ChemTreat Steel Seminar September p 13,, 2012
Introduction to Purate® for Chlorine Dioxide Applications pp
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Behavior Based Safety Your responsible for your safety behavior. When starting a task turn on your mental safety guard. Be mentally aware of unsafe conditions. Think about the task at hand. Don’t be distracted. Overconfident or indifference can cloud your thinking. Plan your work , work your plan.
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Agenda Introduction to AkzoNobel and the Eka brand Purate® and chlorine dioxide relationship SVP-Pure SVP P ® chlorine hl i di dioxide id generator t ttechnology h l Cooling water applications Biofilm and chlorine dioxide Chlorine dioxide benefits Di Discussion i ChemTreat’s Steel Industry Water Conference 9-12 to 9-14-2012 , Clearwater Beach FL * Confidential * Do Not Duplicate without Permission
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01
AkzoNobel and Eka Chemicals
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Our company in brief • • • • • •
The world’s largest paint and coatings company and leading specialty chemicals supplier The world’s largest sodium chlorate producer Employ around 59,000 people in more than 80 countries Revenue €15.4 billion Global Fortune 500 company Number one on recent Dow Jones Sustainability y Index
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Organization
AkzoNobel Board of Management Corporate Staff
Coatings BUs
Chemicals BUs
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Organization
AkzoNobel Board of Management Corporate Staff
Chemicals BUs
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AkzoNobel Organization
Chemicals BUs
Pulp and Performance Eka Chemicals
€1 Billion Sales
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World’s Largest Sodium Chlorate Manufacturer NaClO3 Plants in 7 Countries
Norway S d Sweden
Canada
France
U.S.
Chile
Brazil
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Global Chlorine Dioxide Leader - Chemical Production - Generator Manufacturing - 40+ years with ClO2
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Partnership
+ Global Chlorine Dioxide Leader
Trusted Water Treatment Partner
- Chemical Production
- Applications Know How
- Generator Manufacturing
- Local Service & Support
- 40+ years with ClO2
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02
Chlorine Dioxide
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A few important dates 1811 - 14
Chlorine Dioxide discovered by Sir Humphrey Davy
1854
Patent granted for Pulp Bleaching Watt and Burgess
1943
Used for potable water treatment in Niagara Falls, NY
1940’s
p mills in the US started using g chlorine Paper dioxide for pulp bleaching
1970’s
First used as biocide in cooling water
1999
Purate® small scale ClO2 Process Introduced
2012
That’s today… Wait, no- something else!
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A few important dates 1811 - 14
Chlorine Dioxide discovered by Sir Humphrey Davy
1854
Patent granted for Pulp Bleaching Watt and Burgess
1943
Used for potable water treatment in Niagara Falls, NY
1940’s
p mills in the US started using g chlorine Paper dioxide for pulp bleaching
1970’s
First used as biocide in cooling water
1999
Purate® small scale ClO2 Process Introduced
2012
Purate® 13 years in 32 countries
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A few important dates Purate® 13 years in 32 countries- Yes, we have been busy traveling the globe but more importantly… importantly customers have had the vision to see the inherent value of an oxidizing biocide that works better than chlorine and others in many applications
2012
Purate® 13 years in 32 countries
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Global Installations
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US Installations
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Top markets for ClO2
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How are Purate and chlorine dioxide related?
Purate® is AkzoNobel’s unique blend of sodium chlorate and hydrogen peroxide used for the onsite production of chlorine dioxide since 1999. AkzoNobel produces more sodium chlorate than anyone else.
Purate® + Sulfuric Acid
Chlorine Dioxide
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The basics
Purate® Chlorine Dioxide Process
Purate® + Sulfuric Acid
NSF Approved
Chlorine Dioxide + byproducts
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For the chemists
Purate® Chlorine Dioxide Process
NaClO3 + ½ H2O2 + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ O2 + H2O
Purate®
Reliable Industrial Water Treatment
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MASS: Pound for pound, kilo for kilo
Purate® Chlorine Dioxide Process
Purate P t ®+S Sulfuric lf i A Acid id 4.15 kg
Chl i Dioxide Chlorine Di id + byproducts b d t
4 - 5 kg
1 kg
FDA Approved
Cost effective Odor Control ChemTreat’s Steel Industry Water Conference 9-12 to 9-14-2012 , Clearwater Beach FL * Confidential * Do Not Duplicate without Permission
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Chlorine dioxide benefits
Non-reactive with h Ammonia • Does not form chloramines • Decreased halogen demand Up to 13 times more effective than chlorine
Less Corrosive No Microbial Immunity
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Chlorine dioxide benefits
Cleaner l Cooling l System • Less frequent Surface Condenser cleaning • Cleaner cooling tower Sump walls Tower fill Wooden structure
Environmentally Friendly • No trihalomethanes in discharge • “Chlorine “Chl i ffree”” process
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Chlorine dioxide benefits
Reduced d d Acid d Usage Fl ibilit Flexibility Continuous or Intermittent Feed
Bi fil R Biofilm Removall and d Kill
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Water treatment issues
Mineral Scale Corrosion Fouling g Microbiological Contamination
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FIFRA Label
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FIFRA Label EPA Registration Numbers
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FIFRA Label EPA Registration Numbers
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Case 1: Screen- Hypochlorite vs. ClO2 After change to ClO2
Hypo treatment
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What is biofilm?
Suspended Solids
Microbial Cells • • •
• Dirt • Particulate Iron • Debris
Algae Fungus Bacteria
Polysaccharides •
Polymeric y Carbohydrate y
Water (>90%)
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Biofilm reactions
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Biofilm structure HOCl- & HOBr- Repelled ClO2 Penetrates
ClO2 + MB
ClO2- + H+
ClO2 SRB’s
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Case 2: Pipe with biofilm
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Case 2: Pipe with biofilm Chlorine dioxide biocide treatment •90% reduction of incrustation in trial pipe • Anaerobic A bi bacteria b t i reduction d ti from f 107 to t 101 off (UFC/ (UFC/cm²) ²)
Pipe without ClO2 treatment
Pipe with ClO2 treatment
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Corrosion
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SVP-Pure® ClO2 Generators
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Purate® ClO2 Generators
An Inside Look Look… Water
ClO2
Flow Vacuum
Purate
Acid
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What happens inside the AD SVP-Pure® generator?
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Purate® ClO2 Generators
Purate® Pump p
Acid p Pump
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Purate® ClO2 Generators
Purate® Pump p
Acid Pump p
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Off the shelf
Generator controls -Remote R t Set S t Rate R t (Remote 4-20mA) -Flow Pacing -Remote Monitoring -M/C Set Rate (read/write) -Start St t / Stop St (toggle) -Motive Water Flow Rate (read) -Reactor Vacuum (read) -Actual Rate (read - if analyzer equipped) -ClO2 ClO2 conc. (read - if analyzer equipped)
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Why our customers like Purate®?
Safe - PHA Reliable Cost Effective Efficient
40+ yrs ClO2 experience Commitment to Safety Calibration Tubes
Quality construction Two chemical feeds No chlorine hl gas Easy to Operate
Manual or automatic Advanced controls 1 - 100 kg/hr ClO2 Flow pacing
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Why our customers like Purate®?
Safe - PHA Reliable Cost Effective Efficient
40+ yrs ClO2 experience Commitment to Safety Calibration Tubes
Quality construction Two chemical feeds No chlorine hl gas Easy to Operate
Manual or automatic Advanced controls 1 - 100 kg/hr ClO2 Flow pacing
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Keeping Safety at the Top
These 3 principles dominate our thinking
Safe
Purate Cost Reliable
Effective
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Material Handling
• Purate® is an oxidizer that can greatly aid combustion and has components of sodium chlorate and hydrogen peroxide. • Sulfuric Acid (H2SO4) is corrosive liquid that can cause skin irritation and burns • Chlorine Dioxide (ClO2)is a gas in solution that can cause skin irritation and is a vapor inhalation hazard
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Product Stewardship •Annual Site Audits •Sites are visited on a annual basis •Written Written report •Safety/interlock checks •Customer feedback
•Process Process Hazard Analysis •Each generator series has had a PHA •PHA updated as models progress •PHA available on web
•Technical Bulletins •Many topics including bulk storage, booster pump sizing, Purate® safety, safety sulfuric acid acid, stoichiometry and more •Bulletins included in manuals •Bulletins available to customer access area of web
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How can customers get Purate?
Purate is available in: • • • •
Bulk trailers ISO containers IBC totes Railcar
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Purate® Unloading Connection
The famous “Banjo” Banjo valve
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Be careful comparing ClO2 technologies
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Primary ClO2 Processes Chlorite NaClO2 + ½ Cl2
ClO2 + NaCl
NaClO2 + ½ NaOCl + HCl
ClO2 + 1½ NaCl + ½ H2O
5 NaClO2 + 4 HCl
4 ClO2 + 5 NaCl + 2 H2O
NaClO2 + ½ NaOCl + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ NaCl + ½ H2O
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Primary ClO2 Processes Chlorite NaClO2 + ½ Cl2
ClO2 + NaCl
NaClO2 + ½ NaOCl + HCl
ClO2 + 1½ NaCl + ½ H2O
5 NaClO2 + 4 HCl
4 ClO2 + 5 NaCl + 2 H2O
NaClO2 + ½ NaOCl + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ NaCl + ½ H2O
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Purate® advantages vs. chlorite • No chlorine gas • 2 chemical process • Efficiency • Total cost • Process safety • Equipment quality • No unstable feed chemicals • Fewer deliveries
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Primary ClO2 Processes Chlorite NaClO2 + ½ Cl2
ClO2 + NaCl
NaClO2 + ½ NaOCl + HCl
ClO2 + 1½ NaCl + ½ H2O
5 NaClO2 + 4 HCl
4 ClO2 + 5 NaCl + 2 H2O
NaClO2 + ½ NaOCl + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ NaCl + ½ H2O
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Primary ClO2 Processes Chlorite NaClO2 + ½ Cl2
ClO2 + NaCl
NaClO2 + ½ NaOCl + HCl
ClO2 + 1½ NaCl + ½ H2O
5 NaClO2 + 4 HCl
4 ClO2 + 5 NaCl + 2 H2O
NaClO2 + ½ NaOCl + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ NaCl + ½ H2O
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Primary ClO2 Processes Chlorite NaClO2 + ½ Cl2
ClO2 + NaCl
NaClO2 + ½ NaOCl + HCl
ClO2 + 1½ NaCl + ½ H2O
5 NaClO2 + 4 HCl
4 ClO2 + 5 NaCl + 2 H2O
NaClO2 + ½ NaOCl + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ NaCl + ½ H2O
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Primary ClO2 Processes Chlorite NaClO2 + ½ Cl2
ClO2 + NaCl
NaClO2 + ½ NaOCl + HCl
ClO2 + 1½ NaCl + ½ H2O
5 NaClO2 + 4 HCl
4 ClO2 + 5 NaCl + 2 H2O
NaClO2 + ½ NaOCl + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ NaCl + ½ H2O
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Primary ClO2 Processes Chlorite NaClO2 + ½ Cl2
ClO2 + NaCl
NaClO2 + ½ NaOCl + HCl
ClO2 + 1½ NaCl + ½ H2O
5 NaClO2 + 4 HCl
4 ClO2 + 5 NaCl + 2 H2O
NaClO2 + ½ NaOCl + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ NaCl + ½ H2O
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Primary ClO2 Processes Chlorite NaClO2 + ½ Cl2
ClO2 + NaCl
NaClO2 + ½ NaOCl + HCl
ClO2 + 1½ NaCl + ½ H2O
5 NaClO2 + 4 HCl
4 ClO2 + 5 NaCl + 2 H2O
NaClO2 + ½ NaOCl + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ NaCl + ½ H2O
Purate® NaClO3 + ½ H2O2 + ½ H2SO4
ClO2 + ½ Na2SO4 + ½ O2 + H2O
Purate®
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Economics- The hard way PRE-CURSOR ANALYSIS FOR CHLORINE DIOXIDE FROM SALT (NaCl)
(1)
NaCl + H2O
(2)
3 NaOCl
e-
Time
NaOCl + H2 NaClO3 + 2 NaCl
Chlorite based chemistry Chlorite-based
Chlorate based chemistry Chlorate-based
Efficiency = 90%
Purate® (3B)
(3A) NaClO3 + 2HCl
Commercial chlorate (NaClO3) production via electrolysis of salt (NaCl)
Chlorine Dioxide Generation
ClO2 + ½Cl2 + H2O + NaCl
NaClO3 + ½H2O2 + ½H2SO4 Efficiencyy 95%
ClO2 + ½O2 + ½Na2SO4 + H2O
(4) 2ClO2 + H2O2 + 2NaOH
2NaClO2 + 2H2O + O2
Commercial Chlorite Production
Chlorite Additional Step p2
(5) NaClO2 + ½Cl2 Efficiency 95%
ClO2 + NaCl
Re-Generation of Chlorine Dioxide from Chlorite
Chlorite Additional Step 3
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Chlorine Dioxide
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Chlorine dioxide Chlorine dioxide is a chemical used as a biocide for disinfection in water, an odor control agent in the rendering industry and as a bleaching agent in the paper industry. industry, industry Chlorine dioxide (formula ClO2) is known as an excellent slimicide, but it must be generated onsite due to transportation restrictions imposed from the D.O.T.
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Chlorine dioxide Chlorine dioxide is a chemical used as a biocide for disinfection in water, an odor control agent in the rendering industry and as a bleaching agent in the paper industry. industry, industry Chlorine dioxide (formula ClO2) is known as an excellent slimicide, but it must be generated onsite due to transportation restrictions imposed from the D.O.T. • Steel •Drinking water disinfection • THM reduction in drinking water • Fe and Mn removal • Cooling tower biocide • Pulp bleaching • Rendering scrubbers • Odor control • Ethanol production • Ship ballast water treatment • Phenol, cyanide, H2S destruction • Food processing • Wastewater treatment • Paper machine slime control
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Chlorine dioxide Chlorine dioxide is a chemical used as a biocide for disinfection in water, an odor control agent in the rendering industry and as a bleaching agent in the paper industry. industry, industry Chlorine dioxide (formula ClO2) is known as an excellent slimicide, but it must be generated onsite due to transportation restrictions imposed from the D.O.T. • Steel •Drinking water disinfection • THM reduction in drinking water • Fe and Mn removal • Cooling tower biocide • Pulp bleaching • Rendering scrubbers • Odor control • Ethanol production • Ship ballast water treatment • Phenol, cyanide, H2S destruction • Food processing • Wastewater treatment • Paper machine slime control
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Chlorine dioxide Chlorine dioxide is a chemical used as a biocide for disinfection in water, an odor control agent in the rendering industry and as a bleaching agent in the paper industry. industry, industry Chlorine dioxide (formula ClO2) is known as an excellent slimicide, but it must be generated onsite due to transportation restrictions imposed from the D.O.T.
Typically suited for system volumes measured in hundreds of thousands, not thousands……
• Steel •Drinking water disinfection • THM reduction in drinking water • Fe and Mn removal • Cooling tower biocide • Pulp bleaching • Rendering scrubbers • Odor control • Ethanol production • Ship ballast water treatment • Phenol, cyanide, H2S destruction • Food processing • Wastewater treatment • Paper machine slime control
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Power Generation
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Power Generation Water Consumption
41% of freshwater withdrawals 136 – 277 billion gallons of fresh water a day to cool U.S. thermal power plants * per U.S. Department of Energy’s National Energy Technology Laboratory.
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Reclaimed water
Grey Water Water source made up of partially or fully treated sewage effluent • • • •
Ammonia Biological Oxygen Demand (BOD) Suspended Solids Phosphate
57 Facilities in the USA 30 facilities in California and Florida * as of 2007 per U.S. Dept. of Energy
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Reclaimed water
Grey Water Demand
…….Projected to grow from 1.7 billion gallons in 2001 to 12 billion gallons by 2015
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Power Generation
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Italian trifecta!
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In the Middle East
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European “twins”
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Hometown water
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Clean in the mountains of Tennessee
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The Fort Knox for totes
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Wastewater Oxidation (cyanide) in China
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