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Fibre Modification Enzymes Peter Wheeler

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Fibre Modification Enzymes

Peter Wheeler

Overview

• Introduction to enzymes

– What are they?

– How do they work

• Catalysis

• Useful applications in the paper industry

– Cases

• Questions

What are enzymes?

• Each living cell contains thousands of

different kinds of enzymes.

• These enzymes do all of the work necessary

for the cell to live and function.

• Enzymes are essential to life & all living

things.

• Enzymes catalyze all the activities of life.

• Enzymes catalyze many other reactions

• Enzymes are not living things.

Enzymes are Proteins

• Proteins are macromolecules of amino

acids.

• Primarily 20 amino acids are used in living

things as building blocks for proteins.

• The shape and other properties of each

protein is dictated by the precise sequence

of amino acids in it.

• 90% of the protein in a cell is enzyme

Enzyme - structure

• Primary structure: the amino acid sequence

• Secondary structure: spatial relationships of groups of amino acids (e.g. α-helices & β-pleated

sheets)

• Tertiary structure: total 3-D shape of the enzyme

• Quaternary structure: an enzyme can be made up

of a complex of 2 or more polypeptide chains

Enzyme structure

Examples of enzyme shapes

Comparative sizes

0.001 0.01 0.1 1 10 100 1000 10000

EN Z YMES

B EN TON ITE

PITC H PAR TICL ES

STAR CH

POL YMER S (10mm)

C L AY

SMALL F IN ES

L AR GE F IN ES

H W F IB ER

SW F IB ER

LENGTH ηmLength µm

How do enzymes work?

• Enzymes are catalysts

– Lowering the activation energy for reactions

– Speeding up naturally occurring reactions

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

How do enzymes work?

Enzymes in actionhttp://www.kscience.co.uk/animations/model.swf

Where are enzymes used?

May be easier to ask where aren’t they used?

Where are enzymes used?

And of course… The Pulp and Paper Industry

Many kinds of enzymes

• Hydrolase

• Ligase

• Lyase

• Oxidoreductase

• Isomerase

• Lipase

• Amylase

• Protease

• Xylanase

• Cellulase

• adds water across a bond

• bonds (C-C, C-N, C-O etc.) using ATP

• cleaves bonds, except by hydrolysis or oxidation

• transfer of electrons

• structural change in a molecule (cis to trans)

• hydrolyzes a triglyceride

• breaks down a starch molecule

• breaks down protein molecules

• hydrolyzes xylans – bleaching

• cleaves bonds in cellulose molecules

Fiber Modification

• Cellulases catalyze reactions in various components of the fiber structure– Allowing mechanical refining to have a

greater effect• Enzymes give the papermaker many

opportunities to improve operations with this approach

– Reductions in applied energy at refining

– Fiber source rationalization

– Improved quality (strength, formation, etc.)

Refining Model

Enzyme

• Cellulase degrades cellulose in fiber wall structure, initiates wall stripping & fines generation

• Refining then delaminates cell walls, causes cell wall to collapse and starts fibrillation which provides the strength of fiber with more bonding sites

Buzyme 2535 after 6 Hours

Sh

eet

Pro

pert

y

Refining Energy

Burst (Mullen)Fold

Tensile

Tear

OpacityPorosity

EFFECT OF BEATINGON PULP PROPERTIES

Increase in ValueBreaking LengthBurst IndexDouble Folds

ShrinkageDensityAir Resistance

Decrease in ValueTear IndexOpacity

Applied Energy

Re

lati

ve

Str

en

gth

Untreated

Enzyme Treated

Enzyme’s AffectOn Fiber Strength

Case Histories

Application overview

Linerboard

Tissue

Printing & Writing

Current applications

FME application list by product

Linerboard Tissue Printing & Writing / Specialty

1 Case History - Linerboard

• FIBRE: 100% recycled, mostly brown

• GRADE: Linerboard

• GOAL: Increase compression strength

• METHOD: Treated stock at the pulper with cellulase enzyme, only 25 minutes contact time

• NOTE: Mill does not refine

1 Case History - Linerboard

• Maintained ring crush specification, while eliminating dry strength additive

• Production increase due to better drainage

Results

2 Case History -Tissue

• FIBRE: Recycled/Softwood Kraft

• GRADE: Towel

• GOAL: Increase tensile strength to

middle of specification, reduce kraft fiber usage

• METHOD: Treated stock at the pulper with

0.5 to 1.0 kg/ton BZM 2535, about 3 hours of contact time

Machine Trial of Buzyme 2535 - Towel

0

5

10

15

20

25

30

35

40

45

Pre-trial Trial

Kra

ft U

sag

e (

%)

245

250

255

260

265

270

275

Ten

sil

e S

tren

gth

SWK Usage

Tensile

2 Case History - Tissue

0

5

10

15

20

25

Pre-trial Trial

Kra

ft U

sag

e (

%)

0

50

100

150

200

250

300

Ten

sil

e S

tren

gth

SWK Usage

Tensile

Machine Trial of Buzyme 2535 - Towel

2 Case History - Tissue

• 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

Results

2 Case History - Tissue

• FIBRE: MOW, HL1, HL2

• GRADE: Consumer tissue

• GOAL: Reduce refining energy, drying requirement. Improve quality

• METHOD: Treated stock at blend chest with cellulase enzyme. Approx 1.5 hr contact

3 South African Trial - Tissue

3 South African Trial - Tissue

Machine Trial of Maximyze 2545 in Tissue – Operational Results

-10%

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

Production rate T/hr Specific Energy kWh/ton Total drying energy

% i

mp

rovem

en

t Average result for trial.

Refiner eventually set at

1kWh/ton

3 South African Trial - Tissue

Machine Trial of Maximyze 2545 in Tissue – Quality Results

-3%

-2%

-1%

0%

1%

2%

3%

4%

5%

6%

7%

8%

Crepe % Tensile MD Tensile CD Stretch

% i

mp

rovem

en

t

3 South African Trial - Tissue

Results• Refining

– Reduced specific energy by 77%

• Dropped refiner to 1kWh/ton

– Averted plate wear and replacement costs

– Total drying energy reduction of 7%

• Quality (at reduced refining)

– Crepe ratio increased by 7%

– CD tensile increased by 5%

– No change in MD tensile

– Minor drop in stretch

4 Case History - Printing & Writing

• FIBRE: HW Kraft Eucalytus

• GRADE: Printing / Writing

• GOAL: Reduce vessel element picking during printing

• METHOD: Enzyme treatment was employed on brown stock prior to bleaching

4 Case History - Printing & Writing

• Reduced vessel segments by 30%

• Reduced tear strength slightly

Results

4 Case History - Printing & Writing

FQA Vessel Element Analysis

1.00

0.67 0.67

0.58

0.40

0.50

0.60

0.70

0.80

0.90

1.00

1.10

Control Buzyme 2511(1 #/ton)

Buzyme 2511(4 #/ton)

BZM 2511 (1 #/t) &

BZM 2523 (0.25 #/t)

Rela

tive

Are

a

Buzyme 2524 after 60 MinMixed Southern HW Pulp

5 Case History – Fine Paper

• FIBRE: Acacia

• GRADE: Fine paper

• GOAL: Improve properties; reduce energy

• METHOD : Treated stock at the pulper with

0.75 kg/ton LBKP BLX 13057, 2 hours of contact time

5 Case History – Fine Paper

• MD tensile improved 9.74% and CD tensile unchanged.

• NBKP from 2.29% to 0% .

Tensile

0

1

2

3

4

5

6

7

8

9

18:3

519:5

521:4

022:5

00:0

51:4

53:3

04:5

56:2

58:0

09:4

011:2

013:2

015:1

517:0

518:5

520:5

523:4

51:4

03:2

516:1

518:4

020:1

022:1

523:1

01:2

53:2

05:3

07:2

58:2

59:2

010:1

511:3

012:3

013:2

514:2

014:4

5

19:1

519:5

520:4

021:3

522:2

0

11:3

312:1

513:1

013:5

014:2

515:1

516:0

516:5

017:4

019:0

020:0

521:0

522:4

023:3

00:1

51:2

52:1

03:1

04:3

05:0

06:0

27:3

58:3

59:2

510:1

010:5

511:4

512:3

014:4

015:3

516:3

516:5

017:2

018:1

518:5

519:3

520:3

521:1

5

19-Sep 20-Sep 23-Sep 24-Sep 25-Sep 26-Sep

Date & Time

Te

ns

ile

(k

g/1

5m

m)

Tensile MD Tensile CD

MD Tensile min. 5.3 (kg/15min)

CD Tensile min. 2.9 (kg/15min)

Stock pulp

not enough

T R I A LP r e - t r i a l

NBKP : 2.29 % NBKP : 0 %

5 Case History – Fine PaperBursting

100

120

140

160

180

200

220

240

18:3

519:5

521:4

022:5

00:0

51:4

53:3

04:5

56:2

58:0

09:4

011:2

013:2

015:1

517:0

518:5

520:5

523:4

51:4

03:2

516:1

518:4

020:1

022:1

523:1

01:2

53:2

05:3

07:2

58:2

59:2

010:1

511:3

012:3

013:2

514:2

014:4

5

19:1

519:5

520:4

021:3

522:2

0

11:3

312:1

513:1

013:5

014:2

515:1

516:0

516:5

017:4

019:0

020:0

521:0

522:4

023:3

00:1

51:2

52:1

03:1

04:3

05:0

06:0

27:3

58:3

59:2

510:1

010:5

511:4

512:3

014:4

015:3

516:3

516:5

017:2

018:1

518:5

519:3

520:3

521:1

5

19-Sep 20-Sep 23-Sep 24-Sep 25-Sep 26-Sep

Date & Time

Bu

rsti

ng

(kP

am

2/g

)

BuBursting min. 136 (kPam2/g)

Stock pulp

not enough

P r e - t r i a l TRIAL

Burst improved 8.4%

5 Case History – Fine Paper

• Porosity initially unchanged, improved 25.15% on halting one DDR

Porosity

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

18:3

519:5

521:4

022:5

00:0

51:4

53:3

04:5

56:2

58:0

09:4

011:2

013:2

015:1

517:0

518:5

520:5

523:4

51:4

03:2

516:1

518:4

020:1

022:1

523:1

01:2

53:2

05:3

07:2

58:2

59:2

010:1

511:3

012:3

013:2

514:2

014:4

5

19:1

519:5

520:4

021:3

522:2

0

11:3

312:1

513:1

013:5

014:2

515:1

516:0

516:5

017:4

019:0

020:0

521:0

522:4

023:3

00:1

51:2

52:1

03:1

04:3

05:0

06:0

27:3

58:3

59:2

510:1

010:5

511:4

512:3

014:4

015:3

516:3

516:5

017:2

018:1

518:5

519:3

520:3

521:1

5

19-Sep 20-Sep 23-Sep 24-Sep Average 25-Sep 26-Sep Average

Date & Time

Po

ros

ity

(m

l/m

in)

PorositPorosity Max. 1200 (ml/min)

P r e - t r i a l TRIAL

2 DDR

3 DDR , average 238 KW 3 DDR, average 222 KW

2 DDR, average 201 KW

5 Case History – Fine Paper

• Power / Refining energy – From 3 DDR to 2 DDR refiners and maintained same porosity. Dropping energy requirement by 100 kW.

Power Consumption (kW)

0

50

100

150

200

250

300

350

18:3

519:5

521:4

022:5

00:0

51:4

53:3

04:5

56:2

58:0

09:4

011:2

013:2

015:1

517:0

518:5

520:5

523:4

51:4

03:2

516:1

518:4

020:1

022:1

523:1

01:2

53:2

05:3

07:2

58:2

59:2

010:1

511:3

012:3

013:2

514:2

014:4

5

19:1

519:5

520:4

021:3

522:2

0

11:3

312:1

513:1

013:5

014:2

515:1

516:0

516:5

017:4

019:0

020:0

521:0

522:4

023:3

00:1

51:2

52:1

03:1

04:3

05:0

06:0

27:3

58:3

59:2

510:1

010:5

511:4

512:3

014:4

015:3

516:3

516:5

017:2

018:1

518:5

519:3

520:3

521:1

5

19-Sep 20-Sep 23-Sep 24-Sep 25-Sep 26-Sep

Date & Time

Po

we

r (k

W)

Pressure in 1 Pressure in 2 Pressure in 3

2 DDR3 DDRPre-trial

5 Case History – Fine Paper

•No change to Wax Pick

Picking (A)

8

10

12

14

16

18

20

18:3

519:5

521:4

022:5

00:0

51:4

53:3

04:5

56:2

58:0

09:4

011:2

013:2

015:1

517:0

518:5

520:5

523:4

51:4

03:2

516:1

518:4

020:1

022:1

523:1

01:2

53:2

05:3

07:2

58:2

59:2

010:1

511:3

012:3

013:2

514:2

014:4

5

19:1

519:5

520:4

021:3

522:2

0

11:3

312:1

513:1

013:5

014:2

515:1

516:0

516:5

017:4

019:0

020:0

521:0

522:4

023:3

00:1

51:2

52:1

03:1

04:3

05:0

06:0

27:3

58:3

59:2

510:1

010:5

511:4

512:3

014:4

015:3

516:3

516:5

017:2

018:1

518:5

519:3

520:3

521:1

5

19-Sep 20-Sep 23-Sep 24-Sep 25-Sep 26-Sep

Data & Time

Pic

kin

g (

A)

Picking W Picking F

Picking W min. 14 (A)

Picking F min. 14 (A)

Stock pulp

not enough

5 Case History – Fine Paper

Decrease noticed in Tear. Approx 8% MD and Approx 5% CD.

Tearing (gr)

0

10

20

30

40

50

60

18:3

519:5

521:4

022:5

00:0

51:4

53:3

04:5

56:2

58:0

09:4

011:2

013:2

015:1

517:0

518:5

520:5

523:4

51:4

03:2

516:1

518:4

020:1

022:1

523:1

01:2

53:2

05:3

07:2

58:2

59:2

010:1

511:3

012:3

013:2

514:2

014:4

5

19:1

519:5

520:4

021:3

522:2

0

11:3

312:1

513:1

013:5

014:2

515:1

516:0

516:5

017:4

019:0

020:0

521:0

522:4

023:3

00:1

51:2

52:1

03:1

04:3

05:0

06:0

27:3

58:3

59:2

510:1

010:5

511:4

512:3

014:4

015:3

516:3

516:5

017:2

018:1

518:5

519:3

520:3

521:1

5

19-Sep 20-Sep 23-Sep 24-Sep 25-Sep 26-Sep

Date & Time

Teari

ng

Tearing MD

Tearing CD

MD Tearing min. 44gr

CD Tearing min. 53gr

P r e - t r i a l TRIAL

5 Case History – Fine Paper

Smoothness improvements Wire Side : 15.93% and Felt Side : 16.43%

Smoothness (Sec/10cc)

0

10

20

30

40

50

60

18:3

519:5

521:4

022:5

00:0

51:4

53:3

04:5

56:2

58:0

09:4

011:2

013:2

015:1

517:0

518:5

520:5

523:4

51:4

03:2

516:1

518:4

020:1

022:1

523:1

01:2

53:2

05:3

07:2

58:2

59:2

010:1

511:3

012:3

013:2

514:2

014:4

5

19:1

519:5

520:4

021:3

522:2

0

11:3

312:1

513:1

013:5

014:2

515:1

516:0

516:5

017:4

019:0

020:0

521:0

522:4

023:3

00:1

51:2

52:1

03:1

04:3

05:0

06:0

27:3

58:3

59:2

510:1

010:5

511:4

512:3

014:4

015:3

516:3

516:5

017:2

018:1

518:5

519:3

520:3

521:1

5

19-Sep 20-Sep 23-Sep 24-Sep 25-Sep 26-Sep

Date & Time

Sm

oo

thn

ess

Smoothness W

Smoothness F

Smoothness W = 20-35 Sec/10cc

Smoothness F = 20-35 Sec/10cc

P r e - t r i a l T r i a l

Conclusion

• Fibre modification enzymes– “Chemical refining”

– Range of applications

• Energy savings

– Drying

– Refining

• Quality improvements

– Strength

– Formation

– Smoothness etc

• Allow fibre substitution / rationalization

– Cheaper fibre

– Filler

– Giving papermakers more options for process optimization

http://molvis.sdsc.edu/atlas/morphs/lacrep/index.htm

Questions?