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PSE 476
Lecture #8
Kraft Pulping: Early Reactions and
Kraft Pulping Lignin Reactions
1
Agenda
Basic Chemical Pulping Discussion
Loss of Components During Kraft Pulping
Reactions in the Early Portion of the Cook
Saponification
Neutralization of Extractives
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.
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
HC
HCOH
CH2OH
CH2OH
CH H3CO
CH
CH
H2COH
HOCH
O
HC
CHO
12
Kraft Pulping
23
OCH3
O
17
O
HOCH
CH
H2COH
HC
H2COH
H3C O
OH
HC
Soluble
Fragments
CHO
CH
CH
22
OCH3
O
18
21
H3CO
HO
24
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
15
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
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
Saponification of Fats
(Review slide from PSE 406)
O
H2C O C
HOCH2CHCH2OH
R
-
OH
Glycerol (glycerine)
H2C O C
OH
R
H2O
O
H2C OH
O C
Lignans
Resin Acids
Monoterpenoids
O
CH3O
O
COOH
HO
COOH
OCH3
OH
10
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)
11
12
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
13
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)
14
Kraft Pulping:
EffectiveAlkali
Alkali(g/l
(g/lNaOH)
NaOH)
Effective
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
15
16
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
Alkaline Media
HC
HC R1
-
- R1
OCH3
OCH3
O -
* Notes
18
HC OH
HC
OCH3
OCH3
OThese arrows indicate that a pair
of electrons are moving
Nucleophillic
attack
site!
O
Quinone Methide
(very reactive)
19
HC
OCH3
O
20
H2C R1
HC
HC
O-
OCH3
HC
HC
- R1
H2C
OCH3
R
O
Notes
+ C
- R1
H2C +
C
C
R1
OCH3
O
OCH3
O
21
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?
22
R
HC
R
HC
O
(-)
(-)
OH
CH3O
O
CH3O
(-)
O
R
HC
O
OH
(-)
No Reaction
CH3O
OR
23
HC
CH3O
CH3O
H2COH
HC
HC
HC O R
-
OH
O-
OCH3
O-
OCH3
H2COH
CH3O
H2COH
HC
O
HC O R
HC
-
O-
OCH3
CH3O
HC
+ -O
OH
HS
O-
OCH3
24
H C
H2COH
CH3O
H2COH
H2COH
HC
CH3O
O
HC O R
CH3O
O
Formaldehyde
HC
HC
OCH3
OH
O-
HO-
OCH3
CH3O
CH3O
H2CO H
HC
O-
OCH3
HC
HC
HC
+
OCH3
O
O-
OCH3
HCHO
Vinyl Ether
25
Appendix
Basic Wood Chemistry
26
Cellulose*
Hemicellulose*
Lignin*
Extractives
% 30
20
10
0
Douglas Redwood
Fir
* Data for Cellulose, Hemicellulose & Lignin on extractive free wood basis
27
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
28
Hemicelluloses
Branched little uncolored sugar polymers (~
50 to 300 sugar units)
Composition varies between wood species.
-
Major hemicelluloses:
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
30
Glucomannan Structure
1
-D-Gal
4--D-Glc-14--D-Man-14--D-Man-14--D-Man-1
6
2,3
Acetyl
31
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
32
Lignin Nomenclature
Side Chain
1
6
5
Notes
2
3
4
OCH3
OH
Phenylpropane Unit
C9
Methoxyl Group
Phenolic Hydroxyl
Common Names
33
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
34
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%).
35