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The Basics
Tom Powe
Sr. Technology
Services Engineer
CHLORINE DIOXIDE PROCESS
The Basics
• ClO2 Properties/Safety
• Vacuum Processes
• Control Strategy
CHLORINE DIOXIDE
PHYSICAL PROPERTIES
• General
– Formula ClO2
– Molecular Weight 67.45
• Appearance
• 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
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
• ATMOSPHERIC
• VACUUM
• OTHER
VACUUM PROCESS
• Advantages • Disadvantages
– Safer to operate
Less violent
decomposition
VACUUM PROCESS FLOW DIAGRAM
Sulfuric Acid
Saltcake Saltcake
Sodium Chlorate ClO Generator Saltcake Saltcake
ClO2 2Generator Filtration Dissolving
Filtration Dissolving
Reducing Agent
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
Generator
Condensate Circ. Pump
Pump
Saltcake
Filter Pump
VACUUM PROCESS FLOW DIAGRAM
with Saltcake Washing
Vent
Vent Scrubbing
Vent Scrubbing Chilled Water
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
• Generator Level
• Generator Chemistry
• Generator Pressure
Do They
correlate?
• Generator Temperature
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
• Change the steam flow at the same time you change the
feed flows.