the first
part of a study of the chemistry of bagasse processing aimed at establishing an
integrated industry. Bagasse pith is the fine part screened out and discarded as waste
during the preparation of raw material for bagasse pulping plant. By using dilute
sulphuric acid at a concentration less than 2 % by weight and at a temperature lower
than 165% pith is hydrolysed to pentoses in a yield of 80-90% based on potential
pentoses in pith. Hydrolysis of pentosans in pith, within the scope of experiment,
seems to be a first order reaction. However, the semi-logarithmic time plot for the
hydrolysis of potential pentoses in the residue consists of two straight lines of different
slope. This may be explained on the assumption that bagasse pith contains two major
fractions of pentosans that are hydrolysed at different rates. Saemans equation for
hydrolysis of wood with sulphuric acid may be adapted to represent dependence of
rate constant K on acid concentration C and reaction temperature T in hydrolysis
of the two major parts of pentosans in bagasse pith.
K I = 6.4 x 105C1.02exp (- 6378/T)
Kz= 10.7C0.363exp (- 2826/T)
1. Introduction

Depithing is ordinarily necessary for preparation of raw bagasse in a pulp mill. The discarded pith
portion and fine fibre amounts to 30% of the raw bagasse on dry basis and has to be disposed of
in order to keep the mill running. In a modern pulp mill, wet depithing is preferable for better
quality of product and health of workers. However, this means that the residue is wet and thus not
suitable for direct use as a fuel. Systematic hydrolysis of this damp, fibrous residue with dilute
acid into furfural vapour, glucose solution and ligneous solid seems to be one of the best methods
of disposal. The work reported here refers to the hydrolysis of pentosans in pith into pentose or
furfural, which is the reaction first occurring during the systematic hydrolysis of the fibrous residue.
The effects of concentration of sulphuric acid and temperature upon hydrolysis rate are studied.
2. Experimental
2.1. Hydrolysis

One part of pith (on a dry weight basis) is mixed thoroughly with ten parts of dilute sulphuric acid
at a concentration between 0.5 and 2.0% by weight. The mixture is put in the autoclave shown in
Figure 1. The autoclave and its cooked contents are cooled rapidly to room temperature. The cold
contents are discharged and separated into liquor and solid by filtration.
The weight of the liquor is determined and it is then analysed for pentose, furfural and glucose.
The solid is dried at room temperature and its weight and moisture content are determined. It is
analysed for potential pentose, potential glucose and lignin.
2 3 . Analysis
2.2.1. Total pentose Pt in the liquor hydrolysate
Acidify 50 g of the liquor hydrolysate with 24 g of 37 % HCI solution. The acidified liquor thus
contains 12% HCI by weight. Analyse it for pentose according to Dorkes method.
283

C. I. Nee and W. F. Yee

284

l
-

Figure 1. Apparatus for hydrolysis of bagasse pith. 1 , Hydrolyser; 2, steam jacket; 3, pressure gauge; 4, stop
valve; 5, steam reducing valve; 6, steam trap; 7, bagasse pith; 8, steam in; 9, water out; 10, water in; 1 1 , condensate
out.

2.2.2. Furfural in the liquor hydrolysate expressed in pentose as Pf


Neutralise 300 g of the liquor hydrolysate with dilute alkali solution to pH 7.0. Distil out furfural
according to Dorkes method. Acidify the neutral furfural distillate with concentrated HCI solution
until the resulting acidic solution contains 12 parts ofHC1 per 100 parts of it. Determine the furfural
content by Dorks method and express in pentose as Pt.
2.2.3. Pentose in liquor hydrolysate, P
P=Pt-Pe

2.2.4. Glucose in liquor hydrolysate


Acidify 5 g liquor hydrolysate with 0.015 g of 72% HzS04 solution. The acidified liquor is heated
on a steam bath at 100C for 1 h. Cool the hydrolysed liquor, neutralise and dilute to 10 g. Take
1.O g of this hydrolysate (equivalent to 0.5 g of the original liquor hydrolysate). Determine the
volume XI (in cm3) of 0.005 N NazSz03 solution required by both the pentose and glucose in the
solution according to Shaffer-Somogyi method.2 Calculate pentose content, PO,in 0.5 g liquor
hydrolysate by using the result obtained in section 2.2.3. The equivalent volume of 0.005 N NazSz03
solution, Xo, may be calculated by Shaffer-Somogyi formula as follows:
xo=Po - 0.004
0.1 103
Let X be the equivalent volume of 0.005 N NazSz03 solution corresponding to the glucose in
0.5 g liquor hydrolysate, then

x= x1- xo

Let glucose in 0.5 g liquor hydrolysate be Y,then


Y = 0.1099

x+ 0.048

2.2.5. Potential pentose in residue


Weigh out I g of residue and determine its pentose content by the method in section 2.2.1.

2.2.6. Potential glucose in residue


Put 1 g of residue in a weighing bottle and add 5 g of 72 % sulphuric acid solution. Stir the mixture
until it becomes homogeneous. Allow to settle at 5C for 16 h. Wash the contents of the weighing

Hydrolysis of pentosans in bagasse pith

285

bottle with 115 g of water into a n Erlenmeyer flask, thus giving a sulphuric acid concentration in
the flask of 3%. Fit the flask with a reflux condenser and heat the flask in a steam bath for 2 h.
Cool and filter the product obtained. Neutralise and weigh the filtrate. Determine potential glucose
in the neutralised filtrate by the method in section 2.2.4. The residue is used for lignin determination.

2.2.7. Lignin content in the residue


Wash the residue from section 2.2.6 until the washings are free from so42-.Dry the washed filter
and weigh.
2.2.8. Chemical analyses of bagasse pith
Ash,a 2.10%; hot water solubility,b 1.60%; ligniri, 21.5 %; potential glucose, 39.18%; potential
pentose, 32.58 %.
3. Results

The first order plots of potential pentose against time, shown in Figure 2, gave curves that obviously
consisted of two straight lines, one corresponding to a rapidly hydrolysable portion and the other

0.01

0.0023
0.2~
0.1

0.0024

0.0025

0.0024

0.0025

0.0026

kN

LL

0.001

Time (rnin)
Figure 2. Hydrolysis fate of pentosans in bagasse
pith. a, 0.5% HS.04; b, 1.0% HeS04; C, 2.0%
HzS04.

0.0023

0.0026

Reciprocal of absolute temoeroture

Figure 3. Effect of temperature on reaction velocity


constant. a, 0.5% HzS04; b, 1.0%HzS04; C, 2.0%
HzS04.

to a more resistant portion. Ki was designated as the reaction velocity constant for the former and
K2 as that for the latter.
Plots of reaction velocity constant against reciprocal of temperature, shown in Figure 3, gave
values of activation energy ES shown in Table 1 according to Arrhenius' equation. Plots of reaction
b

According to methods of TAPPI TI5 0s-58.


According to methods of TAPPI TI 0s-59.

C. 1. Nee and W. F. Yee

Table 1. Activation energy of hydrolysis of pentosans in bagasse pith

Ea kal mol-l)

Slope, mt x (- 1)
Acid concentration (%)
~

0.5

1 .O

Reactive part
Resistant part

2.0
~~

3195
1121

~~

2617
1217

mt

0.5

2556
1343

.o

2.0

E.

_ ~ _ _ .

2789
1227

14620
5130

11975
5569

11696
6146

12764
561 5

Table 2. Slope of the straight line obtained by plotting reaction


velocity constant K versus cpncentration of HzS04 solution
125C
~ _ _ -.
_ ~Reactive part
0.906
Resistant part
0.323

145C
.

I .013
0.360

165C

me

1.142

1.020
0.363

. ~ .

0.406

velocity constant against acid concentration gave straight lines shown in Figure 4. Values for slope
of these lines mc are given in Table 2.
The dependence of the reaction velocity constant on temperature and acid concentration was
represented by an empirical equation proposed by Saernan for hydrolysis of wood chips with
dilute sulphuric acid s ~ l u t i o n It
. ~ is adapted here for hydrolysis of pentosans in bagasse pith.

K = HCmcexp (- Ea/RT)
where K = reaction velocity constant (min-l), H=constant (min-l), C=concentration of sulphuric
acid solution (wt %), mc= slope of the straight line obtained by plotting K against C, Ea= activation
energy (cal mol-l), R=gas constant (1.987 cal deg-1 mol-l), T= temperature (K).

0.01

5
C

0125025 0 5 0 1.00 2.00 4.00

0.04

In

Figure 4. Effect of the concentration of acidic solution


on reaction velocity constant of hydrolysis of pentosans.
a, 165C; b, 145C; c, 125C.

i~

0.001
0.125 0.25 0.50

1.00 2.00 4.00

Sulphuric acid concentration I%)

The value of H in the equation may be found by substituting values of K , C, T,mc and E, into it.
Mean values of H for the two parts of pentosans in bagasse pith had been thus found to be 6.4 x lo5
and 10.7 respectively. Then,
K1 = 6.4 x 105C1.02exp (-6378/T)
KZ= 10.7C0.363
exp (- 2826/T)

Hydrolysis of pentosans in bagasse pith

287

4. Discussion

Both the concentration of sulphuric acid and the reaction temperature have positive effects on the
reaction velocity constant K , especially with the reactive pentosans. Let AT= increment of temperature, AC= increment of acid concentration, Co= initial acid concentration, AK= increment of
reaction velocity constant, KO=initial value of K . Then AK % KO"for the pentosans in pith will be
shown as follows:
Reactive part
Resistant part
For each 10C of AT
46.8
18.7
100% of AC%Cob 103.0
28.4
For any particular value of C and T, within the scope of experiment, K1 is always larger than
Kz. The activation energy Ea1, required by the faster reaction having a reaction velocity constant
K1, is larger than Eaz required by the reaction having a constant Kz. This feature may be explained
as follows: pentosans of various degrees of polymerisation are chemically bonded to other constituents in bagasse pith. They must be detached from other constituents before hydrolysis. Due to
reaction rate, the energy for detaching the pentosans is related solely to that part of the pentosans
with a lower degree of polymerisation and therefore more reactive to hydrolysis. In other words,
Eel comprises not only the energy of activation necessary for the reactive part of the pentosans
but also the total energy for detaching all pentosans from other constituents of bagasse pith. The
result is then:
K i > Kz
Eai > Eaa,
For any particular condition, the minimum error of the experimental K value based on the
calculated K value, or vice versa, may be obtained by comparing these two values as follows
( C = l % , T=398.1K, for example):
Ki

KZ

Experimental
0.075
0.0083

Calculated
6 . 4 105x
~
11.02exp(-6378/398.1)=0.065
10.7 x 1 0.3~3exp (- 2826/398.1)= 0.0089
Mean absolute value

Error (%)
13.3
- 6.0
1101

Acknowledgement
The authors wish to thank the Taiwan Sugar Corporation for permission to publish this paper.
References
1 . Dorke, C. Methods of Cellulose Chemistry D. Van Nostrand Co., New York, 1947, 2nd edn, p. 315.
2. Horwitz, W. Methods ofAndysis ofA.0.A.C. Association of Official Agricultural Chemists, 1970,llth edn, p. 536.
3. Saeman, J. F. Ind. Engng Chem. 1945, 31, 43.

a
b

AK%Ko=incrernent of K per cent initial value of K.


AC%Co=incrernent of acid concentration per cent initial acid concentration.