Bleaching pulp with chlorine

Chlorination and extraction have traditionally been employed in the first two stage of pulp bleaching
sequence as means of effectively delignify the pulp. Chlorine react with non carbohydrate
compound rendering them to water soluble and soluble in alkaline medium.

Chlorine Delignification Process Conditions

Pulp consistency - 2.5 to 3.5 %

Chlorine charge - 3 to 4% of OD pulp

Temperature - 20-30°C

Retention Time - 45 - 90 minutes

pH - below 2.0

Advantages of chlorine bleaching

• Cost effective
• Decrease chemical demand in subsequent bleaching stages

Disadvantages

• High AOX generation raising environmental as well as health concern.

• Increase effluent load
• High degradation of pulp if processes condition not optimised.
• Loss of strength property of pulp

Bleaching Pulp with Chlorine Dioxide

With growing concern about the environmental impact of chlorinated organic compounds,
elemental chlorine has been replaced by chlorine dioxide which produces approximately five times
less AOX than the former. With the banishment of elemental chlorine from pulp bleaching
sequences, ECF bleaching cycles reduce dioxins and absorbable organic halides (AOXs) to well below
regulatory limits.

Advantages

 High final brightness and brightness stability

 Reduced effluent colour
 Excellent for shive and dirt removal - the best
 Highly selective - little degradation of pulp
 Less organic chlorine than Cl2 and ClO-
 Radical scavenger
Disadvantages

 Highly explosive – hence generate on-site

 Highly corrosive - need suitable 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 – decomposition 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

Chlorine dioxide generation

The production of chlorine as a by-product became an important criterion for the selection of
chlorine dioxide generators. Hence, chlorine dioxide generation technology has advanced
substantially during the past 50 years.

Clo2 is gas at room temperature and liquefies at 11°C. However the chemical is unstable and
potentially explosive in pure form. In air mixture it is easily detonated by exposure to heat, light
mercury, and various organic substance. Rich mixture can produce severe explosions: lower
concentration below 20% produce only mild detonations described as puffs. Chlorine dioxide is
somewhat more soluble in water then chlorine (10-11 gm per litter) science it cannot be shipped
either impure form as a concentrated solution, it is generated at mill site. It is generated as a gas
from chemical reduction of sodium chlorate in a highly acidic solution. The gas is then absorbed in
cold water to produce clo2 solution at a concentration of about 7 gm/litter.

Numerous method of onsite generation have bean developed. Originally the methods differed
primarily with respect to reducing agent that was used to react with chlorate. More recent
developments have been more concerned reducing the quantity of by-product chemicals.
The processes of the first generation, the Mathieson, the Solvay, and the R2, use sulphur dioxide,
methanol, and sodium chloride, respectively as reducing agents. The corresponding overall reactions
for the Mathieson, Solvay and R2 processes are displayed in Eqs., respectively:

Mathieson process - 2NaClO3 + SO2 + H2SO4 ------> 2ClO2 + 2NaHSO4

Solvay - 4NaClO3 + CH3OH + 2H2SO4 ---> 4ClO2 + 3H2O + HCOOH + 2Na2SO4

R2 - NaClO3 + NaCl + H2SO4 --------> ClO2 + 0.5Cl2 + Na2SO4 + H2O

All three processes operate at atmospheric conditions, and thus require high charges of sulfuric acid
to assure a high chlorine dioxide yield (defined as molar percentage of the sodium chlorate
converted to chlorine dioxide). The drawback of these processes is the generation of large amounts
of spent acid solution, expressed as tons of Na2SO4 losses per ton chlorine dioxide produced.

The only advantage of the R2 process over the Mathieson and Solvay processes is the much faster
reaction, which results in lower investment costs. However, the specific spent acid solution
production is almost twice that of the Mathieson and Solvay technologies. Moreover, the R2 process
generates 0.6 t of Cl2 t–1 of ClO2, with about 1g L–1 chlorine in the chlorine dioxide solution. The
residual 0.5 t Cl2 t–1 of ClO2 is primarily used to produce sodium hypochlorite.

The R3 and SVP (single-vessel process) processes were developed in a response to reduce the
amount of waste acid produced during the course of chlorine dioxide manufacture. As these
processes operate under vacuum, at higher temperatures, and employ a catalyst, both high
production and high yield are maintained at a far lower solution acidity as compared to the R2
process, which enables neutral anhydrous sodium sulphate to be crystallized. The neutral salt cake
can be filtered-off and removed from the system. Thus, the salt cake production is approximately
34% less as compared to the Mathieson and Solvay processes, and about 66% less than that of an R2
process.

R3 - 2NaClO3 + 2NaCl + 2H2SO4 -------> 2ClO2 + Cl2 + 2Na2SO4 + H2O

R-6 ClO2 generation Technology

Generally, chlorine dioxide manufacture is based on the reduction of sodium chlorate at high acidity.
In non-integrated processes, sodium chlorate is purchased as a crystalline solid or as a concentrated
(40–45%) aqueous solution, whereas in an integrated process sodium chlorate is prepared by the
electrolysis of a sodium chloride solution according to the following equation:

NaCl + 3H2O -----> NaClO3 + 3H2 (6H+ + 6e)

The evolving hydrogen (H2) is recycled to produce hydrochloric acid, which is used in the integrated
processes, known as R6, Lurgi or Chemetics processes, to reduce chlorate to chlorine dioxide. The
redox reaction in the chlorine dioxide generation can be written as:

NaClO3 + 2HCl -----> ClO2 + 0.5Cl2 + NaCl + H2O

where the by-product sodium chloride is recalculated to the electrolysis cell. The excess chlorine gas
evolved from Eq. is fed to the HCl synthesis unit together with make-up chlorine, where it is burned
together with the hydrogen produced from the chlorate electrolysis unit to produce hydrochloric
acid (HCl). The three unit operations chlorate electrolysis, chlorine dioxide generator and
hydrochloric acid synthesis; comprise
the key steps in an integrated
chlorine dioxide plant. The advantage
of an integrated system is that it
prevents the formation of any
sulphur-based by-products. However,
an integrated system produces a
chlorine dioxide solution with a
relatively high level of residual
elemental chlorine in the range 11–
23% of the chlorine dioxide
concentration.

Performance Data

ClO2 Solution Specification

ClO2 : 8 – 10 g/L

Cl2 : 0.2 g/L

HCl: 0.5 – 1.0 g/L Consumption per

tonne of ClO2

Raw Materials: Chlorine 0.7 tonne

Power: 8,500 – 9,500 kWh D.C.

Features:

• Lowest production cost

• High purity (low chlorine product)
• No purchased chlorate, acid, methanol, or peroxide is required
• Security of supply for feedstocks
• Improves the balance of pulp mill chlorine/ caustic consumption
• No solids handling
• No salt cake for disposal
 The overview of different type of Clo2 generation technology

Process Type Pressure Reducing By product

agent Na2SO4 Cl2 Cl2 In 10
[t/t ClO2] [t/t ClO2] gpl ClO2
Methison Non Atmospheric SO2 3.5
integrated
Solvay Non Atmospheric CH3OH 3.5
integrated
R2 Non Atmospheric NaCl 6.8 0.6 1.0
integrated

R3. SVP Non Vacuum NaCl 2.3 0.6 2.0

integrated
R3 H Non Vacuum HCl 1.1 0.6 1.5-2.5
integrated
R6 Lurgi Integrated Vacuum HCl 0 0.7 1.1-2.3
Chemetics
R8. SVP Non Vacuum CH3OH 1.1 0.01 0.1
MeOH integrated
R9 Non Vacuum CH3OH 0-1.1 0.01 0.1
integrated
R10 Non Vacuum CH3OH 0.9 0.01 0.1
integrated

Nonetheless, the amount of elemental chlorine formation is high due to the addition of sodium
chloride as a reducing agent. The urgent need to eliminate chlorine and to further reduce the
amount of sodium sulphate during chlorine dioxide production promoted the development of a new
methanol-based process. This process, known as R8, SVPMeOH and SVP-LITE processes, account for
the majority of the installed ClO2 capacity. The plants are similar with respect to the overall
operation and the process technology employed. The generation system consists of a generator and
a reboiler. In the generator, the sodium chlorate is reduced to chlorine dioxide while sodium
sesquisulfate is formed as a by-product. The chlorine dioxide is separated as a gas which, after a
concentration process, is dissolved in chilled water, where a concentration of approximately 10 g L–1
is adjusted. The chlorine dioxide solution is pumped to storage tanks for subsequent use in the
bleach plant. The sodium sesquisulfate is filtered off from the generator slurry, dissolved to a
saturated, acidic aqueous solution which is stored in a tank for further use (e.g., in tall oil plant). The
overall reaction comprising the R8 process may be expressed according to:

3NaClO3 + 2H2SO4 + 0.85 CH3OH ------> 3ClO2 + Na3H (SO4)2 + 2.3H2O + 0.8 HCOOH

Model experiments revealed that the generation of chlorine dioxide in the methanol-chlorate
process involves three distinct phases, namely initiation, start-up, and steady-state. In the initial
phase, no chlorine dioxide is formed, while chlorous acid and elemental chlorine are generated.
Chlorous acid is generated continuously from the reduction of chlorate by methanol and then
further reduced to hypochlorous acid, which then is converted to elemental chlorine. Chlorine
dioxide is formed from the reaction between chlorine and chlorous acid in the presence of chloride,
which acts as a catalyst. Apparently, chlorine dioxide is only generated when the chloride
concentration exceeds a certain level. Chlorine is usually present in a chlorine dioxide solution
because of the necessary presence of chloride in the generator.

The presence of low concentrations of chloride which actually leads to elemental chlorine formation
is essential to avoid the termination of chlorine dioxide production. The situation where chlorine
dioxide generation stops is known as a so-called “white-out” because a white gas consisting of
chlorine and water vapour appears.

In industrial practice, the chlorine dioxide solution contains elemental chlorine in a concentration
ratio of 100:1, as depicted in Table. At the same time, methanol is oxidized stepwise by chlorate to
form formaldehyde, then formic acid, and finally carbon monoxide in the case of complete
oxidation. Some of the methanol and its oxidation products may leave the generator along with
chlorine dioxide. Besides the very low concentration of chlorine, the R8 process has the advantage of
producing less salt cake (–52%) and higher chlorine dioxide yield (97% versus 93%) as compared to
the R3/SVP processes. However, the development of the methanol-based chlorine dioxide process
continued by focusing on the further reduction of the amount of salt cake. The sesquisulfate is
electrolyzed to form sodium hydroxide and sulphuric acid in the R9 process. There, the acid is
recirculated to the generator and the alkali fed to the bleach plant. Depending on the size of the
electrolytic cell, the amount of salt cake can be minimized in a range indicated in Table. The
metathesis of the sesquisulfate into neutral sodium sulphate crystals is the key element of the R10
process. The remaining solution containing residual salt and sulphuric acid is recirculated to the
generator. The metathesis is effected in such a manner as to minimize the additional evaporative
load imposed on the chlorine dioxide-generating process by the metathesis medium. The extent of
sulphate precipitation can be further enhanced by the addition of some methanol. Hydrogen
peroxide is another reducing agent which generates chlorine dioxide from chlorate. The
stoichiometry of this process is represented in Eq.

2NaClO3 + H2O2 + H2SO4 ------> 2ClO2 + Na2SO4 + 2H2O + O2

The peroxide-based process exhibits faster reaction kinetics as compared to the methanol-based
process. Consequently, the former can be operated at a sulphuric acid concentration of only 2 mol
L–1 sulphuric acid as compared to that of 4.5– 5.0 mol L–1 for the methanol-based process.
However, the high costs of hydrogen peroxide limit the attractiveness of the peroxide-based process
for chlorine dioxide generation. Alternatively, combining hydrogen peroxide and methanol causes a
considerable increase in the rate of chlorine dioxide generation. Furthermore, it largely eliminates
molecular chlorine as a by-product. Even when substituting only 10% of the methanol with hydrogen
peroxide, the reaction rate of chlorine dioxide formation is doubled. The high reaction rate can be
explained by the rapid reaction between hydrogen peroxide and chlorine, which results in chloride
and oxygen formation. Additionally, the reaction of hydrogen peroxide with dichlorodioxide (Cl2O2)
leads to a faster accumulation of the necessary chloride, which is a catalyst in the methanol-based
chlorine dioxide generation process. Besides costs, the most important criterion for the selection of
a chlorine dioxide plant is the amount of by-products generated. The level of elemental chlorine
must be kept to the lowest possible amount to ensure low AOX formation, while the quantities of
sodium sulphate - sulphuric acid solution must be adjusted to fit the Na/S ratio of the respective
Kraft mill. During the past decade, chlorine dioxide has been increasingly delivered “over the fence”
by companies specializing in chlorine dioxide generation. This concept is achieving growing
acceptance as the Kraft mills are no longer involved in the technology of chlorine dioxide generation.