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Pulping and Bleaching

PSE 476

Lecture #8
Kraft Pulping: Early Reactions and
Kraft Pulping Lignin Reactions
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Agenda
Basic Chemical Pulping Discussion
Loss of Components During Kraft Pulping
Reactions in the Early Portion of the Cook
Saponification
Neutralization of Extractives

Initial Lignin Discussion


Kraft Pulping Lignin Reactions

Wood Chemistry
For the students who do
not recognize this
molecule (did not take
PSE 406), there is a
short appendix at the
end of this lecture to
help you. Additionally,
the class notes are
available for review.

Pulping
The goal of kraft pulping
is to remove the majority
of lignin from chips (or
other biomass) while
minimizing carbohydrate
loss and degradation.
Removal of lignin is
accomplished through
treatment of raw material
with NaOH and Na2S at
elevated temperatures.

The Goal of Lignin Reactions


in Kraft Pulping
H2COH
CH2
CH2

H2COH
CH
CH
OH
OCH3
6

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H3CO
OH

H COH
HC
CH2OH

OH C CH CH2OH
O

H3CO
OCH3

H3CO
5

HC

HC
HC
H2C

HC

HOH2C

OH
3

HC
O

O
H3CO

CH

CH

OHC CH CH2OH
O
CH2OH
H3CO

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C O
CH
CH2OH

H2 COH

C O

HC
HC

CH
CH2

OCH3

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H2COH
HC
CH

HC
HCOH

CH2OH

CH2OH
CH H3CO
CH

CH
H2COH
HOCH
O
HC
CHO
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Kraft Pulping

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OCH3
O

17
O

HOCH
CH

H2COH
HC

H2COH

H3C O

OH

HC

Soluble
Fragments

CHO
CH
CH
22
OCH3
O

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Carbohydrates are also


degraded during pulping

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H3CO
HO

During kraft pulping, the


large insoluble lignin
molecules are converted
into small alkali soluble
fragments.

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13
O

H2 COH

CH

10

27

H3CO

OH

CH
HC O

CH

CH2
H3CO
CH
CH

H3CO

H3CO

HCOH
HCOH
H2 C O

HC
O

OCH3

HOCH
H2C

OCH3

CH2OH

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H2 COH
CH

CH
H C O Carbohydrate

CH2OH
28

HO

26
H3CO

CH3

CH3O

19

HC
O
CH
H2COH

CH2
HC
H COH

OCH3
O

11
20

H3CO

OCH3

OH
OH

Yield of Wood Components


After Kraft Pulping
Notes

* Yields = % of wood (pulp) components

Initial Reactions:
Low Temperature
Carbohydrates
Alkaline hydrolysis of acetyl groups on xylan (see next
slide).
Removal of certain soluble carbohydrates.
- Certain galactoglucomannans.
- Arabinogalactans.

Extractives
Alkaline hydrolysis of fats (saponification), waxes, and other
esters.
Neutralization of extractives.
- There are a number of acidic extractives which consume NaOH.

Alkaline Hydrolysis:
Example Using Acetyl Groups
CH2OH
OH
HO

OH

CH2OH

O
-

HO

OH
HO

O C CH3
O

OH

CH2OH

O
OH
OH
O C CH3
O

OH
O

HO
+

OH

HO C CH3
O

Esters are cleaved in alkaline solutions through hydrolysis


reactions forming carboxylic acids and alcohols.
Hydrolysis of acetyl groups occurs readily in alkaline solutions.
Reaction occurs rapidly even at room temperature.

Reaction consumes alkali.

Saponification of Fats
(Review slide from PSE 406)

Treatment of fats with alkali converts them to fatty acids


and glycerol through saponification.
OH

O
H2C O C

HOCH2CHCH2OH

R
-

OH

Glycerol (glycerine)

H2C O C
OH
R
H2O

Once again this reaction


consumes part of the alkali
charge.

O
H2C OH

O C

Acidic Extractive Species

Lignans

Resin Acids

Monoterpenoids
O

CH3O
O

COOH

HO

COOH

OCH3
OH

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Consumption of Alkali

ResidualNaOH
NaOH
Residual
(moles/kgwood)
wood)
(moles/kg

44
33
22
11
00

00 Impregnation
zone

50
50

100
100

150
150

Time
Time(minutes)
(minutes)

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Where Does All the Alkali


Go?
Spruce wood was soda pulped at a NaOH
concentration of 19% (as Na2O).
12.5% (or 66% of alkali) consumed to lower
lignin content of wood to 2.8%.
2.3-3% used in dissolution of lignin.
1.3% for hydrolysis of acetyl and formyl groups.
8.2-8.9% for neutralization of acidic products
- Some extractives
- Mostly carbohydrate degradation products (discussed later).

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Lignin Removal during Kraft


Pulping
This chart shows the lignin removal rate during a kraft cook. It is
important to note that the rate of lignin removal is temperature
dependent. What does this fact tell us about of lignin removal in
this slide?
200
200

80
80

150
150

60
60

100
100

40
40

Lignin
Lignin

20
20

50
50

Temperature
Temperature

00
00

50
50

100
150
100
150
Time
Time(minutes)
(minutes)

200
200

Temperature(C)
(C)
Temperature

LigninYield
Yield(%)
(%)
Lignin

100
100

00
250
250

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Lignin Removal
In the last slide, the rate of lignin removal appears to
be linear over a large portion of the cook; even as the
temperature increases.
This means that lignin removal in the first portion of
the cook is easier than as the cook proceeds.
Lignin removal has been broken into three sections:
Initial Phase (fast lignin removal reactions)
Bulk Phase (slow lignin removal reactions)
Residual Phase (really slow lignin removal)

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Kraft Pulping:

EffectiveAlkali
Alkali(g/l
(g/lNaOH)
NaOH)
Effective

Reaction Phases of Lignin Removal


60
60
50
50
40
40
30
30

170 C

20
20
10
10

70C
70C
137C

Initial Phase
Impregnation zone

Bulk Phase
Residual Phase

00
00

Notes

55

10
15
20
10
15
20
Yield
Yieldof
ofLignin
Lignin(%)
(%)

25
25

30
30

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Kraft Pulping Lignin Reactions

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Dissolution of Lignin
In review the goal in kraft pulping is the cleavage of
lignin into alkali soluble fragments.
Cleavage is affected by the following factors:

Type of linkage
Presence of free phenolic hydroxyl group
Functional groups (benzyl hydroxyl, carbonyl)
Type and amount of nucleophiles (OH-, HS-)
Reaction temperature

We are going to first look at the chemical mechanisms


of the reactions and then the kinetics.
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Sites for Nucleophilic Attack


The cooking chemicals
used in kraft cooking
(NaOH and Na2S: OHand HS-) both act as
nucleophiles* because of
their free pair of
electrons.
Sites for nucelophilic
attack in lignin are those
areas of reduced electron
density (partially
positive sites).

Alkaline Media
HC

HC R1
-

- R1

OCH3

OCH3

O -

R1 = OH, OAr or OAlk

* Notes

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Formation of Quinone Methide

HC OH

HC

OCH3

OCH3
OThese arrows indicate that a pair
of electrons are moving

Nucleophillic
attack
site!

O
Quinone Methide
(very reactive)

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Formation of Nucleophilic Attack


Sites
A free phenolic hydroxyl
group is needed for the
formation of a quinone
methide.
The oxygen of the quinone
group (carbonyl) attracts the
electron density on the
double bond thus making
the carbon more positive.
This in turn shifts the
electron densities of the
other bonds on this
conjugated system.

HC

OCH3
O

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Two Additional Examples of


Nucleophilic Addition Sites
H2C

H2C R1
HC
HC

O-

OCH3

HC
HC

- R1

H2C

OCH3

Coniferaldehyde type structures

R
O

Notes

+ C

- R1

R1 = OH, OAr or OAlk

H2C +

C
C

R1

OCH3
O

OCH3
O

R = OAr, Ar or Alk, R1 = OH, OAr, or OAlk

This structure contains an-keto


group. Notice that a free phenolic
hydroxyl groups is not needed!

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Important Issues!!!!
When learning about alkaline pulping
mechanisms, remember to ask yourselves
these questions!
Which reactant are we concerned with: OH- or HS-?
Does the lignin structure have a free phenolic
hydroxyl group or is it etherified?
Which linkage are you hoping to cleave?
Is there an -carbonyl or benzyl hydroxyl?

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Reactions of -O-4 Linkage


Phenolic and Etherified
In kraft pulping, -O-4
linkages do not react
with HS Reaction with OH-

Phenolic Units: -O-4 are


very rapidly cleaved by
alkali. This is the fastest of
the lignin degradation
reactions. (Will occur at low
temperatures)
Etherified Units: -O-4
linkages are stable (no
reaction).
Please work out reaction
mechanism.

R
HC

R
HC

O
(-)

(-)

OH
CH3O
O

CH3O

(-)

O
R
HC

O
OH

(-)

No Reaction

CH3O
OR

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Reactions of -O-4 Linkages:


Free Phenolic Hydroxyl/Benzyl Hydroxyl
Reaction with OH- alone
The ether linkage is not
cleaved; a vinyl ether
structures is formed.
Vinyl ether linkages are
difficult to cleave.

Reaction with HS- (OHpresent)

HS- is a very strong


nucleophile which cleaves
the -O-4 linkage.
Reaction is very rapid even
at lower temperatures.

HC

CH3O

CH3O

H2COH

HC

HC

HC O R
-

OH
O-

OCH3

O-

OCH3

Vinyl Ether Linkage

H2COH

CH3O

H2COH

HC

O
HC O R

HC
-

O-

OCH3

CH3O

HC

+ -O

OH
HS

O-

OCH3

* Mechanisms on following pages

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Kraft Reactions of -O-4 Linkage


(Free Phenolic Hydroxyl)
HO

H C
H2COH

CH3O

H2COH

H2COH

HC

CH3O

O
HC O R

CH3O
O

Formaldehyde

HC

HC

OCH3
OH

O-

HO-

OCH3

Notice that the


-O-4 bond is
not cleaved.
Notes

CH3O

CH3O

H2CO H
HC

O-

OCH3

HC

HC

HC

+
OCH3
O

O-

OCH3

HCHO

Vinyl Ether

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Appendix
Basic Wood Chemistry

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What is the Chemical


Makeup of Wood?
60
50
40

Cellulose*
Hemicellulose*
Lignin*
Extractives

% 30
20
10
0

Douglas Redwood
Fir

Yellow Balsam Fir


Pine

* Data for Cellulose, Hemicellulose & Lignin on extractive free wood basis

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Cellulose
Very long straight chain polymer of glucose (a sugar): approximately 10,000 in a row in wood. Cotton is nearly
pure cellulose.
Think about a very long string of beads with each bead being a glucose molecule.
Cellulose molecules link up in bundles and bundles of bundles and bundles of bundles of bundles to make fibers.
Uncolored polymer.

Cellobiose Unit
HO
O

OH

CH2OH

CH2OH

HO

OH

HO

OH

Cellulose

CH2OH

O
HO

CH2OH

OH

O
O

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Hemicelluloses
Branched little uncolored sugar polymers (~
50 to 300 sugar units)
Composition varies between wood species.
-

5 carbon sugars: xylose, arabinose.


6 carbon sugars: mannose, galactose, glucose.
Uronic Acids: galacturonic acid, glucuronic acid.
Acetyl and methoxyl groups (acetic acid & methanol).

Major hemicelluloses:

Xylans - big in hardwoods


Glucomannans: big in softwoods

Minor hemicelluloses: pectins, others.


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Xylan Structure

4--D-Xly-14--D-Xly-14--D-Xly-14--D-Xly4--D-Xly

4-O-Me--D-Glc

O
HO

OH

HO

H3CO
CO 2H

O
O

OH

HO

-L-Araf

OH

HO

OH

O
O

O
HOH2C

OH
OH

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Glucomannan Structure

1
-D-Gal

4--D-Glc-14--D-Man-14--D-Man-14--D-Man-1
6
2,3
Acetyl

There are different structured glucomannans in


hardwoods and softwoods (and within softwoods)
Glucomannans are mostly straight chained polymers
with a slight amount of branching. The higher the
branching, the higher the water solubility.

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Lignin
Phenolic polymer the glue that holds
the fibers together.
Lignin is a very
complex polymer
which is connected
through a variety
of different types of
linkages.
Colored material.

H2COH
CH2
CH2

H2COH
CH
CH
OH
OCH3
6

16

H3CO
OH

H COH
HC
CH2OH

OH C CH CH2OH
O

H3CO
OCH3

H3CO
5

HC

HC
HC
H2C

HC

HOH2C

OH
3

HC
O

O
H3CO

CH

CH

OHC CH CH2OH
O
CH2OH
H3CO

14

C O
CH
CH2OH

H2 COH

C O

HC
HC

CH
CH2

OCH3

25

H2COH
HC
CH

24

13

HC
HCOH

CH2OH
O

CH2OH
CH H3CO
CH

CH
H2COH
HOCH
O
HC
CHO
12

23
OCH3
O

17
O

HOCH
CH

H2COH
HC

H2COH

H3C O

OH

H2 COH

CH

10

27

H3CO

OH

CH
HC O

CH

CH2
H3CO
CH
CH

H3CO

H3CO

HCOH
HCOH
H2C O

HC
O

OCH3

HOCH
H2C

OCH3

CH2OH

15

26

CH
H C O Carbohydrate

CH2OH
28

HO
H2 COH
CH

H3CO

CH3

CH3O

HC

CHO
CH
CH
22
OCH3
O

18
21

H3CO
HO

19

HC
O
CH
H2COH

CH2
HC
H COH

OCH3
O

11
20

H3CO

OCH3

OH
OH

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Lignin Nomenclature

Side Chain

1
6
5

Notes

2
3
4

OCH3

OH

Phenylpropane Unit
C9

Methoxyl Group

Phenolic Hydroxyl

Common Names

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Lignin Reactions:
Linkage Frequencies
Linkage
-O-4

Softwood
%
50

-O-4

2-8

-5

9-12

5-5

Hardwood
%
60

10-11

4-0-5

-1

-O-4

-O-4

C
C

-1
C

C
C

O
-

5-5

O
4-O-5

-5

Notes
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Extractives
The term extractives refers to a group of unique chemical
compounds which can be removed from plant materials through
extraction with various solvents.
Typically these chemicals constitute only a small portion of the tree
(<5%).

In some tropical species this can be as high as 25%.

Extractives are produced by plants for a variety of uses.

The most common use by plants is protection.

Extractives can cause serious problems for processing.


Pitch is a term which is often used when describing some groups of
extractives.
Extractives are responsible for the characteristic color and odor of
wood.

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