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, 81620 Duzce, Turkey 2 Department of Polymer Engineering, Faculty of Technology, Duzce University, 81620 Duzce, Turkey e-mail: ayhantozluoglu@duzce.edu.tr DÜZCE UNIVERSITY FOREST FACULTY DEPARTMENT OF WOOD CHEMSISTRY AND TECHNOLOGY

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 2500. 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

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

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

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

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

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

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

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

% 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

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

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

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

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

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.

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