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. Tel (919) 515-6185 Fax (919) 515-6302 Fax. Email: richard_venditti@ncsu.edu

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 Th starting molecules th t enzymes The t ti l l that process are called substrates and these are converted t products th t d to d t

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, y y ,p , temperature, concentration of substrate y p yp y Commercial enzyme products are typically mixtures of different enzymes, the enzymes often complement the activity of one another h

Endo-Beta 1,4 Xylanase

Types of Enzymes in Pulp and Paper and R P d Respective S b i Substrates

Amylase --- starch Cellulase --- cellulose fibers Protease --- proteins P t t i Hemicellulases(Xylanase) ---hemicellulose Lipase --- glycerol backbone, pitch Esterase --- esters stickies esters, Pectinase --- pectins
Endo-Beta 1,4 Xylanase

Enzyme Applications in Pulp d Paper i P l and P

Treat starches for paper applications p p pp Enhanced bleaching Treatment for pitch Enhanced deinking E h d d i ki Treatment for stickies in paper recycling Removal of fines Reduce refining energy C ea s Cleans white water syste s te ate systems Improve softness in tissue Clean outs
Endo-Beta 1,4 Xylanase

Starch Conversion for Surface Coatings C i

Amylases are used to cleave starch molecules to reduce the viscosity y 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 tri-glycerides are more stable in water, wont deposit as much

Endo-Beta 1,4 Xylanase

CH2 --------- CH ---------CH2

O C=O
(CH2)15 CH3

Triglycerides Ester-Bonds

O C=O

O C=O

(CH2)15 CH3 (CH2)15 CH3

glycerol
CH2 --------- CH ---------CH2
OH OH OH

Fatty acids
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 y y y these microfibrils, releasing the adhesives y p 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

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

O C=O CH3

O C=O CH3

Ester-Bonds
C=O CH3

PVAlcohol
- (CH2 CH )- CH2 CH - CH2 CH )n OH OH OH

Acetic acid
OH C=O CH3
Endo-Beta 1,4 Xylanase

polyvinyl acetate ( CH CH )n -(-CH2CH-)nOCOCH3

with Esterase

Hydrophobic Surface

without Esterase

Agglomerates of PVAc gg

polyvinyl alcohol + acetic acid -(-CH2CH-)nOH + CH3COOH

OH OH OH OH OH OH OH OH OH OH HO OH OH OH OH OH OH

OH HO OH OH HO OH HO OH HO OH OH OH OH OH OH OH HO

OH OH OH OH HO OH OH HO OH OH OH

OH HO OH OH

Polyvinyl alcohol y y
Endo-Beta 1,4 Xylanase

Hydrophilic

Electron micrographs
Untreated Treated

Endo-Beta 1,4 Xylanase

Optimyze Plus 735 trial data

stickies transfer on reel samples
during Optimyze Plus 735 evaluation
160 140 120 count PPM BLX dosage 0.8 0.6 0.4 0.2 0 3/4 3/24 4/13 5/3 5/23 1.2 12 1 BL X 13064 d o sag e (lb /t)

stickies

100 80 60 40 20 0 2/12

Endo-Beta 1,4 Xylanase

Caustic replacement: neutral deinking f newsprint d i ki t l d i ki for i t deinking

Caustic is used in pulping recycled fibers to swell fibers, improving paper making p potential Cellulase enzymes can be used in j conjunction with or as a substitute for the caustic to swell fibers Neutral deinking has some advantages g g 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 p g g improved strength at higher freeness Often better runnability or less dryer gy q energy required
Endo-Beta 1,4 Xylanase

Fibrillation

4/29/2009

Endo-Beta 1,4 Xylanase

Fiber Modification
Enzymes can assist this de-lamination de lamination process Conditions fiber for refining Reduces refining energy Changes the refining curve Old rules do not apply pp y Laboratory Testing
Endo-Beta 1,4 Xylanase

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

METHODS:

Endo-Beta 1,4 Xylanase

45 40

Machine Trial of Buzyme 2545 in Napkin i N ki grade d

275 270

35 30 Kraft Usage (%) 25 260 20 15 10 250 5 0 245 255 265 Tensile Stre ength

SWK Usage Tensile

Pre-trial

Trial

Endo-Beta 1,4 Xylanase

25

Machine Trial of Buzyme 2545 in Napkin i N ki grade d

300 250

20

200 15 150 10 100 Tensile Stren ngth Kraft Usage (%)

SWK Usage Tensile

5 50

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 R fi i energy reduced 14% d d 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 soluble, 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 fibers, Softness increases of up to 25% P&G has several patents, some donated h l t t d t d to NCSU

Endo-Beta 1,4 Xylanase

Case History
MILL: FIBER: GRADE: GOAL:

METHODS:

Quebec 95% SWD/5% Recycled Fiber y Premium Bath Reduce refining energy, increase softness and bulk, maintain bulk tensile 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 y y y y y
11

10

Average Bulk to Tensile Increase of 3.5%

B/BW

7 12 14 16 18 20 22

GMT/BW Buzyme 2535 Linear (Buzyme 2535) Gloxylated PAM Linear (Gloxylated PAM) Endo-Beta 1,4 Xylanase

Results
Shut down refiners Maintained tensile Bulk/basis weight increased by avg of 3 5% avg. 3.5% Able to reduce BWT due to increase in tensile Machine speed increase of 100 FPM due to FPM, better drainage

Endo-Beta 1,4 Xylanase

ROI for Fiber Modification

Reduction in refiner energy Less fines generation
Better drainage Softer feel Less dusting g Cleaner white water

Reduction in starch or CMC Fiber substitution

C ld use more MOW l Could MOW, less virgin i i
Endo-Beta 1,4 Xylanase

Improved biodegradability of pulp mill waste water ill

Cellulases and Hemicellulases used to degrade cellulose and other high molecular weight polymers COD/BOD ratio of domestic sewage i fd i 2:1 COD/BOD ratio of paper mill waste water up to 5:1 yd o ys s of cellulose es Hydrolysis o ce u ose 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 boil-outs, molecules in deposits and solubilize deposits

Endo-Beta 1,4 Xylanase

Summary
Enzymes are g y 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 t h bl hi l Future: high valued functionalized fibers, improved pu p g, spec a ed pape p o ed pulping, specialized paper properties, conversion of wastes to fermentable sugars.
Endo-Beta 1,4 Xylanase