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 – Molecular Weight • Appearance – Gaseous – Aqueous Solution Greenish Yellow Pale Yellow to Deep Green (Color proportional to strength) ClO2 67.45 .

18 ppm 19 ppm .1 ppm per 8 hr shift 5 ppm 1 .10 ppm 10 .5 ppm 5 .CHLORINE DIOXIDE PHYSICAL PROPERTIES • Exposure Limits – TLV – Exposure • Odor – Detectable – Noticeable – Irritating – Dangerous – Fatal 0.2 ppm 2 .

CHLORINE DIOXIDE SOLUBILITY in Water ClO 2 Soln Concentration [gpl] 20 15 10 5 0 0 20 40 60 80 100 120 140 ClO 2 gas Partial Pressure [mmHg] 0 5 10 15 Temperature °C .

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

> decomposition. • > the volume of gas. > decomposition.ClO2 DECOMPOSITION SEVERITY • > ClO2 gas concentration. . • > initial operating pressure. > decomposition.

+ H+ + Reducing Agent ⇒ ClO2 + H2O Chlorate Supply • Any Alkali Metal Chlorate Will Work – (NaClO3.9+% of All ClO2 Processes use NaClO3 . KClO3. etc) • Industry Practice uses NaClO3 – 99.CHLORINE DIOXIDE PRODUCTION ClO3.

CHEMISTRY FUNDAMENTALS ACID Acid • H2SO4 Saltcake Na2SO4 REDUCING AGENT Choice of Reducing Agent Determines the ByProduct Gas Gas R Agent • CH3OH CH2O2 • H2O2 O2 .

PROCESS TYPES • ATMOSPHERIC • VACUUM • OTHER .

• Acidity Varies by Process Chemistry • The By-Product Salt is Discharged as a Dry Crystal .VACUUM PROCESS • React the Chlorate. Acid & Reducing Agent in a Vacuum Crystallizer • The Generator/Crystallizer operates in the range from 150 .250 mmHg absolute.

WHY A VACUUM PROCESS? • Advantages – Sulphate By-Product may be used by the Mill – Very Efficient NaClO3 use – Safer to operate Less violent decomposition • Disadvantages – Higher Capital Cost Versus Atmospheric Systems – More complex operation .

VACUUM PROCESS FLOW DIAGRAM Vent Scrubbing Vent Scrubbing Chilled Water ClO2 Product Gas Condensing Gas Condensing Cooling Water Cooling Water ClO Storage ClO2 2 Storage ClO Absorption ClO2 2 Absorption Vacuum System Vacuum System HP Steam or vacuum pump Cooling Water Cooling Water Sulfuric Acid Sodium Chlorate Reducing Agent LP Steam Condensate Gas Condensing Gas Condensing Water Caustic ClO Generator ClO2 2 Generator Saltcake Saltcake Filtration Filtration Saltcake Saltcake Dissolving Dissolving Heat Addition Heat Addition Water Air Saltcake Solution To Mill .

VACUUM PROCESS FLOW DIAGRAM HP Steam Vent System Ejector Vent Fan Filter Ejector Hot Water Saltcake Filter Filter Receiver Cooling Water Air Misc. Acid Feed Saltcake Sol. Pump Saltcake Filter Pump NaClO3 Feed To Bleach Plant Absorber Reducing Agent Feed Absorber Pump ClO2 Storage Condensate Pump . Vents Chilled Water System Condenser Deluge/Spray Quench Generator Generator Condenser Chilled Water Vent Scrubber Dissolving Tank Saltcake Soln. Pump Reboiler LP Steam Scrubber Pump Cooling Water Condensate Tank Condensate Generator Circ.

1 Filtration No.1 Saltcake Saltcake Recrystallizer Recrystallizer Water Caustic Heat Addition Heat Addition Filtrate Storage Filtrate Storage Saltcake Saltcake Filtration No.2 Saltcake Saltcake Dissolving Dissolving Water Air Saltcake Solution To Mill .2 Filtration No.VACUUM PROCESS FLOW DIAGRAM with Saltcake Washing Vent Vent Scrubbing Vent Scrubbing Chilled Water ClO2 Product Gas Condensing Gas Condensing Cooling Water Cooling Water ClO Storage ClO2 2 Storage ClO Absorption ClO2 2 Absorption Vacuum System Vacuum System HP Steam Cooling Water Cooling Water Sulfuric Acid Sodium Chlorate Methanol LP Steam Condensate Gas Condensing Gas Condensing Air ClO Generator ClO2 2 Generator Saltcake Saltcake Filtration No.

YIELD 100 Yield Components Yield (%) 99 98 97 96 Lite/R-8 SCW/R10 HP • Feeds – Chlorate Feed • Losses – Chlorate for side reactions – Chlorate in Saltcake – Chlorate lost as ClO2 in the vents 95 • Calculation Yield = (Feeds-Losses)/Feeds .

5 1 0.5 2 1.5 0 Lite SCW HP .SALTCAKE FILTRATION REQUIREMENTS 3 T Saltcake/T ClO2 2.

PROCESS TRADE NAMES Reducing Agent Acid NaCl H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 Acidity Low Low High Moderate Moderate High High High Low High High Salt Form Crystal Crystal Solution Crystal Crystal Crystal Solution Crystal Crystal Solution Solution Name By SVP-Conventional Eka R-3 Process Sterling R-2 Process Hooker SVP-Lite SVP-SCW R-8 Process Solvay R-10 SVP-HP HP-A Mathieson Eka Eka Sterling Solvay Sterling Eka Eka Olin-Mathieson CH3OH H2O2 SO2 .

16 0.06 1.06 .0 0.64 Chlorate.33 1. Ton/Ton ClO2 Salt Cake.44 1.64 Peroxide Based 1.Chemicals ITEM Methanol Based 1.PROCESS COMPARISONS .16 0.75 0. Ton/Ton ClO2 Sulfuric Acid. Ton/Ton ClO2 Reducing Agent. Ton/Ton ClO2 0.75 1.64 Methanol Based with Washing 1.

3 Methanol Based with Washing 5.0 89. Ton/Ton ClO2 Cooling & Hot Water. Ton/Ton ClO2 HP Steam.Utilities ITEM Methanol Based 4. Ton/Ton ClO2 Chilled Water.PROCESS COMPARISONS .92 1.2 298 341 292 .76 91.1 Peroxide Based 4.1 91.6 LP Steam. Ton/Ton ClO2 0.26 1.

KEY PROCESS CONTROL VARIABLES • Generator Level • Generator Chemistry • Generator Solids Level • Chemical Feed Flows • Generator Pressure • Generator Temperature • ClO2 Solution Concentration Do They correlate? .

25 2.73 6.50 1.91 6.41 1.13 1.10.94 1. Add these two numbers together.36 8.72 2.03 1.56 8.18 TARGET: 10.0 RANGE: 9.88 1.97 9.53 6.60 1.95 8.16 2.51 5.07 2.35 2.34 7.93 7.5 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.0 .82 NORMALITY 5. Make the appropriate chemical feed flow adjustment .32 6.30 5.RULE OF 10 GUIDELINES SODIUM CHLORATE GPL 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 SULFURIC ACID GPL 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 MOLARITY 0.75 7.32 1.10 5.44 2.22 1.97 2.14 7.54 7.12 6.79 1.16 8.69 1.71 5.54 2.77 8.63 2.

GENERATOR LIQUOR TARGET ZONE “Rule of 10” 7 6 Chlorate (M) 5 4 3 2 1 0 5 6 A+C=9 7 8 Acidity (N) White-Out Zone Sluggish Reaction 9 10 A + C = 11 11 A + C = 10 .

the level will decrease and generator concentrations will increase. • If an excess of water is boiled away in the generator.GENERATOR LEVEL CONTROL • Maintaining a constant level in the generator is critical for controlling generator concentrations. An inverse effect occurs when not enough water is boiled away. of lowpressure steam to the reboiler should be made to minimize level swings. generally 500#/hr or less. . • Also small adjustments.

• Change the steam flow at the same time you change the feed flows.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. • The changes in production rate must be done slowly. .

• • . The operation of a chlorine dioxide vacuum process is mill specific.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 key to smooth operation of a chlorine dioxide vacuum process is generator level control.

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