1. Boras, 2016
Rheological, Chemical and Thermal Properties of Enzymatic/Mechanically Pretreated Pulp
Ayhan TOZLUOĞLU 1, Bayram POYRAZ2, Yalcin COPUR1
1 Forest Product Engineering, Faculty of Forestry, Duzce University, Duzce, Turkey
2 Department of Polymer Engineering, Faculty of Technology, Duzce University, Duzce, Turkey
DÜZCE UNIVERSITY FOREST FACULTY DEPARTMENT OF WOOD CHEMSISTRY AND TECHNOLOGY

2. NaBH4 vs Kraft vs sulfite and dissolving pulps NaBH4
Boras, 2016
AIM OF THE STUDY
NaBH4 vs Kraft vs sulfite and dissolving pulps
NaBH4
Effectively degrade lignin
Preserves the carbohydrates
Mechanical pretreatment
Enzymatic pretreatment
Celluclast 1.5 L and Pulpzyme HC Literature has very limited knowledge on the effect of these enzymes.
To produce NFC pretreatment effects on the chemical and crystalline structures, reological and morphological properties and thermal stabilities of samples were examined in this study.
DÜZCE UNIVERSITY FOREST FACULTY DEPARTMENT OF WOOD CHEMSISTRY AND TECHNOLOGY

3. Eucalyptus camaldulensis logs were reduced to chips ↓ PULPING
Boras, 2016
MATERIALS AND METHODS
Eucalyptus camaldulensis logs were reduced to chips
↓ PULPING
Chips were then cooked by kraft-NaBH4. (0.3% NaBH4 o.d. chips).
18% active alkali and 28% sulphidity charges
Liquor-to-wood ratio (L/kg) was 5:1.
The highest pulping temperature was 150 ºC. The highest temperature was reached in 30 min and cooking continued for 150 min after reaching the maximum temperature.
↓ BLEACHING
DÜZCE UNIVERSITY FOREST FACULTY DEPARTMENT OF WOOD CHEMSISTRY AND TECHNOLOGY

4. Boras, 2016
MATERIALS AND METHODS
The pulp was then bleached using Elemental Chlorine Free (ECF) processes of ODEP (oxygen-chlorine dioxide-alkaline-peroxide). (H2)
Oxygen (O) bleaching, 2% NaOH (o.d. pulp) and 0.5% MgSO4 (o.d. pulp), 6 kgf cm-2 (90 ºC for 60 min), 10% consistency.
The chlorine dioxide (D) bleaching, 60 ºC for 60 min. Each pulp (10 g, o.d.) was treated with 97 mL ClO2 (1% w/v) and 3 mL H2SO4 (98% w/v) solution.
The alkaline extraction (E), 60 ºC for 60 min. Each pulp (10 g, o.d.) was treated with 100 mL NaOH solution (2%w/v).
The hydrogen peroxide bleaching (P), 10% pulp consistency, 4% H2O2, 0.5% Na2SiO3, 0.1% MgSO4 and 1.5% NaOH (o.d. pulp), 105 ºC for 120 min
↓ PRETREATMENTS
DÜZCE UNIVERSITY FOREST FACULTY DEPARTMENT OF WOOD CHEMSISTRY AND TECHNOLOGY

5. Mechanical pretreatment Using a Waring blender for 10 min (H2M)
Boras, 2016
Mechanical pretreatment
Using a Waring blender for 10 min (H2M)
Enzmatic pretreatment
Pulpzyme HC 2500 (Novozymes, Bagsvaerd, Denmark)
0 AXU/g (H2ME1)
25 AXU/g (H2ME2)
100 AXU/g (H2ME3)
250 AXU/g (H2ME4)
Celluclast 1.5 L (Novozymes, Bagsvaerd, Denmark)
0 EGU/g (H2ME5)
2 EGU/g (H2ME6)
5 EGU/g (H2ME7)
10 EGU/g (H2ME8)
Using a Waring blender for 10 min (H2MEM1, H2MEM2, H2MEM3, H2MEM4, H2MEM5, H2MEM6, H2MEM7, H2MEM8)
DÜZCE UNIVERSITY FOREST FACULTY DEPARTMENT OF WOOD CHEMSISTRY AND TECHNOLOGY

6. Boras, 2016
SELECTION OF OPTIMUM ENZYMATIC TREATMENTS FOR PULPZYME HC 2500 AND CELLUCLAS 1.5 L FOR FURTHER ANALYSIS !!!
The optimum Pulpzyme HC 2500 and Celluclast1.5 L enzyme concentrations were determined in this study by taking into account the xylan to glucan ratio remaining in the material structure after the enzymatic pretreatments according to HPLC results.
FOR FURTHER ANALYSIS
Rheology
FTIR
Thermal Analysis
SEM
DÜZCE UNIVERSITY FOREST FACULTY DEPARTMENT OF WOOD CHEMSISTRY AND TECHNOLOGY

7. RESULTS AND DISCUSSION
Boras, 2016
RESULTS AND DISCUSSION
Table 1.Yield, kappa and viscosity values of NaBH4 modified kraft and bleached pulps
Bleaching stages
Total Yield, %
Kappa
Viscosity, cP
Kraft
45.7 ± 0.46
18.4 ± 0.15
10.2 ± 0.38
Kraft-NaBH4
45.3 ± 0.61
14.5 ± 0.49
9.85 ± 0.38
Kraft-NaBH4-O
43.6± 0.15
10.1 ± 0.32
8.57 ± 0.29
Kraft-NaBH4-O-D
43.5± 0.23
3.79 ± 0.13
5.60 ± 0.26
Kraft-NaBH4-O-D-E
41.4 ± 0.39
3.45 ± 0.00
5.90 ± 0.17
Kraft-NaBH4-O-D-E-P
39.5 ± 0.18
3.34 ± 0.03
5.43 ± 0.45
DÜZCE UNIVERSITY FOREST FACULTY DEPARTMENT OF WOOD CHEMSISTRY AND TECHNOLOGY

8. Table 2. Chemical composition of pulps after pulping
Chemical Components (%)
Chip
Kraft-NaBH4
Kraft
Glucan
40.0±1.53
62.6 ± 2.04
61.8 ± 2.04
Xylan
8.67±0.19
15.8 ± 0.65
15.3 ± 0.65
Galactan
0.18±0.14
0.10 ±0.03 -
Mannan+Arabinan
0.44±0.20
0.33 ± 0.00
Acid Insoluble Lignin (AIL)
27.6±0.99
1.65 ± 0.69
1.98 ± 0.54
Acid Soluble Lignin (ASL)
0.74±0.01
1.07 ± 0.03
1.05 ± 0.02
% removed material (o.d. chip)
Total material
54.7
54.4
29.1
29.5
17.4
19.5
Total lignin
95.7
95.1

9. Chemical Components (%) Chip Kraft-NaBH4 Kraft-NaBH4 (ODEP) H2 Glucan
Table 2. Chemical composition of pulps after Bleaching (kraft vs NaBH4)
Chemical Components (%)
Chip
Kraft-NaBH4
Kraft-NaBH4 (ODEP) H2
Glucan
40.0±1.53
62.6 ± 2.04
66.2 ± 0.81
Xylan
8.67±0.19
15.8 ± 0.65
15.8 ± 0.85
Galactan
0.18±0.14
0.10 ±0.03 -
Mannan+Arabinan
0.44±0.20
0.33 ± 0.00
0.56 ± 0.20
Acid Insoluble Lignin (AIL)
27.6±0.99
1.65 ± 0.69
1.28 ± 0.05
Acid Soluble Lignin (ASL)
0.74±0.01
1.07 ± 0.03
1.08 ± 0.01
% removed material (o.d. chip)
Total material
54.7
60.5
29.1
34.6
17.4
28.0
Total lignin
95.7
96.7

10. % removed material (o.d. chip)
Pulpzyme HC 2500
Chemical Components (%)
H2M= H2ME1
H2ME2
H2ME3
H2ME4
H2MEM3
Glucan
65.9 ± 0.14
65.5 ± 0.47
66.1 ± 0.74
61.8 ± 0.08
64.9 ± 0.78
Xylan
15.7 ± 0.32
15.5 ± 0.65
15.6 ± 0.11
12.2 ± 0.15
15.3 ± 0.19
% removed material (o.d. chip)
Total material
60.9
61.6
61.9
62.1
62.2
35.6
37.1
41.4
38.7
29.2
31.3
31.5
46.6
33.3
Celluclast1.5 L
H2M= H2ME5
H2ME6
H2ME7
H2ME8
H2MEM6
64.3 ± 0.55
62.0 ± 0.14
62.0 ± 0.88
65.0 ± 0.12
16.3 ± 0.91
13.7 ± 0.34
12.8 ± 0.47
16.9 ± 0.45
63.8
64.7
66.4
65.3
41.9
45.3
47.9
43.7
32.0
44.3
50.3
32.5

11. Figure . Viscosity as a function of the shear rate for wood pulp (H2) and pretreated materials (H2M, H2ME3, H2ME6, H2MEM3 and H2MEM6)

12. Figure . FTIR spectra of wood pulp (H2) and pretreated materials (H2M, H2ME3, H2ME6, H2MEM3 and H2MEM6).

13. Figure . TGA curve of wood pulp (H2) and pretreated materials (H2M, H2ME3, H2ME8, H2MEM3 and H2MEM6).

14. Figure . SEM images: (a) H2, (b) H2M, (c) H2ME3, (d) H2ME6, (e) H2MEM3, (f) H2MEM6

15. CONCLUSIONS
A higher decrease in viscosity was observed with Celluclast 1.5 L enzyme (H2ME6) compared to Pulpzyme HC 2500 (H2ME3) treated sample.
FTIR results indicated that some alterations in crystallinity as well as chemical interactions occurred in cellulose structure during pretreatments.
TGA results showed that samples treated with Celluclast 1.5 L had lower thermal stability compared to Pulpzyme HC 2500.
Enzymes utilized in this study improved the fibrillation.

16. Efficiency of Some Enzymes in Nanocellulose Production Boras, 2016
THANK YOU…
DÜZCE UNIVERSITY FOREST FACULTY Assist. Prof. Dr. Ayhan TOZLUOGLU
DEPARTMENT OF WOOD CHEMSISTRY AND TECHNOLOGY