Clo 2

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 worlds most dominant bleaching agent
Bleaching History
1920s: 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 1940s
Chlorine Dioxide History

1946 1980s used as a later bleaching stage, not for delignification
CEHDED, CEDED
Late 1980s 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: 11C Yellow green to orange gas, with a sharp pungent odor Water soluble, 10 g/L Oxidant Density: 2.4 xs 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- ClO2 + H2O
Oxidation of chlorite ion:

ClO2- ClO2 + e-
Reductive Chemistry
Reducing agents are used to make the e SO2 + 2 H2O SO42- + 4 H+ + 2 eCH3OH + H2O HCOOH + 4 H+ + 4 eCl- Cl2 + eH2O2 O2 + 2 H+ + 2 e-
Making Chlorine Dioxide

2 ClO3- + SO2 2 ClO2 + SO42 4 ClO3- + CH3OH + 4 H+ 4 ClO2 + HCOOH + 3 H2O ClO3- + Cl- + 2 H+ ClO2 + Cl2 + H2O 2 ClO3- + H2O2 + 2 H+ 2 ClO2 + O2 + 2 H2O ClO3- + 6 H+ + 6e- 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, Dsseldorf, 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
High brightness and brightness stability Excellent for shive and dirt removal - the best Highly selective - little degradation of pulp Less organic chlorine than Cl2 and ClORadical scavenger
Bleaching Pulp with Chlorine Dioxide

Disadvantages
Highly explosive hence generate on-site Highly corrosive - need titanium equipment high capital cost Expensive Toxic - handle with care AOX Chlorate formation
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 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 6 5 4 3 2 1 0 0 20 40 60 80 100 ClO2 Substitution, %
AOX, kg/admt
Kappa
Unbl 30 EO 23.5 EOP 20.5 O 16.6
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
Chloroform, kg/odmt
0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 0 0.1 0.2 0.3 0.4
% ClO2 sub
100% 71% 46% 28% 0%
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- ClO2ClO2- + 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 R1 O ClO2 R = Alkyl or R2 R1 = H, Alkyl or Aryl O + H+ - HClO2 R R R1 = H OCH3
+ OH
R ClO2 OCH3 R1 CT - Complex -Complex
R1 = Alkyl or aryl OCH3
OCH3 O
OCH3 R1 O+ R1 O
R1
OCH3
Phenolic structures
Non-phenolic structures
Brage, Ericksson and Gierer, Holzforschung, 45(1):23 (1991)

Basic Phenolic Compound Reactions

CH3 OCH3 O CH3 ClO2 H
-
CH3
CH3 ClO2 OCH3 OCH3 O CH3
OClO
CH3 OCH3 O
- HClO2
OClO
OCH3 O
- HOCl
+ H2O - HOCl
CH3
H3C O CH3O O
COOCH3
CH3
CH2 Bicreosol O OCH3 OCH3 OCH3 ClO2 CH3

- HClO2 + H2O + HClO2
CH3O OH OCH3
+ H2O
O O
O OH CH2OH
CH3 OClOO OCH3

+ H2O - HOCl
H2C OClO-
Dimers and polymers H3C
O - CH OH 3
OCH3 OH
- HOCl
OCH3 OH
COOCH3 O O
CH3 CO2CH3 CO2H
CHO
OCH3 OH

Basic Non-Phenolic Compound Reactions

CH3 CH3 ClO2 + ClO2 OCH3 OCH3
+ OCH3
ClO2
CH3
+
+ ClO2
OCH3
OCH3 OCH3
CH3 H OCH3
+ OCH3
CH3 OCH3
+ OCH3
CH3
+
CH3
+
OCH3 OCH3 ClO2 H

-
CH3O ClO2 CH3
OCH3
ClO2 CH3 H OClO

+ -
ClO2 OClO CH3 OCH3

+
CH3
+
OCH3 OCH3
+ H2O - HOCl - CH3OH
OClO
OCH3
+ H2O - HClO2 - H+
OCH3 OCH3
+ H2O - CH3OH - HOCl - H+
CH3O
OCH3 OClO+ H2O - CH3OH - HOCl - H+
CH3 O HO H CO2CH3
CH3 O OCH3 OCH3
CH3
CH3 O CO2CH3 CO2CH3
OCH3
ClO2 Oxidation of Methylveratrylalcohol Effect of pH on Rate of Reaction

100 Percent Compound I 80 60 40 20 0 0 50 100 Reaction Time (min.)
pH 2 pH 4 pH6 pH 8
150
Effect of pH on the Reaction of ClO2 with Methylveratrylalcohol (MVA)

HO CH3
MVA
OCH3 OCH3
O O H3C O OCH3 H3C OCH3 O OCH3 OCH3 O O
3
HO CH CH3 Cl Cl OCH3 OCH3
5
HO CH CH3
6
Cl
OCH3 OCH3 OCH3
OCH3
Gunnarsson and Ljunggren, Acta Chem. Scand., 50: 442 (1996)
8
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) 86
84 82 Brightness, % 80 78 76 74 72 70 68 66 2 3 5 7 8 10 End pH in the D1 stage

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2
ClO2ClO3ClO3- + ClO2Brightness
Chlorate and/or chlorite, % of available chlorine on pulp
Effect of pH on ClO3- and ClO2- formation in ClO2 prebleaching of oxygen delignified kraft pulp
5.0 Concentration (mM) 4.0 3.0 2.0 1.0 0.0 0 2 4 6 End pH 8 10 12 Chlorite Chlorate
Kappa no. 10.7, kappa factor 0.20, pulp consistency, 3.5%, 60 oC, 60 min
ragauskas@hotmail.com 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) 86
84 82 Brightness, % 80 78 76 74 72 70 68 66 2 3 5 7 8 10 End pH in the D1 stage

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2
ClO2ClO3ClO3- + ClO2Brightness
Chlorate and/or chlorite, % of available chlorine on pulp
Chlorate Forming Reactions
ClO2 + Free Radical + H2O 2ClO2 + HO

-
ClO3HClO2 + ClO3 HOCl +

ClO3 -
(1) (2) (3) (4) (5)
HClO2 + ClO2
2ClO2 + HOCl + H2O ClO2- + HOCl + H2O*
2ClO3- + HCl + 2H+ *ClO3- + HCl + H2O
Dissociation Constants of Hypochlorous and Chlorous acids

C lO 2 - + H + p K a ~ 2 .3
H C lO 2
K1 Cl2 + H2 O
K2
H + Cl + ClOH pK2 ~ 7.5 pK1 ~ 1.8
ClO - + H+
Disproportionation of Chlorous Acid

HClO2 + ClO2
-
Slow
2
HOCl + ClO3
-
(3)
-d(ClO2 )/dt = k1(HClO2) + k2(ClO2 )(HClO2)
pKa~2.3 HClO2 HClO2 + Cl + H

+
ClO2- + H+ Fast 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- + HOCl O Cl Cl O ClO2H2O ClO3- + HCl + H+ (5) 2ClO2 + Cl(6)
-HO-
Oxidized Lignin + Cl-/ 2ClLignin + ClOH/Cl2 Organic-Cl + H2O/ Clragauskas@hotmail.com
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 Pulp Bleaching

1774 Karl Wilhelm Scheele (Swedish Chemist)

Berthollet French chemist

1798 Charles Tennant Scotland

1799 Charles Tennant

Chlorine Dioxide History

Formation of Chlorine Dioxide

Oxidation of chlorite ion:

Making Chlorine Dioxide

Bleaching Pulp with Chlorine Dioxide

Bleaching Pulp with Chlorine Dioxide

ClO2 Delignification Process Conditions

Chlorine Dioxide Puffs

Generators designed for up to 200 mm Hg

AOX vs. ClO2 Substitution

Substitution of Chlorine Dioxide

On an equal weight basis ClO2 is 2.63 times as as reactive as Cl2

Effect of Chlorine Multiple on Dioxin Formation

Substitution of Chlorine Dioxide for Chlorine

ECF = Elemental Chlorine-Free

Basic Cation Radical Mechanism of Chlorine Dioxide

R ClO2 OCH3 R1 CT - Complex -Complex

R1 = Alkyl or aryl OCH3

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

Basic Phenolic Compound Reactions

CH3 ClO2 OCH3 OCH3 O CH3

CH2 Bicreosol O OCH3 OCH3 OCH3 ClO2 CH3

CH3 OClOO OCH3

Dimers and polymers H3C

CH3 CO2CH3 CO2H

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

Basic Non-Phenolic Compound Reactions

OCH3 OCH3 ClO2 H

CH3O ClO2 CH3

ClO2 CH3 H OClO

ClO2 OClO CH3 OCH3

OCH3 OClO+ H2O - CH3OH - HOCl - H+

CH3 O OCH3 OCH3

CH3 O CO2CH3 CO2CH3

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

ClO2 Oxidation of Methylveratrylalcohol Effect of pH on Rate of Reaction

Effect of pH on the Reaction of ClO2 with Methylveratrylalcohol (MVA)

O O H3C O OCH3 H3C OCH3 O OCH3 OCH3 O O

OCH3 OCH3 OCH3

Gunnarsson and Ljunggren, Acta Chem. Scand., 50: 442 (1996)

Effect of End pH in a D1 Stage on Brightness and Chlorite and Chlorate Formation

84 82 Brightness, % 80 78 76 74 72 70 68 66 2 3 5 7 8 10 End pH in the D1 stage

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2

Chlorate and/or chlorite, % of available chlorine on pulp

Effect of End pH in a D1 Stage on Brightness and Chlorite and Chlorate Formation

84 82 Brightness, % 80 78 76 74 72 70 68 66 2 3 5 7 8 10 End pH in the D1 stage

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2

Chlorate and/or chlorite, % of available chlorine on pulp

Chlorate Forming Reactions

ClO2 + Free Radical + H2O 2ClO2 + HO

ClO3HClO2 + ClO3 HOCl +

(1) (2) (3) (4) (5)

2ClO2 + HOCl + H2O ClO2- + HOCl + H2O*

2ClO3- + HCl + 2H+ *ClO3- + HCl + H2O

Dissociation Constants of Hypochlorous and Chlorous acids

H + Cl + ClOH pK2 ~ 7.5 pK1 ~ 1.8

Disproportionation of Chlorous Acid

-d(ClO2 )/dt = k1(HClO2) + k2(ClO2 )(HClO2)