Enzyme Applications in Pulp and Paper: An Introduction to Applications

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1 Enzyme Applications in Pulp and Paper: An Introduction to Applications Dr. Richard Venditti Associate Professor - Director of Graduate Programs Department of Wood and Paper Science Biltmore Hall Room 1204 Raleigh NC Tel. (919) Fax. (919) Slides courtesy of Phil Hoekstra.

2 Enzymes Are proteins that catalyze chemical reactions Biological cells need enzymes to perform needed functions The starting molecules that enzymes process are called substrates and these are converted to products

3 Cellulase enzyme which acts on cellulose substrate to make product of glucose.

4 Enzymes Are extremely selective for specific substrates Activity affected by inhibitors, ph, temperature, concentration of substrate Commercial enzyme products are typically mixtures of different enzymes, the enzymes often complement the activity of one another

5 Types of Enzymes in Pulp and Paper and Respective Substrates Amylase --- starch Cellulase --- cellulose fibers Protease --- proteins Hemicellulases(Xylanase) ---hemicellulose Lipase --- glycerol backbone, pitch Esterase --- esters, stickies Pectinase --- pectins

6 Enzyme Applications in Pulp and Paper Treat starches for paper applications Enhanced bleaching Treatment for pitch Enhanced deinking Treatment for stickies in paper recycling Removal of fines Reduce refining energy Cleans white water systems Improve softness in tissue Clean outs

7 Starch Conversion for Surface Coatings Amylases are used to cleave starch molecules to reduce the viscosity Used for surface sizing and for starch in coatings Not used for dry strength agent additive

8 Bleaching Hemicellulases (xylanases) are used to cleave hemicelluloses in fiber, making the bleaching process more effective May be able to reduce bleaching chemicals by up to 30% Can improve brightness

9 Pitch treatment Lipases used to control pitch in pulping processes Converts tri-glycerides to fatty acids which are more stable in water, won t deposit as much

10 CH CH CH 2 Triglycerides O C=O O C=O O C=O Ester-Bonds (CH2)15 CH 3 (CH2)15 CH3 (CH2)15 CH3 glycerol CH CH CH 2 Fatty acids C=O (CH2)15 CH 3

11 Deinking Paper recycling inks and stickies attach to fibers at the surface of the fibers, stuck to microfibrils Cellulase and hemicellulase enzymes hydrolyze these microfibrils, releasing the adhesives Esterases help breakdown ink particles Enzyme assisted DI reported to remove 30-60% more toners Enzyme assisted DI reported to improve brightness by 4-5 points

12 Control and Removal Methods for Stickies Use of environmentally benign adhesive (recyclable adhesive) Avoidance: Control of recovered paper quality Mechanical removal: screening and water clarification Chemical control: polymers surfactants, others Passivation with inorganics Enzyme hydrolysis Physical adsorption to paper fibers: retention Dispersion Protection: treatment of equipment to limit deposits Mill shut down for clean-up

13 CLASSIFICATION OF STICKIES PRIMARY (Formed in pulper) SECONDARY (Change in environment, ph, temp., etc.)

14 MACRO VS MICRO STICKIES Macrostickies Retained on 6-cut (0.15 mm) slotted screen* Microstickies Accepted by 6-cut (0.15 mm) slotted screen* * Trend is towards 0.10 mm or mm slotted screen

15 Stickies Control Microstickies in dilution water recirculate back into the systems Microstickies agglomerate under shear and ph changes and contribute to macrostickies, secondary stickies Reducing microstickies will make a significant impact on macrostickies Ability to measure both micro and macro is important

16

17 Without Proper Water Clarification (<20% reduction): re-introduction of stickies

18 Enzymes as stickies treatment Esterases used to break ester bonds in polymers used in toners and adhesives Improved paper cleanliness Less deposits, less clean up on PM Can be used as substitute for talc or solvent based dispersants

19 - (CH 2 CH - CH 2 CH -CH 2 CH ) n - PVAc O C=O O C=O O C=O Ester-Bonds CH 3 CH 3 CH 3 PVAlcohol - (CH 2 CH )- CH 2 CH -CH 2 CH ) n - Acetic acid C=O CH 3

20 polyvinyl acetate -(-CH 2 CH-)n- OCOCH 3 Hydrophobic Surface without Esterase with Esterase Agglomerates of PVAc polyvinyl alcohol + acetic acid -(-CH 2 CH-)n- + CH 3 CO HO HO HO HO HO HO HO HO HO Polyvinyl alcohol Hydrophilic

21 Impact on stickies chemistry Optimyze has two impacts on stickies Cleaves ester bonds to reduce size of stickies Surfaces on smaller stickies are converted to alcohol groups Alcohol groups are less tacky Alcohol groups are polar, which allow DAF polymers to grab onto them for removal

22 Electron micrographs Untreated Treated

23 Optimyze Plus 735 trial data stickies transfer on reel samples during Optimyze Plus 735 evaluation stickies count PPM BLX dosage BLX dosage (lb/t) 0 2/12 3/4 3/24 4/13 5/3 5/23 0

24 Caustic replacement: neutral deinking for newsprint deinking Caustic is used in pulping recycled fibers to swell fibers, improving paper making potential Cellulase enzymes can be used in conjunction with or as a substitute for the caustic to swell fibers Neutral deinking has some advantages including less COD in the white water, lower costs

25 Decrease energy in refining Cellulase enzymes cause partial depolymerization of cellulose and swelling of fibers, more flexible fibers Reduction of fines Improves efficiency of refining, can decrease energy consumption or obtain improved strength at higher freeness Often better runnability or less dryer energy required

26 Fibrillation 3/3/2010

27 Fiber Modification Enzymes can assist this de-lamination process Conditions fiber for refining Reduces refining energy Changes the refining curve Old rules do not apply Laboratory Testing

28 Case History MILL: Quebec FIBER: Recycled/Softwood Kraft GRADE: Napkin GOAL: Increase tensile strength to middle of specification, reduce kraft fiber usage METHODS: Treated MOW stock at the pulper with 0.5 to 1.0 kg/tonne BZM 2545, about 3 hours of contact time

29 Machine Trial of Buzyme 2545 in Napkin grade Kraft Usage (%) Tensile Strength SWK Usage Tensile Pre-trial Trial

30 Machine Trial of Buzyme 2545 in Napkin grade Kraft Usage (%) Tensile Strength SWK Usage Tensile Pre-trial Trial Refining energy reduced

31 Results: Machine Trial of Buzyme 2545 in Napkin grade Reduced kraft from 40% to 0% of furnish Increased tensile to a comfortable range Refining energy reduced 14% Drainage is better, but cannot take advantage of it, due to drive limitations

32 Hydrolysis of fines Fines build up in water loop in PM and cause drainage, formation and paper properties problems Cellulase enzymes hydrolyze these fines, making them soluble, improving PM ops Can run PM faster (up to 10% faster in some cases?)

33 Softness in tissue Cellulase enzymes improve softness by hydrolyzing cellulose in fibers, creating weak spots in fibers, making fibers flexible Softness increases of up to 25% P&G has several patents, some donated to NCSU

34 Case History MILL: Quebec FIBER: 95% SWD/5% Recycled Fiber GRADE: Premium Bath GOAL: Reduce refining energy, increase softness and bulk, maintain tensile METHODS: Treated stock at the pulper with 0.5 to 1.0 kg/tonne BZM 2545, about 3 hours of contact time

35 Bulk vs. Tensile Buzyme 2535 vs. Glyoxylated Polyacrylamide Average Bulk to Tensile Increase of 3.5% B/BW GMT/BW Buzyme 2535 Linear (Buzyme 2535) Gloxylated PAM Linear (Gloxylated PAM)

36 Results Shut down refiners Maintained tensile Bulk/basis weight increased by avg. of 3.5% Able to reduce BWT due to increase in tensile Machine speed increase of 100 FPM, due to better drainage

37 ROI for Fiber Modification Reduction in refiner energy Less fines generation Better drainage Softer feel Less dusting Cleaner white water Reduction in starch or CMC Fiber substitution Could use more MOW, less virgin

38 Improved biodegradability of pulp mill waste water Cellulases and Hemicellulases used to degrade cellulose and other high molecular weight polymers COD/BOD ratio of domestic sewage 2:1 COD/BOD ratio of paper mill waste water up to 5:1 Hydrolysis of cellulose fines by enzymes to lower molecular weight sugars that are more biodegradable

39 Clean Ups / Boil Outs Amylase to treat starch deposits in clean ups of starch preparation/application equipment Protease used as biodispersants or enzyme boil-outs, cleave protein molecules in deposits and solubilize deposits

40 Summary Enzymes are green chemicals that can improve operations in pulp and paper Wide variety of enzymes, must be applied with understanding of how they work Several widely accepted applications, starch, bleaching, clean ups Future: high valued functionalized fibers, improved pulping, specialized paper properties, conversion of wastes to fermentable sugars.

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