General

z Oxygen delignification was introduced in

the 1970s in industrial applications.
Oxygen delignification z Oxygen is a cheap chemical.
{A cost efficient way to reduce the consumption
Lecture 12 of other chemicals.
z Environmentally friendly.
{Less chlorinated compounds are formed in the
following ECF bleaching.

General Conditions in oxygen delignification

z Oxygen stage is situated before bleaching z Temperature 80C 100C

processes. z Elevated pressure (~5-6 bar) to achieve
z The stage is called oxygen delignification adequate oxygen dissolution.
or oxygen bleaching. z Alkaline, pH >10
z Approximately 50 % of the residual lignin
can be removed
{Pulp quality problems occur if the limit is
exceeded

1
Reactions of oxygen Reactions of oxygen
z Oxygen is reduced to water in one- Stepwise reduction of oxygen during bleaching :
electron steps and the substrate is

al
al
oxidized.

c
ic

di
ro en
ad

ra
e
pe rog
lr

xid

yl
xy

ox
d
hy
ro

dr
pe

hy
+ e- + H+ + e- + H+ + e- + H+ + e- + H+
z O2 + 4 e- + 4 H+ 2 H2O O2 HO2. H 2O 2 H2O + HO. 2 H2O

pKa 4.8 11.8 11.9

z During the reaction several
intermediates are formed (i.e. hydrogen O2.- HO2- O.-

peroxide, hydroxyl radicals etc.) Superoxide Peroxide anion Oxyl radical

(Carlton W. Dence and Douglas W. Reeve (editors) "Pulp Bleaching, Principles and
Practice" TAPPI PRESS, Atlanta 1996.)

Chemistry of Oxygen Delignification Radical chain reaction

The mechanism of oxygen delignification
z In normal state oxygen is a weak oxidant
z Reactivity can be improved by Initiation RO- + O2 RO. + O-2. (1)
{Raising the temperature RH + O2 R. + HO2. (2)
{Providing a reactive substrate
z Alkaline process conditions ionize free phenolic hydroxyl Propagation R. + O2 RO2. (3)
groups in the residual lignin RO2. + RH RO2H + R. (4)
R R

+ OH-
+ H2O
OMe OMe
Termination RO. + R. ROR (5)
OH O

Radical chain reaction (Carlton W. Dence and Douglas W. Reeve (editors) "Pulp Bleaching, Principles and
Practice" TAPPI PRESS, Atlanta 1996.)

2
Lignin reactions Lignin reactions

z Oxygen is R is H, OAr, or an alkyl group

{a weak oxidant R R R R .

{a radical .
.
z Reacts with dissociated phenolic lignin
OMe OMe OMe OMe
O O O O

structures
R O
R R R . R R O
O2 .
O2-. + .
O
OMe OMe OMe OMe OMe OMe
OMe O
OMe
O O. O O O O O
O O
O

Lignin reactions
Phenolic hydroxyl groups
z As a result of these reactions lignin becomes
Phenolic OH groups in residual lignin, mmol/g lignin
oxidized and more hydrophilic
2,2
It is easier to remove from the pulp
2
z Up to some extent oxygen reacts with phenolic 1,8
structures, but all of these structures are not 1,6
1,4
reactive 1,2
{p-phenols vs. m-phenols 1
0,8
0 50 100 150 200
Delignification time, min

3
p-hydroxyphenyl structures Selectivity

p -hydroxyphenyl structures, mmol/g lignin

z Approximately 50 % of the residual lignin can be
0,2 removed
{Pulp quality problems occur if the limit is exceeded
0,15
z Peroxide is formed in the stepwise reduction of
0,1 oxygen.
0,05 z Peroxide can decompose forming among others
OH
0
hydroxyl radicals (HO.).
0 50 100 150 200 z Hydroxyl radicals are highly reactive and react
Delignification time, min with lignin and polysaccharides.
Oxygen does not remove p-hydroxyphenyl structures. Why?
transition metal = siirtymmetalli; decomposition = hajoaminen

Selectivity Carbohydrate reactions

z Pulps contain transition metals, such as z Degradation of polysaccharides:

Mn, Cu and Fe.
z Transition metals act as catalysts for
peroxide decomposition.
More hydroxyl radicals (HO.) formed.
z Harmful effects of transition metals can be
reduced by addition of magnesium salts
(e.g. MgSO4).
Formation of inactive metal complexes .
transition metal = siirtymmetalli; decomposition = hajoaminen
1) cleavage of glycosidic linkages
2) peeling reaction
z Cleavage of glycosidic linkages is more
significant during oxygen delignification than
peeling reaction.
z As a result of carbohydrate reactions pulp
viscosity and strength properties may decrease.

4
Reaction mechanism for carbohydrates Reaction mechanism for carbohydrates

z Step 1
CH2OH
{Primary oxidation by a hydroxyl radical and CH2OH
O O2 / HO-
CH2OH
O O
O R O R O R
formation of a carbonyl intermediate at the C2- R O
OH
R O
OH HO-
R O

position of a monomeric sugar unit OH O

HO O

z Step 2 - RO-

{A cleavage of the glycosidic bond at C4 by - HOH2C HOH2C CH2OH CH2OH

O
alkoxy elimination O O R
+
O R O
O R
O
O R
CO2-
CO2-
z Step 3
CO2-
HO O O HO O

{Formation of a new reducing end group

Extractives Advantages and Disadvantages

z Unsaturated lipophilic extractives can + Low chemical costs - High capital costs
react with oxygen. + Environmentally - Ineffective in normal
friendly method state
z Alkaline conditions with efficient washing lower chemical necessary to have
can result in extensive deresination during consumption in
high temperature
subsequent bleaching
oxygen bleaching. stages a reactive substrate
less AOX load in D and - Low selectivity at
C bleaching stages higher degrees of
lower BOD and COD delignification
reduced colour of pulp

AOX = a group of halogenated organic compounds; BOD = biochemical (biological)

oxygen demand, COD = chemical oxygen demand