ICCME 2020

Prediction of Kappa Number and

Carbohydrate Degradation in Oxygen
Delignification of Abaca Fiber
 

Department of Industrial and Systems Engineering, Institut

Teknologi Sepuluh Nopember (ITS), Surabaya, Indonesia
 Outline

Introduction

Materials and Methods

Result and Discussion

Conclusion
 Introduction

Experiment's data Do prediction of Do prediction of

Kappa Darmawan (2020) lignin decrease carbohydrate
Nnumber Kraft degradation

Oxygen Find kinetic value Find kinetic value The best

Delignification q, Ea, m, n, A of ƛ, Ea, x, β, A of condition for
lignin decrease carbohydrate OD
degradation
 Process Conditions of
Oxygen Delignification
Oxygen Delignification
1. Kosentrasi
1. Kosentrasi (( Bahan
Bahan kimia
kimia yang
yang
● Process pre-blcaching to reduce the lignin digunakan Alkali)
digunakan Alkali)
contain in pulp.
2. Temperature
2. Temperature
● Can reduce the usage of chemicals in the
bleaching stage. 3. Pressure
3. Pressure (Oxygen)
(Oxygen)
● Can reduce the effect to environment.
4. Time
4. Time

(Bajpai,
8
2012)
 Oxygen Delignification Kinetic

The degree of delignification is measured by determining the

kappa number of the pulp. Most of the kinetic models for oxygen
delignification are empirical in which the delignification rate is
considered to be proportional to the lignin content expressed as
Kappa number (K), hydroxide ion concentration [OH-] and oxygen
pressure (PO2).
  𝑟 𝐿 =− 𝑑𝐾 = 𝑘 [ 𝑂𝐻 − ] [ 𝑃 𝑂 2 ] 𝑛 𝐾
𝑚 𝑞
−
𝑑𝑡

(Dogan,
10
2004).
 Carbohydrate Degradation

Carbohydrate degradation reaction occur in oxygen delignification,

which cause the strength pulp (viscosity) is reduced. Degradation
carbohydrate reaction is defined in terms of decreasing intrinsic
viscosity "Δη", of pulp. Empirical models have also been proposed for
the degradation of carbohydrates, which are as follows:
 𝑟 =− 𝑑 𝜂 =𝑘 [ 𝑂𝐻 − ] 𝑥 [ 𝑃 ] 𝛽 𝜂 𝜆
𝑐 𝑂2
𝑑𝑡

(Ji, 2007)

11
Viscosity
The testing of viscosity pulp is one of
important test to be done to know the
quality of pulp (SNI 14-0936-1989). In this
term the testing of viscosity show the
durability of the fiber in pulp sheet.
Kappa Number
Kappa number is using to predict the amount of
lignin by measured the oxidant demand from
pulp. Kappa number is processed in pulp sample
which has been dried.

Decreased viscosity due to breaking of the

cellulose chain which results in low yield
and pulp strength (Helga, 2009).
Add a full screen image

Material & Method

Material
The Abaca fiber (Musa textilis) contains 63% cellulose, 21% hemicellulose
and 14% lignin and 2% impurity

The kinetic reaction models of oxygen of kappa number reduction and

viscosity change as described in equation (1) and equation (2), respectively
  𝐿 =− 𝑑𝐾 = 𝑘 [ 𝑂𝐻 − ]
𝑚 𝑛 𝑞
−𝑟 [ 𝑃𝑂2] 𝐾
𝑑𝑡
𝑑𝜂
𝑟 𝑐 =−
− 𝑥 𝛽 𝜆
=𝑘 [ 𝑂𝐻 ] [ 𝑃𝑂 2 ] 𝜂
𝑑𝑡

13
Add a full screen image

Variable of Darmawan’s experiment Variable of Prediction

1. Pressure : 2 bar, 3 bar, 4 bar, and 5 bar 1. Pressure : 2 bar, 3 bar, 4 bar, and 5 bar

2. Temperature : 75°C, 85°C, 95°C and 2. Temperature : 70°C, 75°C, 80°C, 85°C,
100°C 90°C, 95°C and 100°C

3. NaOH Concentration: 1%, 2%, and 4% 3. NaOH Concentration: 1%, 2%, 3%, 4%

4. Heating time : 20, 40, and 60 minutes and 5%

4. Heating time : 0-120 minutes (interval

0,1 minutes)
Find q value k and q value of 8 set experiments
Experiment q
2 bar, 2% NaOH, 85oC 4.3
2 bar, 4% NaOH, 85oC 2.6
2 bar, 2% NaOH, 95oC 4
2
  1 1 2 bar, 4% NaOH, 95oC
( 𝐾 ) (𝐾 )
𝑞−1
− 𝑞 −1
0
=𝑘 ( 𝑞 − 1 ) 𝑡 𝑓𝑜𝑟 𝑞 ≠ 1 4 bar, 2% NaOH, 85oC
4 bar, 4% NaOH, 85oC
2
2
1− 𝑞 1 −𝑞
4 bar, 2% NaOH, 95oC 2.5
  𝐾 − 𝐾 0 =kt , q ≠1
𝑦= 4 bar, 4% NaOH, 95oC 2
(𝑞 −1) Mean 2.675

k  q R2
2 0.9194
  7.73 ; t=20 minutes 2.5 0.9422
3 0.9612
Trial q
4 0.9865
y=0.00002815 5 0.9954
5.3 0.9949
y=kt
5.5 0.9942
k=0.00001407 4.3 0.9991

(Dogan,
2004).
Finda Ea Find m

●  
− 𝐸𝑎
𝑘  =𝑘 2 𝑒𝑥𝑝
( )
𝑅𝑇 ●  
 ln
 where constant but concentration and oxygen
Where the value of oxygen pressure and
pressure vary. The Ea value was obtained from
temperature is constant. The m value is obtained
slope ln k vs 1/T. Ea = 24762 joule from slope of ln k vs ln [OH]. m= 0.5682

(Dogan,
2004).
Find n
Find A

ln ( 𝑘 )= ln ( 𝑘 4 ) +𝑛 ln ⌈ 𝑃𝑂 2 ⌉
  After find out the value of Ea, m, and n, the value of A
𝐸𝑎
𝑘  4= 𝐴 exp − [ 𝑅𝑇 ]
[𝑂𝐻 ]
𝑚 can be obtained. The value A can be conducted from
the exponent of A that provide from intercept of lnk
Where the temperature value and NaOH vs –E/RT+mLn[Oh]+nLn[PO2]. A = 33.11
concentration vary. The slope value of lnk vs ln[O2]
is defined for n value. n = 1.4942

(Dogan,
2004) 12
Prediction on Oxygen Delignification by
Different %NaOH
2% NaOH 4% NaOH
Time Kpredik Kexp Lignin %delignifikasi Time ηpredik ηexp Lignin %delignifikasi

0 0 24.43 24.43 3.71

12.45 12.45 1.8924
20 20 6.88 7.33 1.05 44.75
7.88 7.73 1.19 36.64
40 40 5.14 5.599 0.78 58.73
6.11 6.399 0.93 50.93
60 4.28 4.587 0.64 66.04
60 5.11 5.787 0.78 58.95
80
80 3.65 0.56 70.68
4.46 0.68 64.21 100 3.25 0.49 73.94
100 3.99 0.61 67.99 120 2.94 0.45 76.38
120 3.63 0.55 70.86

1% NaOH
Time Kpredik Kexp Lignin %delignifikasi
0 24.43 24.43 3.71
20 8.84 7.78 1.34 28.98
1 ( 𝑞 −1 1 )
40
60
7.12 7.110
6.08 6.77
1.08
0.92
42.79
51.17
  ( 𝑡 )=
𝐾
[( ) 𝑞 −1
𝐾0
+ 𝐾 𝑞 ( 𝑞 −1 ) 𝑡
] 𝑞≠1

80
5.37 0.82 56.91
100
4.83 0.735 61.14
120 4.43 0.67 64.415
Find λ value
Experiment q
2 bar, 2% NaOH, 85oC 14
  𝜆1−1 −
(𝜂 ) (𝜂 ) 1
𝜆− 1
=𝑘 ( 𝜆 − 1 ) 𝑡 𝑓𝑜𝑟 𝜆 ≠ 1 2 bar, 4% NaOH, 85oC 7
0
2 bar, 2% NaOH, 95oC 8
1−𝜆 1− 𝜆
2 bar, 4% NaOH, 95oC 9
 𝑦= 𝜂 −𝜂 0 =kt , 𝜆 ≠ 1 4 bar, 2% NaOH, 85oC 6
( 𝜆 − 1) 4 bar, 4% NaOH, 85oC 9
4 bar, 2% NaOH, 95oC 7
k  4 bar, 4% NaOH, 95oC 9
Mean 8
;  t=20 minutes
q R2
Trial λ 6.15 0.9864
7 0.9851
y=1.13E-40
6.2 0.9863
y=kt 7.15 0.985
8.5 0.9831
k=5.67E-42
9.8 0.9694
8.5 0.9831
14 0.9989

(Dogan,
2004).
Find Ea Find m

●  
𝑘  =𝑘 2 𝑒𝑥𝑝 ( −𝑅𝑇𝐸𝑎 ) ●  
ln
 

 whereconstant but concentration and oxygen
pressure vary. The Ea value was obtained from slope
ln k vs 1/T. Ea = 33251 joule
Where the value of oxygen pressure and
temperature is constant. The m value is obtained
from slope of ln k vs ln [OH]. x= 0.3153
(Dogan,
2004).
Find n
Find A

ln ( 𝑘 )=ln ( 𝑘 4 ) + 𝛽 ln ⌈ 𝑃𝑂 2 ⌉
   After find out the value of Ea, m, and n, the value of A
𝐸𝑎
𝑘  4= 𝐴 exp −[ 𝑅𝑇 ]
[𝑂𝐻 ]
𝑥 can be obtained. The value A can be conducted from
the exponent of A that provide from intercept of lnk
Where the temperature value and NaOH vs –E/RT+mLn[Oh]+nLn[PO2]. A =
concentration vary. The slope value of lnk vs ln[O2]
is defined for β value. β = 1.0877
(Dogan,
2004) 16
Prediction on Carbohydrate degradation with Different
%NaOH 2% NaOH
η
Time ηpredik
1% NaOH
expη ηDerajat % loss Time predik exp Derajat % loss
polimer karbohidrat polimer karbohidrat
0 959.27 959.27 1435.19 0 959.27 959.27 1435.19
20 916.7 914.6 1364.98 0.0437 20 923.92 920.6 1376.87 0.0353
40 885.71 891.48 1314.08 0.0588 40 896.89 908.48 1332.41 0.0503
60 861.52 871.81 1274.48 0.0669 60 875.11 881.81 1296.72 0.059
80 841.77 1242.23 0.072 80 856.96 1267.02 0.0648
100 825.15 1215.16 0.0757 100
841.44 1241.69 0.069
120 810.83 1191.88 0.0785 120 827.92 1219.66 0.0722

4% NaOH
Time ηpredik ηexp Derajat % loss
polimer karbohidrat
0 959.27 959.27 1435.19
20 908.31 909 1351.18 0.05237
40 873.22 871.48 1293.62 0.0666
η
  60 846.7 831.81 1250.3 0.0738
80 825.5 1215.73 0.0783
100
807.92 1187.15 0.0814
120 792.95 1162.87 0.0838
 Result The Best Conditions
Lignin Decrease
 Pressure 2 bar & Temperature
Reference [OH-] PO2 Kappa Active Frequency
Alkali Charge [%] 1 2 3 4 5
exponent exponent Number Energy Factor
Heating time [min] 56.6 38.2 30.3 25.7 22.7
(m) (n) exponent (q) (kJ/mol)
Viscosity [ml/g] 878.52 888.18 893.52 897.14 899.68
Pine [8] 0.47 0.47 3.5 47 2.5
Pine [9] 0.7 0.7 2.0 51 3 x 106
This study 0.568 1.494 2.675 24.979 33.11
 NaOH 2 % & Suhu
(Abaca Oxygen [bar] 2 3 4 5
fiber)
Heating time [min] 38.2 20.8 13.5 9.7
Viscosity [ml/g] 888.18 896.6 902.18 906.03

Carbohydrate Degradation
Pressure
Pressure 22 bar
bar && NaOH
NaOH 2%
2%
Reference [OH-] PO2 Viskositas Active Frequency Temperature
exponent exponent Energy Factor
70 75 80 85 90 95 100
exponen [oC]
(x) t (β) (λ) (kJ/mol)
Heating time
48 44.9 41.6 38.2 34.8 31.4 28
0.43 0.35 11 30.23 8.75x10 -8 [min]
Eucalyptus
0.315 1.087 8 33.25 2.5x10-18 Viscosity 896.4 890.7 888.1 885.7 881.6
893.5 883.6
This study [ml/g] 1 6 8 6 324
Conclusion
The prediction of Abaca fiber was accomplished to obtain best operating condition
for the efficient and effective process. The prediction was completed by obtaining
rection kinetic model derived from experimental data. The decrease in lignin content
can be predicted by knowing the values of kinetics parameters, which are q, m, n, E A,
and A for predicting kappa number. The degradation of carbohydrates can be
predicted by knowing the values of λ , x, β, E m, and Am for predicting viscosity
value. Based on the prediction results, the best process conditions for oxygen
delignification of Abaca fiber (Musa textilis) are at a pressure of 2 bar, temperature
of 85°C and 1% of NaOH for 56.6 minutes with a viscosity of 878.52 ml/g.

27
 References
Ardina, V. (2018). Pengaruh Active Alkali Charge Terhadap Delignifikasi Dan Degradasi Fiber Pada Proses. Thesis. Institute
Technology Sepuluh Nopember.
Bajpai, P. 2012. Oxygen Delignification Environmentally Benign Approaches for Pulp Bleaching. Elsevier. Belanda.
Darmawan, Arya, (2020). Studi Pembuatan Pulp Dari Bahan Non-Wood Menggunakan Metode Kraft Pulping Dengan
Delignifikasi Oksigen. Thesis. Institute Technology Sepuluh Nopember.
Dogan, Ismail. 2004. Mass Transfer and Kinetics in Oxygen Delignification. Turki.
Vijayalakshmi, K. dan Kavitha, A. 2014. Abaca Fibre. Transactions on Engineering and Sciences, Vol. 2, No. 09..
Ji, Yun. 2007. Kinetics and Mechanism of Oxygen Delignification. Electronic Theses and Dissertations. 227
Jafari V, Nieminen K, Sixta H and Van Heiningen A 2015 Cellulose, 22 2055.
Iribarne J and Schroeder LR 1997 Tappi J. 80 241.
Thank You