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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 27695-8005 Tel. (919) 515-6185 Fax. (919) 515-6302 Email: [email protected] Slides courtesy of Phil Hoekstra. Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase Cellulase enzyme which acts on cellulose substrate to make product of glucose. Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase CH2 –--------- CH –---------CH2 Triglycerides OOO Ester-Bonds C=O C=O C=O (CH2)15 CH3 (CH2)15 CH3 (CH2)15 CH3 glycerol Fatty acids CH2 –--------- CH –---------CH2 │ OH OH OH OH │ C=O │ (CH2)15 CH3 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase CLASSIFICATION OF STICKIES PRIMARY SECONDARY (Formed in (Change in pulper) environment, pH, temp., etc.) Endo-Beta 1,4 Xylanase 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 0.075 mm slottedEndo-Beta screen 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase Endo-Beta 1,4 Xylanase Without Proper Water Clarification (<20% reduction): “ re-introduction of stickies” Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase -(CH2 – CH - CH2 –CH -CH2 – CH )n - PVAc OOO Ester-Bonds C=O C=O C=O CH3 CH3 CH3 PVAlcohol Acetic acid -(CH2 – CH )- CH2 –CH -CH2 – CH )n - │ OH OH OH OH │ C=O │ CH3 Endo-Beta 1,4 Xylanase polyvinyl acetate Hydrophobic Surface -(-CH2CH-)n- OCOCH3 without Esterase with Esterase Agglomerates of PVAc polyvinyl alcohol + acetic acid -(-CH CH-)n- OH 2 OH HO OH HO OH OH OH OH OH + CH COOH OH HO 3 HO OH OH OH OH OH HO OH OH OH HO OH OH OH OH OH OH OH OH HO OH OH OH OH OH OH OH HO OH OH OH OH HO Polyvinyl alcohol OH OH OH OH OH Hydrophilic Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase Electron micrographs Untreated Treated Endo-Beta 1,4 Xylanase Optimyze Plus 735 trial data stickies transfer on reel samples during Optimyze Plus 735 evaluation 160 1.2 count 140 PPM 1 BLX dosage 120 0.8 100 80 0.6 stickies 60 0.4 40 BLX 13064dosage (lb/t) 0.2 20 0 0 2/12 3/4 3/24 4/13 5/3 5/23 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase Fibrillation 3/3/2010 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase Machine Trial of Buzyme 2545 in Napkin grade 45 275 40 270 35 30 265 25 SWK Usage 260 Tensile 20 Kraft Usage (%) Usage Kraft Tensile Strength Tensile 15 255 10 250 5 0 245 Pre-trial Trial Endo-Beta 1,4 Xylanase Machine Trial of Buzyme 2545 in Napkin grade 25 300 250 20 200 15 SWK Usage 150 Tensile 10 Kraft Usage (%) Usage Kraft Tensile Strength Tensile 100 5 50 0 0 Pre-trial Trial Refining energy reduced Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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?) Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase Bulk vs. Tensile Buzyme 2535 vs. Glyoxylated Polyacrylamide 11 Average Bulk to Tensile 10 Increase of 3.5% 9 B/BW 8 7 12 14 16 18 20 22 GMT/BW Buzyme 2535 Gloxylated PAM Linear (Buzyme 2535) Linear (Gloxylated PAM)Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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 Endo-Beta 1,4 Xylanase 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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  • FPL Spaceboard Development

    FPL Spaceboard Development

    1988. In: TAPPI proceedings of the 1988 corrugated containers conference; October 24-27; Orlando, FL. Atlanta, GA: TAPPI Press: 11-17. FPL SPACEBOARD DEVELOPMENT The Forest Products Laboratory (FPL) has developed two processing methods ( 1 , 2 ) to form, dewater and consolidate, and dry three-dimensional spaceboard sheets. This paper describes the two processing J. F. Hunt, Mechanical Engineer D. E, Gunderson, Research General Engineer methods; the strength and stiffness values of spaceboard; and the advantages, disadvantages, and 1 USDA Forest Service, Forest Products Laboratory, development challenges of the product and process. One Gifford Pinchot Dr., Madison, WI 53705-2398 BACKGROUND U.S.A. The spaceboard concept emerged from research aimed at ABSTRACT improving the support of linerboard in corrugated fiberboard and the efficient distribution of fibers in structural boards. Experiments at FPL showed that The future direction of structural products from fibers will be toward more efficient fiber the edgewise compression strength of corrugated fiberboard with press-dried linerboard and utilization through efficient design. The Forest Products Laboratory has developed two processing conventional corrugated medium was lower than It was suspected that the corrugated methods to produce three-dimensional structural anticipated. sheets and panels made from fibers. The structural medium was not providing sufficient support to the board that results from combining two sheets or two linerboard. In experiments by Vance Setterholm and panels is called FPL Spaceboard. Dennis Gunderson of FPL, a combined board made from two linerboards fully supported by a low-density foam core yielded higher edgewise compression strength The thickness of the sheet or panel generally than the combined board with the same linerboard determines which processing method to use.