Chlorine-Dioxide Application - Cehmtreat

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.
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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01
AkzoNobel and Eka Chemicals
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
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
Worlds Largest Sodium Chlorate Manufacturer

NaClO3 Plants in 7 Countries
Norway Canada U.S. S d Sweden France
Chile
Brazil
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!
13

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
14

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
15
Global Installations
16
US Installations
17
Top markets for ClO2
1 8
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
NaClO3 + H2O2 + H2SO4
ClO2 + Na2SO4 + O2 + H2O
Purate
Reliable
Industrial Water Treatment

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MASS: Pound for pound, kilo for kilo
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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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
24
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Reduced d d Acid d Usage Fl ibilit Flexibility

Continuous or Intermittent Feed
Bi fil R Biofilm Removal l and d Kill
25
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Water treatment issues
Mineral Scale Corrosion Fouling g Microbiological Contamination
26
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FIFRA Label
27
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FIFRA Label
EPA Registration Numbers
28
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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
30
What is biofilm?
Microbial Cells
Algae Fungus Bacteria
Suspended Solids
Dirt Particulate Iron Debris
Polysaccharides
Polymeric y Carbohydrate y
Water (>90%)
31
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Biofilm reactions
32
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Biofilm structure
HOCl- & HOBr- Repelled ClO2 Penetrates
ClO2 + MB
ClO2- + H+
ClO2
SRBs
33
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Case 2: Pipe with biofilm
34
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
35
Corrosion
36
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SVP-Pure ClO2 Generators
37
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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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Acid p Pump
Purate Pump p
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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
43
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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
44
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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
50
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
51

52
Purate advantages vs. chlorite

No chlorine gas 2 chemical process Efficiency Total cost Process safety Equipment quality No unstable feed chemicals Fewer deliveries
53

54

55

56

57

58

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
59
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
61
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.
62
Chlorine dioxide
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
64
Chlorine dioxide
65
Typically suited for system volumes measured in hundreds of thousands, not thousands
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.
67
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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
72
European twins
73
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Hometown water
74
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Clean in the mountains of Tennessee
75
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The Fort Knox for totes
76
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Wastewater Oxidation (cyanide) in China
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Chlorine-Dioxide Application - Cehmtreat

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ChemTreat Steel Seminar

September p 13, , 2012

Introduction to Purate for Chlorine Dioxide Applications pp

Behavior Based Safety

AkzoNobel and Eka Chemicals

Our company in brief

AkzoNobel Board of Management Corporate Staff

AkzoNobel Board of Management Corporate Staff

Pulp and Performance Eka Chemicals

Worlds Largest Sodium Chlorate Manufacturer

Norway Canada U.S. S d Sweden France

A few important dates

1943 1940s 1970s 1999 2012

A few important dates

1943 1940s 1970s 1999 2012

Purate small scale ClO2 Process Introduced Purate 13 years in 32 countries

A few important dates

Purate 13 years in 32 countries

Top markets for ClO2

How are Purate and chlorine dioxide related?

Purate + Sulfuric Acid

Purate Chlorine Dioxide Process

Purate + Sulfuric Acid

Chlorine Dioxide + byproducts

For the chemists

Purate Chlorine Dioxide Process

NaClO3 + H2O2 + H2SO4

ClO2 + Na2SO4 + O2 + H2O

Industrial Water Treatment

MASS: Pound for pound, kilo for kilo

Purate Chlorine Dioxide Process

Purate P t +S Sulfuric lf i A Acid id

Chl i Dioxide Chlorine Di id + byproducts b d t

Chlorine dioxide benefits

Non-reactive with h Ammonia

Less Corrosive No Microbial Immunity

Chlorine dioxide benefits

Cleaner l Cooling l System

Chlorine dioxide benefits

Reduced d d Acid d Usage Fl ibilit Flexibility

Bi fil R Biofilm Removal l and d Kill

Water treatment issues

Mineral Scale Corrosion Fouling g Microbiological Contamination

Case 1: Screen- Hypochlorite vs. ClO2

Case 2: Pipe with biofilm

Case 2: Pipe with biofilm

Pipe without ClO2 treatment

Pipe with ClO2 treatment

SVP-Pure ClO2 Generators

Purate ClO2 Generators

An Inside Look Look

What happens inside the AD SVP-Pure generator?

Purate ClO2 Generators

Purate ClO2 Generators

Off the shelf

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

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