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CHLORINE DIOXIDE PROCESS

The Basics

Tom Powe
Sr. Technology
Services Engineer
CHLORINE DIOXIDE PROCESS
The Basics

• ClO2 Properties/Safety

• General Introduction to ClO2 Processes

• Vacuum Processes

• Control Strategy
CHLORINE DIOXIDE
PHYSICAL PROPERTIES

• General
– Formula ClO2
– Molecular Weight 67.45

• Appearance

– Gaseous Greenish Yellow


– Aqueous Solution Pale Yellow to Deep Green
(Color proportional to strength)
CHLORINE DIOXIDE
PHYSICAL PROPERTIES

• Exposure Limits
– TLV 0.1 ppm per 8 hr shift
– Exposure 5 ppm

• Odor
– Detectable 1 - 2 ppm
– Noticeable 2 - 5 ppm
– Irritating 5 - 10 ppm
– Dangerous 10 - 18 ppm
– Fatal 19 ppm
CHLORINE DIOXIDE SOLUBILITY
in Water
ClO 2 Soln Concentration

20

15
[gpl]

10

0
0 20 40 60 80 100 120 140
ClO 2 gas Partial Pressure [mmHg]

0 5 10 15

Temperature °C
DECOMPOSITIONS

Reaction • Initiators
– Heavy Metals
2 ClO2 ⇒ Cl2 + 2 O2 + Heat – Rust
– Organic Materials
– Sunlight
– High Temperature
– High
Concentration
– Electrical Sparks
ClO2 DECOMPOSITION
SEVERITY

• > ClO2 gas concentration, > decomposition.

• > initial operating pressure, > decomposition.

• > the volume of gas, > decomposition.


CHLORINE DIOXIDE PRODUCTION

ClO3- + H+ + Reducing Agent ⇒ ClO2 + H2O

Chlorate Supply
• Any Alkali Metal Chlorate Will Work
– (NaClO3, KClO3, etc)
• Industry Practice uses NaClO3
– 99.9+% of All ClO2 Processes use NaClO3
CHEMISTRY FUNDAMENTALS

ACID REDUCING AGENT

Acid Saltcake Choice of Reducing Agent


• H2SO4 Na2SO4 Determines the By-
Product Gas
R Agent Gas
• CH3OH CH2O2
• H2O2 O2
PROCESS TYPES

• ATMOSPHERIC

• VACUUM

• OTHER
VACUUM PROCESS

• React the Chlorate, Acid & Reducing Agent in a


Vacuum Crystallizer

• The Generator/Crystallizer operates in the range


from 150 - 250 mmHg absolute.

• Acidity Varies by Process Chemistry

• The By-Product Salt is Discharged as a Dry Crystal


WHY A VACUUM PROCESS?

• Advantages • Disadvantages

– Sulphate By-Product – Higher Capital Cost


may be used by the Versus Atmospheric
Mill Systems

– Very Efficient NaClO3 – More complex


use operation

– Safer to operate
Less violent
decomposition
VACUUM PROCESS FLOW DIAGRAM

Vent Scrubbing Chilled Water


Vent Scrubbing

ClO2 Product Gas Condensing Cooling Water


Gas Condensing
Cooling Water

HP Steam or vacuum pump


ClO Storage ClO Absorption Vacuum System
ClO2 2Storage ClO2 2Absorption Vacuum System

Cooling Water Gas Condensing


Gas Condensing
Cooling Water Water Caustic

Sulfuric Acid
Saltcake Saltcake
Sodium Chlorate ClO Generator Saltcake Saltcake
ClO2 2Generator Filtration Dissolving
Filtration Dissolving
Reducing Agent

LP Steam Heat Addition Saltcake Solution


Heat Addition Air
Condensate Water To Mill
VACUUM PROCESS FLOW DIAGRAM
HP Steam Vent

Filter Ejector System Ejector


Vent
Hot Fan
Water
Saltcake
Filter Misc.
Cooling Chilled
Air Vents
Water Water
Filter Receiver

System
Condenser
Vent
Deluge/Spray Scrubber
Quench

Generator
Dissolving Chilled Scrubber
Tank Generator Water Pump
Condenser
Saltcake Soln.

Acid
Feed Cooling
Saltcake Water
Sol. Pump
Reboiler
LP Steam
To Bleach
NaClO3 Plant
Condensate Feed Absorber
Tank

Condensate Reducing Agent Feed Absorber ClO2


Pump Storage

Generator
Condensate Circ. Pump
Pump
Saltcake
Filter Pump
VACUUM PROCESS FLOW DIAGRAM
with Saltcake Washing
Vent

Vent Scrubbing
Vent Scrubbing Chilled Water

ClO2 Product Gas Condensing Cooling Water


Gas Condensing
Cooling Water

ClO Storage ClO Absorption Vacuum System HP Steam


ClO2 2Storage ClO2 2Absorption Vacuum System

Cooling Water Gas Condensing


Gas Condensing
Cooling Water
Air

Sulfuric Acid
Saltcake Saltcake Water Caustic
ClO Generator Saltcake Saltcake
Sodium Chlorate ClO2 2Generator Filtration No.1 Recrystallizer
Filtration No.1 Recrystallizer
Methanol

Saltcake Saltcake
Filtrate Storage Saltcake Saltcake
LP Steam Heat Addition Filtrate Storage Filtration No.2 Dissolving
Heat Addition Filtration No.2 Dissolving
Condensate

Saltcake Solution
Water Air To Mill
YIELD
100
Yield Components
99
• Feeds

Yield (%)
98
– Chlorate Feed

97
• Losses
– Chlorate for side reactions 96
– Chlorate in Saltcake
– Chlorate lost as ClO2 in the 95
vents

HP
Lite/R-8

SCW/R-
• Calculation

10
Yield = (Feeds-Losses)/Feeds
SALTCAKE FILTRATION REQUIREMENTS

2.5
T Saltcake/T ClO2

1.5

0.5

0
Lite SCW HP
PROCESS TRADE NAMES

Reducing Agent Acid Acidity Salt Form Name By

NaCl H2SO4 Low Crystal SVP-Conventional Eka


H2SO4 Low Crystal R-3 Process Sterling
H2SO4 High Solution R-2 Process Hooker

CH3OH H2SO4 Moderate Crystal SVP-Lite Eka


H2SO4 Moderate Crystal SVP-SCW Eka
H2SO4 High Crystal R-8 Process Sterling
H2SO4 High Solution Solvay Solvay
H2SO4 High Crystal R-10 Sterling

H2O2 H2SO4 Low Crystal SVP-HP Eka


H2SO4 High Solution HP-A Eka

SO2 H2SO4 High Solution Mathieson Olin-Mathieson


PROCESS COMPARISONS - Chemicals

ITEM Methanol Methanol Peroxide


Based Based with Based
Washing
Chlorate, 1.64 1.64 1.64
Ton/Ton
ClO2
Reducing 0.16 0.16 0.33
Agent,
Ton/Ton
ClO2
Sulfuric Acid, 1.0 0.75 0.75
Ton/Ton
ClO2
Salt Cake, 1.44 1.06 1.06
Ton/Ton
ClO2
PROCESS COMPARISONS - Utilities

ITEM Methanol Methanol Peroxide


Based Based with Based
Washing
LP Steam, 4.3 5.1 4.6
Ton/Ton ClO2

HP Steam, 0.92 1.26 1.76


Ton/Ton ClO2

Chilled Water, 91.0 89.1 91.2


Ton/Ton ClO2

Cooling & 298 341 292


Hot Water,
Ton/Ton ClO2
KEY PROCESS CONTROL VARIABLES

• Generator Level

• Generator Chemistry

• Generator Solids Level

• Chemical Feed Flows

• Generator Pressure
Do They
correlate?
• Generator Temperature

• ClO2 Solution Concentration


RULE OF 10 GUIDELINES

SODIUM CHLORATE SULFURIC ACID


GPL MOLARITY GPL NORMALITY
100 0.94 250 5.10
110 1.03 260 5.30
120 1.13 270 5.51
130 1.22 280 5.71
140 1.32 290 5.91
150 1.41 300 6.12
160 1.50 310 6.32
170 1.60 320 6.53
180 1.69 330 6.73
190 1.79 340 6.93
200 1.88 350 7.14
210 1.97 360 7.34
220 2.07 370 7.54
230 2.16 380 7.75
240 2.25 390 7.95
250 2.35 400 8.16
260 2.44 410 8.36
270 2.54 420 8.56
280 2.63 430 8.77
290 2.72 440 8.97
300 2.82 450 9.18
TARGET: 10.0 RANGE: 9.0 - 10.5

To calculate the "Rule of 10" number: Find the chlorate molarity and the acid normality on the
above chart that corresponds to the test performed on the generator solution. Add these two
numbers together. Make the appropriate chemical feed flow adjustment
GENERATOR LIQUOR TARGET ZONE

“Rule of 10”

7
6
5
Chlorate (M)

White-Out Zone
4
3
2
Sluggish Reaction
1
0
5 6 7 8 9 10 11
Acidity (N)

A+C=9 A + C = 10 A + C = 11
GENERATOR LEVEL CONTROL

• Maintaining a constant level in the generator is critical


for controlling generator concentrations.

• If an excess of water is boiled away in the generator, the


level will decrease and generator concentrations will
increase. An inverse effect occurs when not enough
water is boiled away.

• Also small adjustments, generally 500#/hr or less, of low-


pressure steam to the reboiler should be made to
minimize level swings.
PROCESS ADJUSTMENTS

• When making adjustments to the generator operation


keep in mind that the generator holds a large inventory
of chemicals.

• To avoid overshooting your target adjustments should


be made slowly.

• Change the steam flow at the same time you change the
feed flows.

• The changes in production rate must be done slowly.


SUMMARY

• The chlorine dioxide manufacturing process has evolved


from salt-based atmospheric systems to the methanol and
peroxide based vacuum systems that dominate the industry
today.

• The operation of a chlorine dioxide vacuum process is mill


specific.

• The key to smooth operation of a chlorine dioxide vacuum


process is generator level control.
Questions?