[PPT] - LMS Biobleaching Process Parameter Studies Process Parameter PowerPoint Presentation

SLIDE 1

LMS Biobleaching Process Parameter Studies Process Parameter Studies

Art J Ragauskas Art J. Ragauskas Institute of Paper Science and Technology

SLIDE 2

Pulp Bleaching

Purpose of bleaching is 2-fold:

– to remove the residual lignin – to brighten the pulp

Current bleaching technologies
Current bleaching technologies

consist of: – O2, ClO2, H2O2, & O3 – Capital intensive – Limited selectivity D has environmental limitations – D has environmental limitations – New bleaching agents needed!

SLIDE 3

LACCASE-MEDIATED BIOBLEACHING BIOBLEACHING

SLIDE 4

Laccase: Overview

Laccase

OH Cu1+

HisN

Cu1+ NHis

1+Cu

Type II Type III H O H Cu2+ Cu2+

HisN

O NHis

2+Cu

O2 SCys Cu1+ Type I SCys Cu2+ H

Oxidoreductase enzyme

E.I. Solomon et al

Fully Reduced Fully Oxidized

y

Reduces O2 to H2O

2

concomitantly oxidizes concomitantly oxidizes

MW varies 65 000 140 000
Catalysis occurs due to 4

copper atoms/active site

MW varies 65,000-140,000.
Carbohydrate content ~10-45 (% wt).
Active sites near surface

Active sites on surface

SLIDE 5

Laccase: Overview

Proposed to be involved in lignin biosynthesis
Oxidize a wide array of phenolic substrates
Oxidize a wide array of phenolic substrates

HO OR OCH3

HO

HO O OCH3 MeO OH OH OCH3 OR2

OCH3 H3CO O O OCH3 Laccase/O2

OH MeO OMe HO OMe OMe OH

OH CO2H H3CO OH OCH3 H3CO OH Hi hi W d S i T h 24 22(1990) Higuchi, Wood Sci. Techn., 24, 22(1990)

SLIDE 6

Laccase Biobleaching

Pulp Fiber O2 Low MW Co-factor - Mediator

SLIDE 7

Laccase Biobleaching LMS-Process g

O LACCASE MEDIATOR LIGNIN O2 LACCASE MEDIATOROX LIGNIN H2O LACCASE

OX

MEDIATOR LIGNIN

OX OX

SLIDE 8

Laccase Biobleaching

C di i LMS(E)

Laccase Lac/ABTS Lac/HBT Lac/NHA Lac/VA

Conditions LMS(E)

LMS: 45oC, 1-2 h, 5-20% csc,

pH 4 6 1 4% mediator +40 psi

50 60

pH 4 - 6, 1-4% mediator, +40 psi

E: 70oC, 1-3 h, 1-2% NaOH

30 40 50

elignificatin

H4NO3S N S N N N S SO3NH4

ABTS

10 20

% De

S f f

N N N O O OH N OH O

SW Kraft HW Kraft

Highly selective for lignin, little degradation of pulp carbohydrates

N N OH HN NH O HBT VA NHA Call -1995 Amman 1997

degradation of pulp carbohydrates

Ragauskas et al: Enzyme and Micro. Technol., 23, 422 (1998), TAPPI J., 83(9), 66(2000);

J. Wood Chem. Technol., 20(2), 169(2000)

SLIDE 9

LMSVA Biobleaching High/Low Kappa Kraft P lps Kraft Pulps

Conditions

45 50

LMS 5.4 x 105 U laccase/gr od pulp 45oC 2h 120 psi O 9% csc

30 35 40 45

45oC, 2h, 120 psi O2, 9% csc, med.= VA EP

15 20 25 30 Kappa #

80oC, 1.5 h, 0.5% H2O2, 10% csc

5 10 15 SW1 SW1-LMS(EP) SW2 SW2-LMS(EP) HW1 HW1-LMS(EP) HW2 HW2-LMS(EP)

LMS applicable to low and hi h k k ft l high kappa kraft pulps

SLIDE 10

LMSVA Biobleaching: Lignin Reactivity

1 2

Start LMS(EP)

mmol/g lignin

0 8 1 1.2

OMe

OMe OH

0.4 0.6 0.8

OH

0.2

SW(50 0 K) SW(27 5 K) SW(50 0 K) SW(27 5 K) SW(50.0 K) SW(27.5 K) SW(50.0 K) SW(27.5 K)

LMS ti it i il i h li i ll C5 d d i SW LMS reactivity primarily via phenolics, especially C5 noncondensed in SW

Delving into the Fundamental LMS Delignification of High-Kappa Pulps. Biotechnology in the Pulp and Paper Industry, 151-164 (2002).

SLIDE 11

Biobleaching High and Low Kappa Pulps Biobleaching High and Low Kappa Pulps

Pulp % Delign. % Yield SW kappa 50 43 99.9 SW kappa 28 62 100.0 HW kappa 27 65a 98.6 pp HW kappa 11 70a 99.1

ak

i il h i id

akappa primarily hexenuronic acids

SLIDE 12

Yield Kappa Relationships

50 48 50

d, % LMS(E* ) 50(LMS)E*DED

44 46

n Wood Pulping 50(OO) 50(OO)DED ( )

40 42

Yield on 30DED

38 40

Y 30ODED

10 20 30 40 50 60

Kappa Number

SLIDE 13

LMSVA Bleaching Sequence Studies LMSVA Bleaching Sequence Studies

LMS based sequences

e l t ECF i fi l

90

equal to ECF in final brightness properties

LMS yield gains occur

from higher selectivity for

50 60 70 80 rightness

from higher selectivity for high kappa pulps

What is not yet

established:

10 20 30 40 TAPPI Br

established:

NPE effects
Mixing effects

B r

w

n s t

c

k M S ( L M S ) ( E P O ) L M S ) ( E P O ) D E P O ) D E D ( . 6 % ) P O ) D E D ( . 8 % ) P O ) D E D ( 1 . % ) B r

w

n s t

c

k O O O O D ( E P O ) ( E P O ) D ( . 4 % ) ( E P O ) D ( . 6 % ) ( E P O ) D ( . 8 % )

Carryover effects

L M S L M S ( L M L M S ( L M S ) ( E P O L M S ( L M S ) ( E P O L M S ( L M S ) ( E P O O O D ( E O O D ( E O O D ( E

SLIDE 14

NPE’s on LMS NPE s on LMS

Most LMS studies have been

preformed using ‘clean systems’

All kraft pulps and process

streams have nonprocesss elements present (Ca Mg Fe Mn elements present (Ca, Mg, Fe, Mn, Cu, Ni, etc) Exp Design

Exp. Design
Perform LMS(E) and repeat with

NPEs

Compare delignification and

viscosity properties of biobleached l pulps

SLIDE 15

LMSVA Bleaching: Effects of NPEs

55 60

VA

g

40 45 50

pa #

30 35 40

Kapp

20 25

BS S(E) l(E) l(E) (E) 4(E) 4(E) 4(E) 4(E) B LMS( LMS-0.1%NaCl( LMS-1.0%NaCl( LMS-1% MNSO4(E LMS-1%NiSO4(E LMS-1%FeSO4(E LMS-1%CuSO4( LMS-1%MgSO4(

>> no observed NPE impact on delignification

SLIDE 16

LMSVA Bleaching: Effects of NPEs

55 60

VA

g

40 45 50

sity/cP

30 35

Visco

`

20 25

B S L M S ( E ) N a C l ( E ) N a C l ( E ) S O 4 ( E ) S O 4 ( E ) S O 4 ( E ) S O 4 ( E ) S O 4 ( E ) L M L M S

.

1 % N a C L M S

1

. % N a C L M S

1

% M n S O L M S

1

% N i S O L M S

1

% F e S O L M S

1

% C u S O L M S

1

% M g S O

>> slight NPE impact on pulp viscosity

SLIDE 17

LMSVA Bleaching: Effect of Mixing LMSVA Bleaching: Effect of Mixing

bj i Objective Assess the impact of mixing on an LMS stage Experimental Procedure Biobleaching Sequence LMS(EPO)

LMS:Lac: 1.4 x 107 U/10 gr pulp, 45 min., 4.5 pH, 4% VA, 120 psi O2

LMS:Lac: 1.4 x 10 U/10 gr pulp, 45 min., 4.5 pH, 4% VA, 120 psi O2 Quantum reactor, 10% csc, 55oC,

(E+P+O): 70oC, 1 h, 10% csc, 60 psi, 0.5% H2O2, 2.5% NaOH

( ) , , , p ,

2 2,

SLIDE 18

LMSVA Bleaching: Effect of Mixing

LMS Mixing Conditions: Quantum g Q

A. 600 rpm for 10 sec every 2 min.

B 1200 rpm for 5 sec every 2 min

B. 1200 rpm for 5 sec every 2 min.
C. 2400 rpm for 2.5 sec every 2 min. [constant refining energy]

Pulp Kappa # Viscosity/cP TAPPI Brightness Brownstock 33.3 30.4 25.9 A(E+P+O) 14.6 23.6 34.2 B(E+P+O) 14.4 23.2 34.2 C(E+P+O) 14.3 23.1 33.3

SLIDE 19

LMSVA Bleaching: Effect of Mixing

i i di i

VA

g g

LMS Mixing Conditions:

D. 600 rpm for 10 sec every 2 min.
E. 3600 rpm for 10 sec every 2 min. [variable mixing energy]

P l K # Vi it / P TAPPI B i ht Pulp Kappa # Viscosity/cP TAPPI Brightness Brownstock 33.3 30.4 25.9 D(E+P+O) 14.2 23.8 32.9 E(E+P+O) 14.0 22.7 32.6

SLIDE 20

LMSVA Bleaching: Effect of Mixing

LMS Mixing Conditions: F 600 rpm for 10 sec every 2 min – 20% csc (Quantum)

F. 600 rpm for 10 sec every 2 min. – 20% csc (Quantum)
G. 2400 rpm for 10 sec every 2 min. – 20% csc (Quantum)

H 48 10% (P ddl i )

H. ≈48 rpm- constant – 10% csc (Parr reactor, paddle mixer)

Pulp Kappa # Viscosity/cP Brownstock 33.3 30.4 F(E+P+O) 14 2 22 9 F(E+P+O) 14.2 22.9 G(E+P+O) 14.1 23.6 H(E+P+O) 16 3 H(E+P+O) 16.3

Provide efficient mixing is occurring in a LMS-stage, detrimental

shear effects were not observed

SLIDE 21

Black Liquor Carryover on LMS q y

Most LMS studies have been

preformed using ‘clean systems’

All kraft pulps are delignified in the

presence of black liquor carryover and this is know to influence O D and P this is know to influence O, D and P.

Effect on LMS is unknown

Exp Design

Exp. Design
Perform LMS(E) with and without

Black liquor carryover

Compare delignification and viscosity

properties of biobleached pulps

SLIDE 22

LMSVA Bleaching: Effect of Carryover

50 40 # 30 Kappa 20 BS 0% Solids 0.1% Solids 0.5% Solids 1.0% Solids 5.0% Solids

% Solids carryover added

2% charge of VA in LMSVA

SLIDE 23

LMSVA Bleaching: Effect of Carryover LMSVA Bleaching: Effect of Carryover

50

4% VA

40 20 30 Kappa # 10

Brownstock 1% Carryover 5% Carryover 10% Carryover 20% Carryover 30% Carryover

Carryover levels of 10% black liquor solids are not detrimental towards an LMS stage

SLIDE 24

LMS - BIOBLEACHING LMS BIOBLEACHING

Effect of Temperature – pH on LMS

SLIDE 25

LMSVA Bleaching: Effect of Temperature

VA

g p

50 40 # 30 Kappa 30 20

BS [LMS- 45](E) [LMS- 55](E) [LMS- 65](E) [LMS- 75](E) [LMS- 85](E) [LMS- 95](E)

Temperature limitations of laccase employed limited LMS stage to ∼20–75oC

SLIDE 26

LMSVA Bleaching: Effect of pH

45 50 35 40 pa # 30 35 Kapp 20 25 S E) E) E) E) E) E) E) E) E) BS [LMS-2.9](E) [LMS-4.7](E) [LMS-5.1](E) [LMS-5.3](E) [LMS-6.4](E) [LMS-6.9](E) [LMS-7.0](E) [LMS-7.1](E) [LMS-8.9](E)

pH limitations of laccase employed limit LMS stage to ∼ 3 - 5

SLIDE 27

Laccase Biobleaching: Conclusions/Future Laccase Biobleaching: Conclusions/Future

LMS biodelignification of high kappa pulps is possible and

provides distinct yield benefits

LMS delignified pulps can be bleached to high brightness

l values

NPEs have minimal impact on LMS stage
LMS is not sensitive to shear effects

LMS is not sensitive to shear effects

LMS is not detrimentally impacted by moderate levels of

black liquor carryover q y

pH/temperature profiles of LMS need to be improved

C i di LMS di d b i d

Cost issues surrounding LMS mediator need to be improved

SLIDE 28