Article 2
Article 2
Article 2
www.elsevier.com/locate/ultsonch
Abstract
Based on the enzymatic saccharication of the various pulps in the previous 0.8 l ultrasonic stirred tank reactor, the ultrasoundenhanced saccharication of waste papers such as newspaper, carton paper, oce paper etc. was carried out in the same reactor as
well as larger scale stirred tank reactors of size 3.2 and 6.4 l. The saccharication of each waste paper was less enhanced in the larger
reactor at a given ultrasonic intensity. This could be attributed to the decrease in the ultrasonic intensity per reaction volume, i.e.,
the specic ultrasonic intensity. Most waste papers were more eciently hydrolyzed with increasing specic ultrasonic intensities,
although newspaper was less eciently done for a too high specic intensity. Such an adverse eect might be due to the fact that
some impurities in the newspaper such as lignin were activated by an intensive ultrasonic irradiation to form a rigid and closed
network, which inhibited the access and adsorption of cellulase on to the substrate surface. The previous kinetic model was found to
be applicable to analyze and simulate the saccharication of each waste paper in the dierent ultrasonic reactors. The ultimate
conversion of a substrate based on the total sugar concentration estimated for an innite reaction time could be correlated as a
function of the ratio of initial substrate to enzyme concentrations at a xed specic ultrasonic intensity. Either the apparent rate
constant or the ultimate conversion increased and tended to approach a constant with an increase in the specic ultrasonic intensity
except for the case of newspaper, while neither the apparent Michaelis constant, product inhibition constant nor glucose formation
equilibrium constant was inuenced by the specic ultrasonic intensity.
2004 Elsevier B.V. All rights reserved.
Keywords: Enzymatic saccharication; Waste paper; Ultrasonic stirred tank; Scale-up; Kinetics
1. Introduction
Waste reutilization has become a matter of great
interest since the increased waste emission is threatening
the limited resources and living spaces on the Earth.
Among the various components of the municipal solid
wastes, waste papers rank rst with a percentage of 38%
[1]. Waste papers can be reutilized several times through
manufacturing recycled paper before cellulose bers
374
375
Fig. 1. Schematic diagrams of (a) small scale stirred tank reactor of 0.8 l in working volume and (b) larger scale reactors of 3.2 and 6.4 l in volume for
enzymatic saccharication of waste paper with continuous ultrasonic irradiation.
376
NUKP
Newspaper
Carton paper
Oce paper A, unprinted
Oce paper A, printed
Oce paper B, unprinted
Oce paper B, printed
94.8
75.1
28.6
7.04
5.08
97.4
93.5
T(g l-1)
T22=8.1 g l-1
T11=6.9 g l-1
T=4.8 g l-1
Newspaper
Carton
Office paper A
NUKP
10
T (g l-1)
Newspaper
Carton
Office paper A
NUKP
10
T=6.7 g l-1
5
T=4.2 g l-1
-1
T=3.5 g l
T=2.9 g l-1
-1
T =1.7 g l
T=1.2 g l-1
5
G (g l-1)
G (g l-1)
0
0
12
24
t (h)
36
48
12
24
36
48
t (h)
Fig. 2. Observed time courses of total sugar and glucose concentrations, T and G, in enzymatic saccharications of various waste paper in 0.8 l
ultrasonic stirred tank reactor (S0 7:5 g l1 ) (a) with ultrasonic irradiation of 30 W and (b) without irradiation. Value of ultimate total sugar
concentration T1 was determined by the previous extrapolation method [5]. Solid lines show the calculated time courses from Eq. (5).
or
dt t!0 KM 0:9T1
1
KM 1
0:9
4
dT =dtt!0 kE0 T1 kE0
Fig. 3 shows the determination of the initial rates
dT =dtt!0 from the corresponding time course of total
sugar produced during the enzymatic saccharication of
newspaper and also the results of T1 for the dierent
values of S0 . For the kinetic analysis of the saccharications in the small scale ultrasonic reactor, the values of
the apparent rate constant k and Michaelis constant KM
for each substrate under a given ultrasonic intensity
15
With ultrasonic irradiation of 30 W
T=12.2 g l-1
Slope=(dT/dt)t0
t 0
10
T (g l-1)
377
T=8.0 g l-1
T=4.8 g l-1
S0 [g l-1]
7.5
15
25
0
0
12
24
t (h)
36
48
Fig. 3. Determination of various initial rates from time courses observed for dierent initial newspaper concentrations in 0.8 l reactor
with ultrasonic intensity of 30 W. Solid lines represent the empirical
correlation curves.
Table 2
Simplied kinetic model for enzymatic hydrolysis of cellulose
EG=CBH
BG
Celluose S ! Oligosaccharides O
Glucose G
dT
kE0 T1 T
dt
KM 1 1=KI T 0:9T1 T
where EG, CBH and BG denote endoglucanase, cellobiohydrolase and b-glucosidase, respectively, T1 , k, KM and KI mean ultimate total sugar
concentration, apparent rate constant, apparent Michaelis constant and apparent inhibition constant, respectively, and T O G
378
lnT1 T0 =T1 T
c
0:9T T0
where
b
KM 1
KM
T1
kE0 KI
kE0
1 KM 1
1
0:9 kE0 KI kE0
Table 3
Kinetic model parameters for waste papers and NUKP in the 0.8 l ultrasonic stirred tank reactor
Substrate
Is (W)
k (h1 )
KM (g l1 )
KI (g l1 )
K ()
Newspaper
0
30
13
16
13.4
0.704
2.0
Carton paper
0
30
9.0
10
13.4
0.704
1.0
Oce paper A
0
30
2.5
3.7
13.4
0.704
0.0056
NUKP
0
30
11
24
13.4
0.704
2.7
379
0 W 30 W
Xf (-)
Newspaper
Carton
Office paper A
NUKP (T 22)
NUKP (T 11)
Newspaper
Carton
Office paper A
NUKP
Pure cellulose
(CC31) without
ultrasonic
irradiation
0.5
10
100
1000
S0/E0 (-)
Fig. 4. Apparent ultimate conversion of substrate Xf as a function of the ratio of initial substrate to enzyme concentrations S0 =E0 in 0.8 l ultrasonic
stirred tank reactor for various substrates (E0 0:4 g l1 ; S0 7:5; 15; 25 g l1 ). Lines represent the empirical correlation curves.
380
(a) Newspaper
0 W (T=4.1 g l-1)
30 W (T =5.2 g l-1)
60 W (T =4.6 g l-1)
6.4 l
6.4 l
3.2 l
0
0
0
10
12
24
36
t (h)
48 0
12
24
36
t (h)
48
10
T (g l- 1)
T (g l- 1)
0 W (T=2.4 g l-1)
30 W (T=2.8 g l-1)
60 W (T=3.2 g l-1)
G (g l- 1)
G (g l- 1)
0 W (T=2.8 g l-1)
30 W (T=3.1 g l-1)
60 W (T =3.6 g l-1)
3.2 l
3.2 l
6.4 l
-1
-1
0 W (T=6.7 g l )
30 W (T=7.5 g l-1)
60 W (T=8.1 g l-1)
12
24
36
t (h)
48 0
12
24
36
t (h)
48
(d) NUKP
6.4 l
3.2 l
0 W (T=6.6 g l-1)
30 W (T=7.8 g l-1)
60 W (T=8.0 g l-1)
0 W (T=6.6 g l )
30 W (T=7.3 g l-1)
60 W (T=7.5 g l-1)
G (g l- 1)
G (g l- 1)
(b) Carton
0 W (T=3.6 g l-1)
30 W (T=4.9 g l-1)
60 W (T=4.7 g l-1)
T (g l- 1)
T (g l- 1)
10
0 W ((T=5.9 g l-1)
30 W (T=6.4 g l-1)
60 W (T=7.3 g l-1)
0
0
12
24
36
t (h)
48 0
12
24
36
t (h)
48
12
24
36
t (h)
48 0
12
24
36
t (h)
48
Fig. 5. Observed time courses of total sugar and glucose concentrations, T and G, in enzymatic saccharications of (a) newspaper, (b) carton paper,
(c) oce paper B and (d) NUKP in 3.2 and 6.4 l stirred tank reactors with dierent ultrasonic intensities Is (S0 7:5 g l1 ). Solid lines show the
calculated time courses from Eq. (5).
381
Table 4
Kinetic model parameters for waste paper and NUKP in 3.2 and 6.4 l stirred tank reactors with dierent ultrasonic intensities (S0 7:5 g l1 )
Is (W)
3.2 l reactor
0
6.4 l reactor
30
60
1
k (h )
Newspaper
Carton paper
Oce paper B
NUKP
13
8.0
14
10
18
9.6
17
16
15
11
19
19
060
30
60
15
7.4
16
12
16
9.2
18
14
1
K ()
k (h )
2.0
1.0
3.0
2.7
12
5.6
14
8.5
060
K ()
2.0
1.0
3.0
2.7
382
(b) Carton
(a) Newspaper
20
10
10
0
1
Xf (- )
Xf (- )
0
1
0.5
0.5
0
0
10
20
Is /V (W l- 1)
30
40
10
20
Is /V (W l- 1)
30
40
(d) NUKP
20
k (h- 1)
k (h- 1)
20
10
10
0W
30 W
60 W
Xf (- )
0.5
0W
30 W
60 W
0
1
0
1
Xf (- )
k (h- 1)
k (h- 1)
20
10
20
Is /V (W l- 1)
30
40
0.5
0
0
10
20
30
40
Is /V (W l- 1)
Fig. 6. Relation of apparent rate constant k and apparent ultimate conversion Xf to specic ultrasonic intensity Is =V for (a) newspaper, (b) carton
paper, (c) oce paper B and (d) NUKP in various scale reactors. Solid lines represent the empirical correlation curves.
383
9
4. Conclusions
In this work, the enzymatic hydrolyses of waste
papers such as newspaper, carton paper, oce paper in
the various scale ultrasonic stirred tank reactors were
studied and the eects of the property of waste paper,
ultrasonic intensity and reactor scale were examined
based on our previous kinetic model. The results obtained in this work are summarized as follows:
15
(a) Carton
Is=45 W
V=0.8 l
S0=25 g l-1
T (g l- 1)
10
12
24
t (h)
36
48
20
(b) NUKP
Is=30 W
V=0.8 l
S0=25 g l-1
T (g l- 1)
15
10
12
24
t (h)
36
48
Fig. 7. Prediction of time course of total sugar T in enzymatic saccharication of (a) carton paper and (b) NUKP in the 0.8 l ultrasonic
stirred tank reactor (S0 25 g l1 ). Solid lines show the time courses
predicted from Eq. (5) with kinetic model parameters estimated.
384
ultrasonic intensities Is =V for all the substrates except newspaper. For newspaper, there existed an
optimal value of Is =V giving the maximal values of
k and Xf .
(5) The correlation of k with Is =V and that of Xf with Is =V
and S0 =E0 could be used to predict the time courses of
total sugar and glucose produced during enzymatic
hydrolysis of the substrates examined in the ultrasonic reactor under a given operating condition.
References
[1]
[2]
[3]
[4]
[5]