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: 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
• 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
O O O
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* Endo-Beta 1,4 Xylanase
* Trend is towards 0.10 mm or 0.075 mm slotted screen
 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 O O O
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

-(-CH2CH-)n- HO
OH
OH
OH HO
OH
OH + CH3COOH HO
OH
OH
OH

OH
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

Polyvinyl alcohol
OH HO OH
OH OH
OH HO
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

BL X 13064 d o sag e (lb /t)

120
0.8
100
stickies

80 0.6

60
0.4
40
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

Tensile Strength
Kraft Usage (%)

25
SWK Usage
260
Tensile
20

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

Tensile Strength
Kraft Usage (%)

15

SWK Usage
150
Tensile

10
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%
B/BW

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.

Endo-Beta 1,4 Xylanase