Tailoring Fiber Properties With Oxygen and Peroxide Beyond - PowerPoint PPT Presentation

Tailoring Fiber Properties With Oxygen and Peroxide Beyond Brightness Dongcheng Zhang, Dongho Kim, Lenong Allison, Zheng Dang, Arthur J. Ragauskas Institute of Paper Science and Technology School of Chemistry and Biochemistry Georgia Institute of Technology

Tailoring Fiber Properties – Beyond Brightness: Basic Realities of New Millennium The Ruthless have the Edge Morgan Witzel, Financial Times •“Eventually there comes a time when a company’s core market can grow no further……..Share price begins to slip as investors seek better opportunities elsewhere • Only three means of getting out of the saturation trap • Aggressive method: Compete intensively with rivals, taking market share away from competitors • Acquisition method: Buy or merge companies • Innovative method: Discover a new way to break of the market and develop a new market

Tailoring Fiber Properties – Beyond Brightness: Promising Research Patterns “If you want to succeed, you should strike out on new paths rather than travel the worn paths of accepted success.” – John D. Rockefeller Process Research Publications: +150,000 Product-Platform Research Publications: ~9,000

Tailoring Fiber Properties – Beyond Brightness: Importance of Carboxylate Groups • Main group responsible for surface and bulk charge of kraft fibers. COO HOOC • Important for pulp swelling. COOH OOC COO COO • Increase pulp fiber softness and collapsibility. [-COO ][H ] • Improve pulp strength properties. K specific = [-COOH] • Improve beatability. • Capable of ion-exchange reactions.

The Fate of Fiber Charge: Topochemistry of Acid Groups -ECF SW Kraft Pulp Experimental: Grafted acid groups on holocellulose, controlling topochemistry 1 [-COO - ] BLANK 0.6 BULK SURFACE 0.2 1 2 3 4 5 SEM Lumen Position Barzyk, Page, and Ragauskas (1996)

The Fate of Fiber Charge: Topochemistry of Acid Groups -ECF SW Kraft Pulp Scott- Bond (J) 0.25 0.2 BLANK 0.15 BULK 0.1 SURFACE 0.05 0 170 220 270 320 370 2 / g) Light Scattering Coefficient (cm Conclusion: Surface acid groups yield unique strength properties

The Fate of Fiber Charge: Fiber Acid Groups: Key parameter to enhance fiber-fiber bonding, swelling, wet-end chemical retention 5 O 4 O – C Breaking Length (km) BLANK 3 BULK 2 SURFACE 1 0 170 220 270 320 370 Light Scattering Coefficient (cm 2 / g) Light Scattering (cm 2 /g) Barzyk, Page, and Ragauskas (1996) Attachment of CMC onto Kraft ECF Fiber (Lindstrom, 2000) - pH 8, 0.05 M CaCO 3 , csc 2.5%, 120 o C, 2h - 1 – 4% charge

Pulp Mill Current Status

The Fate of Fiber Charge: Fiber Charge - Mill Status 0.08 0.07 Acid content (meq/gr) 0.06 0.05 0.04 0.03 0.02 0.01 0 ) ) ) ) ) ) ) ) ) e e 2 W W ) W W W s W t t Q u i i D f f S S S S S S A t l l p u u - t ( ( / ( ( ( ( y S S s S C C C C C l C o a P p - - - - - - c t t ( t t t t f f f f f u f a a a a a a W W E r r r r r r 0.035 K K K K K ( K S S C ( ( - C C t - f - a t t f f r a a K r r K K 0.03 0.025 Acid content (meq/gr) 0.02 0.015 Little, if any, control of 0.01 Fiber charge 0.016 – 0.07 meq/gr 0.005 Fiber resource only current control mechanism 0 Kraft-A Kraft-A Kraft-A Kraft-A Kraft-A Kraft-A Kraft-B Kraft-B

The Fate of Fiber Charge: Mill Status OD(EOP)D Mill Tensile Strength and • Bulk/Surface Acid Groups 100 120 Tensile Index 95 Bulk A cid 100 90 peroxide 85 eq/g 80 Tensile Inde Acid Content, 80 µ 75 60 70 40 Gradual loss of 65 Surface Acid groups x10 acid groups due in part 60 20 to degradation of lignin 55 Finally P increases 50 0 k t * * ) k a * ) o t ) 3 d 4 t a ) c M 3 a - 4 Brightness o R e o M - 1 M R C e 1 R r ( t R S F ( e ) r 0 ( e P h t e ( 2 D a Strength-acid groups c n r O s e f O t M n w s a a E f n e M W s o 1 ( a r n r D e B 1 r a 2 T f D e r O T 1 R D 1 Stage D

The Fate of Fiber Charge During Peroxide Bleaching and Oxygen Delignification What Contributes to Fiber Charge Unbleached Kraft Pulps - Lignin - Polysaccharides > Uronic Acids > Hexenuronic Acids > Oxidized Reducing Ends ECF Bleached Pulps - Polysaccharides > Uronic Acids > Oxidized Reducing Ends > Oxidized Fragments?? 1um - Oxidized Lignin Fragments ??

The Fate of Fiber Charge During Peroxide Bleaching and Oxygen Delignification Polysaccharide Degradation Polysaccharide Retention CH 2 OH CH 2 OH CH 2 OH O O OR OR O OR O 2 /HO - HOH 2 C HOH 2 C OR OH OH O O OR OR OR HO RO OH OH O - OR O OR OH O - O O 2 - RO- HOH 2 C OR O CH 2 OH CH 2 OH CH 2 OH OH O O O OR HO - OR OR OR O O O - -HOO - HO COOH O O OH O HOH 2 C HOH 2 C OR O HOO - OR O H + OR OR O O COOH HOOC HO - HOH 2 C OR O OR COOH HO

Fate of Fiber Charge Peroxide Bleaching

The Fate of Fiber Charge: Peroxide-Stage Carboxylic acid groups content versus Peroxide Bleaching Time 11 Carboxylica acid content (meq/100go.d. pulp) 10.8 10.6 10.4 10.2 3% H2O2, 2% NaOH, 10% con. 3% H2O2, 2% NaOH, 5% con. 10 3% H2O2, 2% NaOH, 5% con. 0.3% DTPA 9.8 9.6 9.4 9.2 9 0 20 40 60 80 100 120 140 160 180 200 H2O2 Bleaching Time (min.) Provide new operating protocols to enhance Fiber Charge Sheet Strength, Water Retention Properties via an advanced P-stage

The Fate of Fiber Charge: Peroxide Stage ECF Pulp 44 43 E 42 41 meq/kg pulp EOP-70C 40 39 EOP-105C 38 37 EOP-0.5% MgSO4 36 35 EOP-0.1% MnSO4 34 33 EOP-0.1% FeSO4 1% H 2 O 2 , 1% NaOH

The Fate of Fiber Charge: Peroxide Stage ECF Pulp 44 E 43 42 EOP (1% H2O2) 41 meq/kg pul 40 EP (1% H2O2) 39 38 EP-(1% H2O2/0.5% 37 M gSO4) 36 EP- (1% H2O2/0.1% 35 FeSO4) 34 EP (2% H2O2) 33 1% H 2 O 2 , 1% NaOH, 70 o C

The Fate of Fiber Charge: Peroxide Stage 40 39.5 39 38.5 38 meq/kg pulp 37.5 37 36.5 36 35.5 35 ECF Pulp (E+P) 40C (E+P) 50C (E+P) 60C (E+P) 70C (E+P) 80C

The Fate of Fiber Charge: Peroxide Stage 1% H 2 O 2 , 2% NaOH, 80 o C, 1 h Conditions of H 2 O 2 Carboxylic Acid Content Tensile Tear Index Bleaching (meq./kg O.D. pulp) Index Original(fully 37.00 bleached pulp) H 2 O 2 bleaching 45.40 + 10% + 11% without MgSO 4 H 2 O 2 bleaching 46.00 + 10% + 12% with 0.5% MgSO 4

Oxygen Delignification Fate of Fiber Charge

The Fate of Fiber Charge: O Delignification Acid content 30 220 Kappa number 28 200 Acid, µ mol/g,residual lignin 26 Kappa number 180 24 22 160 20 140 18 120 16 120 Kraft Pulps 100 14 0 20 40 60 80 Time,min 110 Carboxylic acid, µ mol/g fiber 100 90 80 70 1.5% NaOH 2.5% NaOH 3.5% NaOH 60 640 kPa O 2 800 kPa O 2 960 kPa O 2 o C o C o C 85 100 115 50 0 10 20 30 40 50 60 Reaction time, min

The Fate of Fiber Charge: O Delignification 0 C 85 640 kPa 0 C Higher O 2 Pressure 100 30 800 kPa 0 C 115 30 960 kPa Better Delignification 25 Kappa number 25 Kappa number Higher Temperature 20 Better Delignification 20 15 15 10 0 10 20 30 40 50 60 10 Time, min 0 10 20 30 40 50 60 Time, min o C 85 640 kPa 110 o C 110 100 800 kPa o C 969 kPa 115 105 105 Holocellulose Pulp Acid, µ mol/g,fiber Acid, µ mol/g,fiber 100 100 Higher O 2 Pressure 95 95 Some Benefit 90 90 Holocellulose Pulp 85 85 Higher Temperature 0 10 20 30 40 50 60 0 10 20 30 40 50 60 Time, min Time, min Less Fiber Charge

The Fate of Fiber Charge: O Delignification 130 400 Bulk pulp 380 120 Holocellulose 1. 30 – 50% Delignification 360 Residual lignin Acid, µ mol/g, fiber or holocellulose 110 340 Acid, µ mol/g, residual lignin 100 320 2. Holocellulose 90 300 280 80 260 70 240 60 220 50 200 180 40 160 30 14 16 18 20 22 24 26 28 30 Tensile strength Kappa number 12 Tensile index,N.m/g 10 8 6 4 2 0 34.82 38.64 55.40 Acid groups content in holocellulose,mmol/g

The Fate of Fiber Charge: O Delignification OD pulp Kraft SW pulp Screened a Series of Carboxylic Acid Generating Catalysts: O OH OH Cellulose Oxidant Cellulose O O O O HO O HO O Cellulose Cellulose OH OH • Compatible with O-Chemistry • Maintained or improved O-Delignification • No negative effect of cellulose D.P.

The Fate of Fiber Charge: O Delignification Selective Oxidation of Polysaccharides O O- H OH OH O OH Oxidant HO O O O Oxidant O O HO H O Fast H O- -O HO OMe OH OMe MeO Oxidant Slow OH O HO O -O O O- OMe Catalyst: Ruthenium pyrochlore oxide (Bi 2 Ru x O 7-x ) Reported by Arts et al to be good for monosaccharides only! Journal of Carbohydrate Chemistry 15 (1996) 317-29.

The Fate of Fiber Charge: O Delignification Oxygen Delignified Pulp Properties Catalyst % Kappa # Viscosity/mPa.s 0 15.5 19.2 80 0.10 15.5 - Carboxylic acid, µ mol/g,HoloPulp 70 0.18 15.4 18.8 60 0.39 15.4 18.7 50 10% csc, 2.5% NaOH, 800 kPa O 2 ,100 o C 40 O-Catalyst for Fiber Charge Development! 30 20 0.0 0.1 0.2 0.3 0.4 Catalyst, %