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ChemTreat Steel Seminar

September p 13, , 2012

Introduction to Purate for Chlorine Dioxide Applications pp

ChemTreats Steel Industry Water Conference 9-12 to 9-14-2012 , Clearwater Beach FL * Confidential * Do Not Duplicate without Permission

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. Dont 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 t technology h l Cooling water applications Biofilm and chlorine dioxide Chlorine dioxide benefits Discussion Di i
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AkzoNobel and Eka Chemicals

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Our company in brief


The worlds largest paint and coatings company and leading specialty chemicals supplier The worlds 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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Worlds Largest Sodium Chlorate Manufacturer


NaClO3 Plants in 7 Countries

Norway Canada U.S. S d Sweden France

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 - Chemical Production - Generator Manufacturing - 40+ years with ClO2 Trusted Water Treatment Partner - Applications Know How - Local Service & Support

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02

Chlorine Dioxide

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A few important dates


1811 - 14
Chlorine Dioxide discovered by Sir Humphrey Davy Patent granted for Pulp Bleaching Watt and Burgess

1854

1943 1940s 1970s 1999 2012

Used for potable water treatment in Niagara Falls, NY p mills in the US started using g chlorine Paper dioxide for pulp bleaching First used as biocide in cooling water

Purate small scale ClO2 Process Introduced Thats today Wait, no- something else!

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A few important dates


1811 - 14
Chlorine Dioxide discovered by Sir Humphrey Davy Patent granted for Pulp Bleaching Watt and Burgess

1854

1943 1940s 1970s 1999 2012

Used for potable water treatment in Niagara Falls, NY p mills in the US started using g chlorine Paper dioxide for pulp bleaching First used as biocide in cooling water

Purate small scale ClO2 Process Introduced 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 AkzoNobels 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

Chlorine Dioxide + byproducts

NSF Approved

Safe
Drinking Water
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For the chemists

Purate Chlorine Dioxide Process

NaClO3 + H2O2 + H2SO4

ClO2 + Na2SO4 + O2 + H2O

Purate

Reliable
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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 4 - 5 kg

Chl i Dioxide Chlorine Di id + byproducts b d t


1 kg

FDA Approved

Cost effective
Odor Control
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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 f free 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 Removal l 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?

Microbial Cells
Algae Fungus Bacteria

Suspended Solids
Dirt Particulate Iron Debris

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
SRBs

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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 of f (UFC/ (UFC/cm) )

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 Flow Vacuum ClO2

Acid

Purate

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What happens inside the AD SVP-Pure generator?

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Purate ClO2 Generators

Acid p Pump

Purate Pump p

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Purate ClO2 Generators

Acid Pump p

Purate 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 report Safety/interlock checks Customer feedback

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 + Cl2 NaClO2 + NaOCl + HCl 5 NaClO2 + 4 HCl NaClO2 + NaOCl + H2SO4 ClO2 + NaCl ClO2 + 1 NaCl + H2O 4 ClO2 + 5 NaCl + 2 H2O ClO2 + Na2SO4 + NaCl + H2O

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Primary ClO2 Processes


Chlorite NaClO2 + Cl2 NaClO2 + NaOCl + HCl 5 NaClO2 + 4 HCl NaClO2 + NaOCl + H2SO4 ClO2 + NaCl ClO2 + 1 NaCl + H2O 4 ClO2 + 5 NaCl + 2 H2O ClO2 + Na2SO4 + NaCl + 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 + Cl2 NaClO2 + NaOCl + HCl 5 NaClO2 + 4 HCl NaClO2 + NaOCl + H2SO4 ClO2 + NaCl ClO2 + 1 NaCl + H2O 4 ClO2 + 5 NaCl + 2 H2O ClO2 + Na2SO4 + NaCl + H2O

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Primary ClO2 Processes


Chlorite NaClO2 + Cl2 NaClO2 + NaOCl + HCl 5 NaClO2 + 4 HCl NaClO2 + NaOCl + H2SO4 ClO2 + NaCl ClO2 + 1 NaCl + H2O 4 ClO2 + 5 NaCl + 2 H2O ClO2 + Na2SO4 + NaCl + H2O

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Primary ClO2 Processes


Chlorite NaClO2 + Cl2 NaClO2 + NaOCl + HCl 5 NaClO2 + 4 HCl NaClO2 + NaOCl + H2SO4 ClO2 + NaCl ClO2 + 1 NaCl + H2O 4 ClO2 + 5 NaCl + 2 H2O ClO2 + Na2SO4 + NaCl + H2O

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Primary ClO2 Processes


Chlorite NaClO2 + Cl2 NaClO2 + NaOCl + HCl 5 NaClO2 + 4 HCl NaClO2 + NaOCl + H2SO4 ClO2 + NaCl ClO2 + 1 NaCl + H2O 4 ClO2 + 5 NaCl + 2 H2O ClO2 + Na2SO4 + NaCl + H2O

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57

Primary ClO2 Processes


Chlorite NaClO2 + Cl2 NaClO2 + NaOCl + HCl 5 NaClO2 + 4 HCl NaClO2 + NaOCl + H2SO4 ClO2 + NaCl ClO2 + 1 NaCl + H2O 4 ClO2 + 5 NaCl + 2 H2O ClO2 + Na2SO4 + NaCl + H2O

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Primary ClO2 Processes


Chlorite NaClO2 + Cl2 NaClO2 + NaOCl + HCl 5 NaClO2 + 4 HCl NaClO2 + NaOCl + H2SO4 Purate NaClO3 + H2O2 + H2SO4 Purate ClO2 + Na2SO4 + O2 + H2O ClO2 + NaCl ClO2 + 1 NaCl + H2O 4 ClO2 + 5 NaCl + 2 H2O ClO2 + Na2SO4 + NaCl + H2O

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Economics- The hard way


PRE-CURSOR ANALYSIS FOR CHLORINE DIOXIDE FROM SALT (NaCl) e-

(1) (2)

NaCl + H2O 3 NaOCl

NaOCl + H2 NaClO3 + 2 NaCl Chlorate based chemistry Chlorate-based

Time

Commercial chlorate (NaClO3) production via electrolysis of salt (NaCl)

Chlorite based chemistry Chlorite-based


(3A) NaClO3 + 2HCl
Efficiency = 90%

Purate
(3B) ClO2 + O2 + Na2SO4 + H2O

ClO2 + Cl2 + H2O + NaCl

Chlorine Dioxide Generation

NaClO3 + H2O2 + H2SO4


Efficiency y 95%

(4) 2ClO2 + H2O2 + 2NaOH 2NaClO2 + 2H2O + O2 (5) NaClO2 + Cl2


Efficiency 95%

Commercial Chlorite Production Re-Generation of Chlorine Dioxide from Chlorite

Chlorite Additional Step p2 Chlorite Additional Step 3

ClO2 + NaCl

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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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ChemTreats Steel Industry Water Conference 9-12 to 9-14-2012 , Clearwater Beach FL * Confidential * Do Not Duplicate without Permission

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
64

ChemTreats Steel Industry Water Conference 9-12 to 9-14-2012 , Clearwater Beach FL * Confidential * Do Not Duplicate without Permission

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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Typically suited for system volumes measured in hundreds of thousands, not thousands

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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 Energys 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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