Clo2 PDF

Chemistry of Chlorine Dioxide
Pulp Bleaching
ragauskas@hotmail.com
Bleaching History
• Bleach - blecan (Anglo Saxon) – to fade
• First dates back to ancient Gauls: sunlight on
vegetable fibers moistened with alkaline solution
from wood or vegetable ash
• Process: alkali treatment, exposure on grassy
meadows to sun, washing, repeat, final treatment
with lactic acid from sour milk
– Became known as “grass bleaching”
– Perfected around Haarlem, Holland
– Material generally of linen fibers
Bleaching History
• 1756 – Francis Home (Scotland)
– Discovered that by substituting dilute sulfuric acid for lactic acid in
last step, operating time is reduced.
– Still is a grass bleaching operation and not used yet for paper
– “White” paper made from sorted white rags
• 1774 – Karl Wilhelm Scheele (Swedish Chemist)
– discovered chlorine and pioneered use as a bleaching chemical on
vegetable fibers
• Berthollet – French chemist
– discovered chlorine could be absorbed in solution of caustic potash
and resulting solution had efficient bleaching action with less
degrading effect on the finished goods (product)
Bleaching History
• Thomas Henry – English
– extended use of bleaching solution to paper (rag)
• 1798 – Charles Tennant – Scotland
– formulated calcium hypochlorite by reaction of
chlorine gas with milk of lime
• 1799 – Charles Tennant
– patent on production of bleaching powder by action of
chlorine on slaked lime – became world’s most
dominant bleaching agent
Bleaching History
• 1920’s: Continuous operating bleaching
introduced by Thorne in multi-stage
bleaching
– for purification of pulp from demand for large
tonnages of nitrocellulose during WWI
– 2 stage hypochlorite then added alkaline
extraction in between hypochlorite stages
• Use of Chlorine dioxide investigated from
1920 – 1940, put into production 1940’s
Chlorine Dioxide History
• 1946 – 1980’s used as a later bleaching

stage, not for delignification
– CEHDED, CEDED
• Late 1980’s realized that ClO2 and Cl2 used
together had a higher delignification
efficiency than Cl2 alone
• Environmental regulations dictated the
switch from elemental chlorine (Cl2 &
HOCl) to ClO2 and other TCF methods
Chlorine Dioxide
• Molecular Weight: 67.45
• Boiling Point: 11°C
• Yellow green to orange
gas, with a sharp pungent
odor
• Water soluble, 10 g/L
• Oxidant
• Density: 2.4 x’s water
• Decomposes to Cl2 and O2
with noise, heat, flame,
and minor pressure wave
Formation of Chlorine Dioxide
• Reduction of chlorate in acidic medium:
– ClO3- + 2 H+ + e- Æ ClO2 + H2O
• Oxidation of chlorite ion:

– ClO2- Æ ClO2 + e-
Reductive Chemistry
• Reducing agents are used to make the e-
– SO2 + 2 H2O Æ SO42- + 4 H+ + 2 e-
– CH3OH + H2O Æ HCOOH + 4 H+ + 4 e-
– Cl- Æ ½ Cl2 + e-
– H2O2 Æ O2 + 2 H+ + 2 e-
Making Chlorine Dioxide
• 2 ClO3- + SO2 Æ 2 ClO2 + SO42-
• 4 ClO3- + CH3OH + 4 H+ Æ 4 ClO2 +
HCOOH + 3 H2O
• ClO3- + Cl- + 2 H+ Æ ClO2 + Cl2 + H2O
• 2 ClO3- + H2O2 + 2 H+ Æ 2 ClO2 + O2 +
2 H2O
• ClO3- + 6 H+ + 6e- Æ Cl- + 3 H2O
Chlorine Dioxide
Chemical properties:
One of several known oxides of chlorine.
Chlorine dioxide is a powerful oxidizing agent - an electron receiver. This means

that the chlorine dioxide molecule is in constant search for an additional
electron. → Disinfection The destruction of pathogenic and other kinds of
microorganisms by physical or chemical means
When a bacterial cell comes into contact with chlorine dioxide it donates an
electron from its cell wall, thereby creating a breach in the cell wall through
which cell contents pass in an attempt to bring the concentrations on either
side of the cell membrane to equilibrium. The cell dies through lysis.
Chlorine Dioxide
How long has chlorine dioxide been used?
Chlorine dioxide has found widespread use since the
early 1950s in the treatment of drinking water and
swimming pools.
Today, chlorine dioxide is used by many

large cities in Europe, such as (1956)
Brussels, Zurich, Düsseldorf, Toulouse
and Vienna, to sanitize the drinking
water supply.
Chlorine Dioxide
Chlorine dioxide has many applications:
• Food industry
Fruit and vegetable washing
Meat and poultry disinfection
Sanitizing food process equipment
• Medical
“Tristel” sterilizing solutions for medical instruments
Air disinfection and building decontamination.
(2001 anthrax attacks, US)
• Personal hygiene
Mouthwashes (~0.003%)
Toothpastes
Contact lens cleaners
• Other industry
Cooling systems and towers in the control of
Legionella.(Gram negative bacterium)
Bleaching Pulp with Chlorine Dioxide
Advantages
¾High brightness and brightness stability

¾Excellent for shive and dirt removal - the best
¾Highly selective - little degradation of pulp
¾Less organic chlorine than Cl2 and ClO-
¾Radical scavenger
Bleaching Pulp with Chlorine Dioxide
Disadvantages
¾ Highly explosive – hence generate on-site

¾ Highly corrosive - need titanium equipment -
high capital cost
¾ Expensive
¾ Toxic - handle with care
¾ AOX
¾ Chlorate formation
¾ 26-40% loss in oxidation power
ClO2 Delignification Process Conditions
• Total Chemical Charge: 0.15 – 0.25 kappa
factor
• Chlorine dioxide charge: 25 – 100% of the
total
• Temperature: 30 -60° C
• Total Time: 20 – 60 minutes
• End pH: 1.5 – 3
• Consistency: 3 – 4%
Chlorine Dioxide Puffs
• Puff – deompostion of chlorine dioxide
– 2 ClO2 Æ Cl2 + 2 O2 + heat
– Low speed wave of reaction (< 1m/s)
• Explosion: > 300 m/s
– Generators designed for up to 200 mm Hg
AOX vs. ClO2 Substitution
8
7 Kappa
AOX, kg/admt
6
Unbl 30
5
EO 23.5
4
EOP 20.5
3 O 16.6
2
1
0
0 20 40 60 80 100
ClO2 Substitution, %
Liebergott
Substitution of Chlorine Dioxide
• AOX Generation
– AOX (kg/t) = 0.1 (Cl2, kg/t active chemical)
– AOX (kg/t) = 0.1(1/2.63)(.526)(ClO2, kg/t active chemical)
0.02(ClO2, kg/t act chemical)
• On an equal weight basis ClO2 is 2.63 times as
as reactive as Cl2
Cl2 + 2e- = 2Cl- ⇒ 71/2 = 35.5
ClO2 + 5e- = Cl- ⇒ 67.5/5 = 13.5
35.5 / 13.5 = 2.63
Chloroform – CHCl3
0.35 % ClO2 sub
Chloroform, kg/odmt
0.3
100%
0.25
71%
0.2 46%
0.15 28%
0.1 0%
0.05
0
0 0.1 0.2 0.3 0.4
Chlorine Factor
Effect of Chlorine Multiple on
Dioxin Formation
Substitution of Chlorine Dioxide
for Chlorine
Old Bleaching Sequences:
(CD)E1D1E2D2 O (CD)E1D1E2D2
ECF Sequences:
D0E1D1E2D2 O D0E1D1E2D2
ECF = Elemental Chlorine-Free

Chlorine Dioxide
O Cl O O Cl O O Cl O
Chlorine Dioxide
• Chemistry
ClO2 + e- ⇒ ClO2-
ClO2- + 3H+ + 2e- ⇒ HClO + H2O
HClO + H+ + 2e- ⇒ Cl- + H2O
ClO2 + 4H+ + 5e- ⇒ Cl- + 2H2O
Equivalent Weight: ClO2 = 67.5/5 = 13.5

Cl2 = 71/2 = 35.5
Basic Cation Radical Mechanism of Chlorine Dioxide
R
OCH3
O
R1
ClO2
R = Alkyl or R2
R
R1 = H, Alkyl or Aryl ClO2
CT - Complex
OCH3 π-Complex
O
R1
+ H+
- HClO2
R R R R1 = Alkyl R R
R1 = H
or aryl
OCH3 OCH3 OCH3 OCH3 OCH3

+
O + OH O O+ O
R1 R1 R1
Phenolic structures Non-phenolic structures
Brage, Ericksson and Gierer, Holzforschung, 45(1):23 (1991)

Basic Phenolic Compound Reactions
CH3
OCH3
O
CH3 CH3 CH3 -
OClO CH3
ClO2 ClO2
H
- OCH3 OCH3 OCH3 OCH3
OClO
O O O O
+ H2O
- HClO2 CH3
- HOCl - HOCl CH3
H3C
COOCH3 CH2
O CH3
Bicreosol OCH3 CH3O
CH3O OH
O O
OCH3
O OCH3 O OCH3
O ClO2 + HClO2 + H2O OH
CH3
CH3 H2C OClO- CH2OH
- HClO2
OClO-
+ H2O OCH3 OCH3
O - CH OH OCH3
3 O OH OH
O
Dimers + H2O
and polymers - HOCl
- HOCl
H3C CH3
COOCH3 CHO
O
CO2CH3
O CO2H OCH3
OH

Basic Non-Phenolic Compound Reactions
CH3
CH3 ClO2 ClO2 CH3
OCH3 + ClO2
ClO2 + +
OCH3 OCH3 OCH3
+ OCH3 OCH3
CH3
CH3 CH3 CH3
H
H
OCH3 + +
OCH3 OCH3 OCH3
+ OCH3 CH3O
+ OCH3 OCH3
ClO2 ClO2 ClO2 ClO2
CH3 - CH3 CH3

OClO CH3
H
H -
OClO +
- OCH3 OCH3 +
OClO OCH3 OCH3
OCH3 + OCH3 CH3O OClO-
+ OCH3
+ H2O + H2O + H2O + H2O
- HOCl - HClO2 - CH3OH - CH3OH
- CH3OH - H+ - HOCl - HOCl
- H+ - H+
CH3 O CH3
CH3 CH3
O O
HO H CO2CH3 OCH3
OCH3 O CO2CH3
OCH3 CO2CH3
ClO2 Oxidation of Methylveratrylalcohol
Effect of pH on Rate of Reaction
100
Percent Compound I
80 pH 2
60 pH 4
pH6
40
pH 8
20
0
0 50 100 150
Reaction Time (min.)
Effect of pH on the Reaction of ClO2 with
Methylveratrylalcohol (MVA)
HO CH3
MVA
OCH3
OCH3
O
H3C O
O
OCH3
H3C
OCH3 OCH3 O
O OCH3
O
3 5 6
HO CH3 HO CH3
CH CH Cl
Cl
Cl OCH3 OCH3 OCH3

Gunnarsson and Ljunggren, Acta Chem. Scand., 50: 442 (1996) OCH3 OCH3 OCH3
8 9 10
Effect of End pH in a D1 Stage on Brightness
and Chlorite and Chlorate Formation
Rapson, H., and C.B Anderson, Tappi, 61 (10):97 (1978)
ClO2-
86
ClO3-
84 1.8
ClO3- + ClO2-
82 1.6
Brightness
Brightness, %
80 1.4
78 1.2
76 1.0 Chlorate and/or
0.8 chlorite, % of
74
available chlorine
72 0.6
on pulp
0.4
70
0.2
68
66
2 3 5 7 8 10
End pH in the D1 stage
Effect of pH on ClO3- and ClO2- formation in ClO2
prebleaching of oxygen delignified kraft pulp
5.0
4.0
Concentration (mM)
3.0 Chlorite
Chlorate
2.0
1.0
0.0
0 2 4 6 8 10 12
End pH
Kappa no. 10.7, kappa factor 0.20, pulp consistency, 3.5%, 60 oC, 60 min
Wang, L. J. and B. H. Yoon, Paper presented at the International symposium on
Cellulose and Lignocellulosics Chemistry 2000, Dec. 16-18, 2000, Kunming, China
Effect of End pH in a D1 Stage on Brightness
and Chlorite and Chlorate Formation
Rapson, H., and C.B Anderson, Tappi, 61 (10):97 (1978) ClO2-
86
ClO3-
84 1.8
ClO3- + ClO2-
82 1.6
Brightness
Brightness, %
80 1.4
78 1.2
76 1.0 Chlorate and/or
0.8 chlorite, % of
74
available chlorine
72 0.6
on pulp
0.4
70
0.2
68
66
2 3 5 7 8 10
End pH in the D1 stage
Chlorate Forming Reactions
ClO2 + Free Radical + H2O ClO3- (1)

- -
2ClO2 + HO HClO2 + ClO3 (2)
- -
HClO2 + ClO2 HOCl + ClO3 (3)
2ClO2 + HOCl + H2O 2ClO3- + HCl + 2H+ (4)
ClO2- + HOCl + H2O* *ClO3- + HCl + H2O (5)
Dissociation Constants of Hypochlorous
and Chlorous acids
H C lO 2 C lO 2 - + H +
p K a ~ 2 .3
K1 K2
Cl2 + H2 O H + Cl + ClOH ClO - + H+
pK1 ~ 1.8 pK2 ~ 7.5
Disproportionation of Chlorous Acid
- Slow -
HClO2 + ClO2 HOCl + ClO3 (3)
- 2 -
-d(ClO2 )/dt = k1(HClO2) + k2(ClO2 )(HClO2)
pKa~2.3
HClO2 ClO2- + H+
- + Fast
HClO2 + Cl + H 2HOCl (7)
Kieffer andGordon, Inorganic Chem., 7(2):239 (1968)
Hong and Rapson, Canadian J. Chem., 46:2053 (1968)
Competitive Reactions of
Hypochlorous Acid
ClO2- 2ClO2 + Cl- (6)

O
ClO2- + HOCl Cl Cl H2O
-HO- O
ClO3- + HCl + H+ (5)
Oxidized Lignin + Cl-/ 2Cl-

Lignin + ClOH/Cl2
Organic-Cl + H2O/ Cl-
Summary
• In D0, the increase in chlorate and bleaching
efficiency levels off at end pH below 3.4,
whereas AOX continues to increase with
decreasing pH.
• In D0, the phenolic hydroxyl content of
lignin in pulp has little effect on either
chlorate formation or bleaching efficiency.
Summary
• The phenolic lignin structures have demonstrated enhanced
reactivity with chlorine dioxide over that of the non-phenolic units.
• The initial stage of ClO2 delignification is believed to be the
abstraction of an electron from the phenolate anion followed by
further degradation caused by additional equivalents of chlorine
dioxide.
• Lactones, muconic acid esters, maleic acid, oxiranes and quinoid
structures are the dominant oxidation products along with significant
levels of methanol.
• Chlorinated organics are produced during ClO2 bleaching, primarily
due to the in situ formation of hypochlorous acid.

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Chemistry of Chlorine Dioxide

• 1946 – 1980’s used as a later bleaching

• Oxidation of chlorite ion:

Chlorine dioxide is a powerful oxidizing agent - an electron receiver. This means

Today, chlorine dioxide is used by many

¾High brightness and brightness stability

¾ Highly explosive – hence generate on-site

– Generators designed for up to 200 mm Hg

ECF = Elemental Chlorine-Free

Equivalent Weight: ClO2 = 67.5/5 = 13.5

OCH3 OCH3 OCH3 OCH3 OCH3

Brage, Ericksson and Gierer, Holzforschung, 45(1):23 (1991)

Brage, Ericksson and Gierer, Holzforschung, 45(1):23 (1991)

CH3 - CH3 CH3

Cl OCH3 OCH3 OCH3

ClO2 + Free Radical + H2O ClO3- (1)

ClO2- + HOCl + H2O* *ClO3- + HCl + H2O (5)

ClO2- 2ClO2 + Cl- (6)

Oxidized Lignin + Cl-/ 2Cl-

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