Centrifugal Smearing Qualitiy

the
FlexPro™ CL
Koch/Invista/Flint Hills Resource Training Seminar
July 30th, 2014
© ChemTreat, Inc. 2014
Confidential – Do Not Duplicate
Topics
• Brief history of corrosion inhibitors
• Difficulties with phosphate programs
• Environmental issues with common inhibitors
• Development of a non‐phosphate scale inhibitor
• Development of a non‐nutrient corrosion inhibitor
• FlexPro™ CL lab data
• Field applications
Confidential – Do Not Duplicate 2
Historic View of Cooling Water Treatment
• Prior to 1980 ‐ Chromates
– Excellent Corrosion Inhibitor
• For steel
• Also for copper and other metals
• Most heat exchangers carbon steel
– Non‐fouling
• 50 ppm Excellent
• 500 ppm, even better
• Could not be overfed
• Broad control range
– Programs operated at pH 6.0‐7.0
• No scale
• The non‐chromate world
– Phosphates
• Weaker corrosion inhibitors
• Operate at less corrosive higher pH
– Higher pH water is more scale forming
• Organic phosphates (phosphonates and
phosphinates) are the most common
calcium carbonate scale inhibitors
Carbon Steel Corrosion Inhibitors
Contain phosphorus Heavy Metals
• Phosphoric acid • Zinc
• Organophosphonates • Molybdenum
• PolyPhosphate
Nutrient rich – requires heavy Banned or limited in discharge

use of halogens to combat algae due to toxicity at high levels in
and micro‐organisms the environment and bio‐solids
Development of FlexPro CL ™ Cooling Water Technology
What is wrong with using phosphate based inhibitors?
Phosphorus
The Trouble With Phosphate
• Difficult to control
– Must balance: Phosphate, Calcium, Polymeric Dispersant, pH, & Temp.
• Too much  Fouling on heat transfer surfaces
• Not enough  Corrosion
• Only effective on steel
– Minimal effect on copper alloys and aluminum
– Co$t of azoles and bromide to control copper corrosion
• Precipitates with well‐water iron and aluminum from clarifier carryover
– Iron and aluminum consume phosphate and form deposits
– Increases polymer demand and Co$t
• Fouling on scorching hot chemical process heat exchangers
– Requires extra polymer  Co$t
• Has trouble with low hardness waters
– Requires calcium to form calcium phosphate film
– Low hardness water requires high phosphate  Co$t
• Algae and Cyanobacteria nutrient
– Increased chlorine and biocide demand Co$t
– High chlorine increases corrosivity
– Fix organic carbon in water as nutrient for bacteria
Professor Justus Von Liebig
• 1803 –1873
• German Chemist
• “Father of the fertilizer industry“
• Credited with developing ‐
Liebig's Law of the Minimum,
“Growth is controlled not by the total
amount of resources available, but by
the scarcest resource (limiting factor).”
Growth Of Cyanobacteria ( PNK)
• Phosphorus
• Nitrogen
• Potassium
• Nutrients allow growth in
waters used for cooling as
well as the surface water
and waterways where it is
discharged
Limit the Nutrient – Limit the Organism
Phosphorus is usually the limiting nutrient for cyanobacteria & algae
CyanoBacteria Algae
(“blue‐green algae”) Eukaryotes ‐ Nucleus
Filamentous and Planktonic
Prokaryotes ‐ No Nucleus
Both Algae and Cyanobacter
Produce Cyanotoxins convert inorganic bicarbonate to
Planktonic or Filamentous organic carbon
Can “fix” nitrogen into water
Rapid die‐off consumes D.O., which affects aquatic life
State Pollutant Discharge Elimination Systems
• In 1972 the US EPA introduced the NPDES – national
pollutant discharge elimination system
– Administered by authorized states
– Requires limits on “pollutants” in discharge
• ChemTreat’s low nutrient corrosion inhibitor technology
(FlexPro™ CL) contains no components that are
traditionally regulated as pollutants by the US EPA in
water discharges
Cyanobacteria “Blue‐Green Algae”
Basis for Emerging Nutrient Regulations
• USEPA – Nutrients are the
cause of degradation in half
the impaired waterbodies
– Associated with algae blooms, low
D.O., fish kills, sediment
accumulation, shifts in flora and
fauna
– THM’s associated with algal
density
– Associated with “dead zone” in
Mississippi River Drainage
Source: USGS Circular 1350 – Nutrients in the
Nations Streams and Groundwater, 2010
Reduced Biocide Demand and Chlorine
Phosphorus is usually the limiting nutrient for algae
No P  No algae  Less chlorine  Less corrosion
Excessive and Poor Use of Oxidizers
What is wrong with using molybdenum and zinc as inhibitors?
Molybdenum and zinc pollution
Zinc and Molybdenum
• NPDES limits created to prevent toxic levels from
building up in the environment
• High levels of zinc can cause health problems,
including skin irritation, vomiting, nausea and
anemia and at worst can the pancreas and affect
protein metabolism
• Molybdenum can cause mineral deficiency and
causes a well documented illness called
molybdenosis
Zinc and Molybdenum
• While chances of human exposure to toxic levels are low, zinc
and molybdenum do impact the environment
• Molybdenum has been banned in some states, as some
waste water treatment facilities recycle solids for fertilizer
• Where bio‐solids are used, molybdenosis has caused mineral
deficiencies in cattle and sheep, to the point of severe illness
and death
Necessity is the Mother of Invention – FlexPro CL ™
We needed another tool in the toolbox!
• Emerging Water Quality regulations
– New Aquatic Nutrient limits on Phosphorous
• TMDL restrictions being incorporated into new NPDES
effluent permits
– Existing Aquatic toxicity limits on Zinc
– Driving Non‐P, Non‐Zn cooling program
development
• Non‐P, Non‐Zn product will not foul
– Similar to chromates, nitrites, and molybdates, FlexPro ™ CL cannot be overfed
– Will not precipitate on high heat transfer areas
– Effective on steel, copper alloys, and aluminum
• Practically non‐toxic to aquatic life
– LC50 ‐ 3,536 ppm Fathead Minnow
– LC50 ‐ 2,967 ppm Ceriodaphnia
What is wrong with using molybdenum and zinc as inhibitors?
Creating a New Inhibitor Package
Development of a Non‐P Scale Inhibitor
• Pilot Cooling Towers used for development work
– 15 gallon sump – evaporates 45 gallons daily
– 100 oF cold supply temp; 107.5 oF hot return temperature
– Heat exchanger skin temperatures = 135 oF to 142 oF
– Heat Flux 26,100 Btu/hr‐ft2
– Visible heat exchanger surface to view scale formation
• Performance expected to depend on water quality
– Evaluated both moderate hardness and low hardness waters
• Two identical pilot cooling towers were dedicated to
the study
• Cycles of concentration stepped up gradually over 3
weeks
– 1 Cycle every 2‐ 3 days up to 4 cycles
– 0.5 Cycle every 3‐days above 4 cycles
• Each run continued until a “crash point” was reached
– Precipitation on heat transfer tubing and in bulk
water
• Heat flux – 26,100 Btu/hr‐ft2; 4 fps (1.2 m/s)
• Skin temp – 135‐142 °F (57‐61 °C);
• Hot bulk water temp. 107.5 °F (41.9 °C); Cold bulk
water temp 100 °F (37.8 °C)
Best programs  5.5 cycles , >500 ppm Calcium, >500 ppm alkalinity
Makeup Water Quality
Scale Development
at Breakpoint
LSI = 2.96
Larson‐Skold = 1.2
Best programs  5.5 cycles , >500 ppm Calcium, >500 ppm alkalinity
Final Formulations Are Effective Scale Inhibitors
LSI: 2.9
100
90
• Controls scale formation in
once through and open
80
evaporative cooling
% CaCO3 Inhibition
70
systems
60
50 • pH control not required
40
30
• Compatibility with
halogens
20
10
• Thermally stable
0
100ppm 150ppm 200ppm 5ppm 32ppm 48ppm 64ppm
CL5632 CL5632 CL5632 PBTC Comp Comp Comp • Very high Ca tolerance
Treatment
Development of a Non‐P Corrosion Inhibitor
• Testing over 4 years was
performed on hundreds of
materials and endless
combinations
• Various tools were used to
evaluate the effectiveness
– Potentistat
• Linear Polarization
• Cyclical polarization
– Spinner Bath
• More dynamic conditions
• 3 day exposure time
– Pilot Cooling Towers and Closed Loops
• Longer exposure time
• Simulates real conditions
How Inhibitors Protect The Metal Surface
Metal surface
+
Inh2+
Inh2+ Inh4+
OR Inh2+ + 2OH‐ → Inh(OH)2
(Fe(Inh)O3)
Protective barrier
Pin‐hole
Film breakdown
Inh2+ Inh4+
Linear Polarization – Comparison With Phosphate
4.5 Control
65ppm CL5632
100ppm CL5632
4.0
30ppm CT708 + 70ppm CL4892
130ppm CL5632
3.5
Corrosion Rate on C1010 / mpy
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0 2 4 6 8 10 12 14 16 18
Time / hr
100ppm CL5632 provides corrosion rates similar to the conventional treatment
Anodic PLUS Cathodic Protection
Mixed, film-forming inhibitor
Effective On Copper Alloys
Synergistic With Traditional Azoles
Alternative Feed Methods – Shot Feed
Higher Corrosivity Requires More Inhibitor
pH: 9.0
9
pH: 8.5
Mild Steel
8.5
Copper
pH: 8.0
pH
7.5
pH: 7.5
0 1 2 3 4 pH: 7.0
Corrosion rate / mpy
© ChemTreat, Inc. 2014 30
Works in High Chloride
Ashland tap + 100ppm CaH + 100ppm Malk +
Chloride – pH 8.0
500
Mild steel
Copper
Chloride / ppm
300
100
0 0.5 1 1.5 2
Corrosion rate / mpy
Soft Water FlexPro ™ CL Program Development
Laboratory Corrosion Study Results
3‐Day exposure at 50 °C (122 °F)
Untreated – 60 mpy Non‐P program < 1 mpy
• Several hundred Non‐P Candidates Screened Over 4 Years
• Best Non‐Phosphorus programs produced < 1 mpy Steel, < 0.1 mpy Copper
• 100x Reduction in steel corrosion rate !!!
Spinner Bath Testing vs. Phosphate
pH 8.0 ‐8.2, 200 ppm Ca (as CaCO3), 150 ppm SO4=, 350 ppm Cl‐, 0.2 ppm FAC
Phosphate Program:
Organic P, Poly P, Ortho P Copper: 0.23 mpy
Polymer, Azole Steel: 2.1 mpy
100 ppm total products
FLexPro™ CL Product Copper: 0.35 mpy
65 ppm with azole Steel: 4.05 mpy
FlexPro™ CL Product Copper: 0.13 mpy
FlexPro™ Product Copper: 0.07 mpy
Aluminum Corrosion Inhibition
Initial water analysis for 3‐day Effectiveness of FlexPro ™CL chemistry

aluminum spinner bath study on aluminum corrosion
Sodium Chloride Brine
146,000 ppm Cl‐, 106,770 ppm Na+, pH 9.0
Before Cleaning After Cleaning
Control
CR: 65 mpy
3000 ppm CL2852
(300 ppm NO2=)
CR: 45 mpy
3000 ppm FlexPro ™CL2632
“open” system (with DO)
CR: 1.5 mpy
3000 ppm FlexPro ™CL2632
Under nitrogen blanket
CR: 0.59mpy
Field Trials
FlexPro™ CL Soft Water Evaluation
Southeast HVAC System Coupons Before & After Cleaning:
64‐Day Exposure
Copper ‐ <0.01 mpy
• Small two‐cell evaporative cooler Mild Steel ‐ 1.4 mpy
• Excessive corrosion due to fluctuating
cycles, treatment concentration, and
halogen residual
– Soft, very corrosive water
• Analysis in the paper
– 4.6 mpy during Spring and Summer
– Zinc was not allowed by permit
– Improved automation cost prohibitive
• FlexPro™ CL program was evaluated
– Wider operating window
– Non‐P, Non‐Zn programs have low fouling
tendency
• Results:
– Steel corrosion reduced – 4.6 mpy  1.4 mpy
– Copper corrosion rate <0.01 mpy
– No deposition on coupons or heat exchangers
FLexPro™ CL Outperformed Standard Phosphorus Program
Midwest Cogeneration Plant Evaluation
High Hardness, High
Sulfate Corrosive Water
Previous Low P Program
FLexPro™ CL Program
2 mpy Average Steel, 0.1‐0.2 mpy Copper
Application At Gulf Coast Chemical Plant
• 9‐Cycle Sabine River
– Moderately corrosive Initial 35‐day steel coupon – 1.07 mpy
• Corrosion rates excellent on conventional
phosphate program, <1 mpy
– Challenging to stay within control band
• Several high temp shell‐side heat exchangers
– Prone to deposition
• Evaluated FlexPro ™ CL program to eliminate
deposition and for ease of control
• Results excellent after 3 ½ months
– Approach temps flat to improving
Water Analysis
Initial 99‐day steel coupon – 0.32 mpy
Application At Gulf Coast Chemical Plant
Most recent 73‐day carbon steel coupon 1/14‐2014‐3/27‐2014
CL‐41 NaBr also reduced by 70%
High Well Water Iron – Air Separation Plant
• Well water iron is a particular challenge for phosphate‐based programs
– Precipitates phosphate corrosion inhibitor and renders it ineffective
– Results in iron phosphate deposits and creates additional demand for the dispersant polymer
• Plant well water has 2‐5 ppm iron
• Required outage to clean fouled heat exchangers
– Evaluated Phosphorus‐Free program to reduce deposits and control corrosion
Phosphate Program FlexPro ™ CL Program – First 35 Days

Heavy Deposits and Corrosion No deposits
1.07 mpy Steel, 0.31 mpy, Cu 0.68 mpy Adm
High Well Water Iron – Air Separation Plant
Tower Water Analysis Approach Temperature (°F)
40
20
Second Set Coupons:
Improved control
77‐Days, 90:10 Cu:Ni – 0.11 mpy
0
Significant improvement in approach temps
Steam Jacketed Vessel Cooling System
• Alternate steam heating and
water cooling of jacket Cooling tower iron for jacketed vessel cooling system
– Steam transitioning to FlexPro ™CL program overlay
• No corrosion inhibitor
• High temp
– Cooling Water
• Oxygenated
• High conductivity
– Passive film from the cooling cycle
must persist through the steam
cycle
– Overlaid Phosphate with Non‐P
Cooling Tower Chemistry for Jacketed Vessel
Sharp reduction in iron corrosion products
Aquatic Effects and EH&S
• Initial goal to develop an • Environmental Health & Safety
environmentally sustainable – Most products in the FlexPro™
alternative to phosphate CL family formulated at pH 3.0 ‐
– Requires minimal aquatic effects 3.5
as well as non‐P (& non‐Zn)
– Less hazardous than most
• Range of FlexPro ™ CL products it replaces
Products
– Typical “100 ppm” product • Strong alkali, pH >12
• Ceriodaphnia – 2,967 mg/L LD50 • Strong acid, pH <2
• Minnow – 3,536 mg/L LD50 – Only two MSDS “hazardous”
– 3,500 mg/L 7d NOEL
ingredients are listed as EPA
• Non‐P and Non‐N product Green Circle “Safer Ingredients”
– No acrylamide or AMPS – No flash point
– No azole
– Not DOT regulated
– 100 ppm product
• Ceriodaphnia – 3,700 mg/L LD50 – No California Prop 65
• Minnow – 6,300 mg/L LD50 – HMIS rating 1‐0‐0‐X
Confidential – Do Not Duplicate • 0‐4 Scale
Conclusions
A non‐phosphorus cooling water treatment is now available:
• Non‐fouling, with a broad control band
• Does not contribute to algae growth
– In the tower
– In the environment
– Non‐N is also available
• Effective in low hardness to high hardness waters
• Effective on steel, copper, and aluminum
• Not affected by well‐water iron or aluminum carryover
• Has minimal aquatic effects and a favorable EH&S profile
Richard Tribble
Prasad Kalakodimi

Centrifugal Smearing Qualitiy

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Nutrient rich – requires heavy Banned or limited in discharge

Necessity is the Mother of Invention – FlexPro CL ™

Untreated – 60 mpy Non‐P program < 1 mpy

Initial water analysis for 3‐day Effectiveness of FlexPro ™CL chemistry

Phosphate Program FlexPro ™ CL Program – First 35 Days

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