Dihydrogen OxideDihydrogen OxideTreatment ChemicalsTreatment Chemicals

BRENNTAG SOUTHWEST – Houston TexasBRENNTAG SOUTHWEST – Houston Texas

Capitol Area TWUA

May 17th 2016Glenn E. Gosnell

OutlineOutline

• Introduction

• Discussion of all the 28 different chemicals used for water and waste water treatment

and SAFETY CLASIFICATIONS

BASIC CHEMISTRY 101BASIC CHEMISTRY 101• ELEMENT – IC’S - ATE’S – IDE’S – ITE’S

• SULFUR – Sulfuric Acid - Sulfate – Sulfide – Sulfite

• CHLORINE –Hydrochloric Acid - Chlorate–Chloride– Chlorite

• NITROGEN – Nitric Acid - Nitrate – Nitride – Nitrite

OTHER NAMES ELEMENTSOTHER NAMES ELEMENTS• CALCIUM – calcite – caliche - LIME• OXYGEN – oxides – ozone – hydroxide - dioxide• HYDROGEN – hydrate – hydride – hydroxide• SODIUM – Sodium Hydroxide = Caustic Soda Names of common chemicals used in W & WW• Hydrogen Sulfide (H2S) – Aluminum Sulfate

(Al2o3 So4)– Aluminum Chloride – Calcium Hydroxide (CaOH) – Ferric Sulfate (Fe3)

Basic Categories for Water & WW Basic Categories for Water & WW TreatmentTreatment

OXIDANTS COAGULANT / FLOCCULANTS

CONTROLERS1 LONER

28 Basic Chemicals / 100’s of Varieties

OxidantsOxidantsConvert Hydrogen Sulfide to Sulfur Convert Hydrogen Sulfide to Sulfur

Ozone (O3)

Chlorine Dioxide (CLO2)

Chlorine (CL)Permanganate (Na-MnO4)

Hydrogen Peroxide (H2O2)

OZONE (OOZONE (O33) ) Inhalation / Combustible Inhalation / Combustible HazardHazard

• Strongest Oxidant Available• On site generation / high electricity use• Two – (2) types of generators

– Liquid Oxygen Tank on site for O supply– Self Producing (less expensive for long term)

• Note: Hydrogen Peroxide addition of ~ 2 mg/L can enhance Ozone (Peroxzone) which produces a radical hydroxyl that is effective for some Taste and Odor compounds and improves efficiencies of an O3 system.

• Effective for cryptosporidium, color, some taste & odor compounds

• Can be used for H2S control in lift stations – corrosive.

Chlorine Dioxide (ClOChlorine Dioxide (ClO22) Hazardous) Hazardous22ndnd Strongest Oxidant Strongest Oxidant

Manufactured on site by using Sodium Chlorite 1 of 3 methods are utilized to produce CL02.

1.) Liquid Sodium Chlorite & Chlorine:

CLO2 generator produces a 2- 3000 PPM injection solution. Bleach can be used along with hydrochloric acid also, but it is problematic.

2.) Electrolytic:

No Chlorine (same manufacturing method for chlorine), however it is not as efficient as chlorine & 25% Sodium Chlorite.

3.) Hydrogen Peroxide / Sodium Chlorate (blend) & Sulfuric Acid:

Mixed to produce CL02. El Paso TX uses this type of CL02 generation. The system is not economical until a 10 MGD flow. Paper mills use this high volume method of CLO2 production for bleaching pulp.

Primarily utilized as an alternate disinfectant in water plants to help Control TTHM formation. CL02’s forte is injection into a raw water transmission line with a minimum of 20 minutes detention time to achieve a 3.5 log removal credit.

CL02 is also very effective on certain types of taste and odor (geosmine excluded) Can be used for WW H2S odor control – normally not economical

CLO2 SOLUTION IS VERY COMBUSTABLE (FUMES) / SODIUM CHLORITE AN OXIDANT – DANGEROUS HAZARD WHEN DRY

Obstacle Drinking Water: residual Chlorite, it must be maintained below 1.0 mg/L and Chlorite monitoring is tightly regulated. Ferrous Chloride can be used to reduce Chlorite residuals. Chlorite is beneficial for bio-film control in distribution systems.

CLO2 injection prior to Ozone is extremely effective on T&O and also eliminates Chlorite residuals

Chlorine (CLChlorine (CL22) ) Extreme HazardExtreme Hazard

– Liquid Chlorine (Gas): Bulk, Ton Containers and 150 lb cylinders

– Bleach: Sodium Hypochlorite / can be used for H2S control in lift stations – expensive but effective.

– Electrolytic: Same process the Chlorine manufactures use, produced on site using pure salt and electricity

– DRY: Calcium Hypochlorite (HTH)

Chlorine is manufactured from salt (Sodium Chloride) primarily mined along the Gulf coast by washing out or mining the salt domes which are 1000 to 15000 feet below the surface. The washed out domes are then used to store petrol of all types, including the strategic oil supply.

Chlorine is manufactured using the electrolytic process and energy cost reflect pricing

The water industry uses approximately 5% of the chlorine manufactured, most CL production goes into plastics (PVC & CPVC) and house hold cleaners and a multitude of products.

The manufacturing process produces 2 pounds of Caustic Soda (NaOH) for every 3 pounds of chlorine.

Chlorine is the primary disinfectant in most water treatment plants in the country. Free Chlorine is used in well water and most Surface water plants use Chloramines…a combination of chlorine and ammonia.

PermanganatePermanganate / Potassium & Sodium / Potassium & SodiumOxidant / HazardousOxidant / Hazardous

• No CT credits / beneficial though• Great for Taste and Odor (geosmine MIB) potable water• SUV and DOC reduction• Good for Iron and Manganese oxidation / Well Water & Surface • Odor control WW - H2S instant conversion to sulfur for lift stations /

anaerobic sludge / belt presses• Manganese is used in the manufacturing process• Liquid Sodium Permanganate – easier application – more expensive• 20 minutes for oxidation to complete for both types• Bio-film control in transmission lines• Careful not to over dose• Long term use can cause Mn accumulation in recycled waters • Hazardous – dust inhalation – will catch clothing / pants on fire!!!!• DO NOT STORE NEAR HYDROCARBONS OR ORGANICS

Hydrogen Peroxide 35-50%Hydrogen Peroxide 35-50%HH22OO2 / 2 / OxidantOxidant & Controller & Controller

• Ozone enhancement / radical hydroxyl• No effect on Manganese – Fe marginal • Great for particular Odor compounds in surface water• Primarily used in Waste Water Odor Control

Breaks down Hydrogen Sulfide (H2S) to elemental Sulfur in 20 minutes and feeds aerobic bacteria

• Detaches Bio-Film / Clams transmission lines – be careful! • No affects on water chemistry / very hazardous

COAGULANTS / FLOCCULANTSCOAGULANTS / FLOCCULANTSMetals / Organics - FlocculentsMetals / Organics - Flocculents

• Aluminum Sulfate • Aluminum Chloride – PACL & ACH • Ferric Sulfate (fe3) & Ferrous Sulfate (fe2)• Ferric Chloride & Ferrous Chloride• Polymers – Poly -Dadmac – Epi-Dadmac (Organic)• Copper Sulfate • Blends of the above• Polymers – Emulsions & Dispersants (true Flocculants- Organic)• Bentonite Clay – coagulant assistance (drilling mud for oil wells)• Sodium Aluminates' – rare for Minnesota area

Aluminum Based CoagulantsAluminum Based CoagulantsSlightly Hazardous – Acidic Slightly Hazardous – Acidic

Aluminum Sulfate 4% Al (liq)• Reduces pH / Alkalinity

7.6 pH or lower for good filter results• Blended w/ Dadmac and Epi polymers

for enhanced performances• Sludge Handling• Can not be polymerized• < 50F (10C) water treatment difficult• Blended with Copper Sulfate for algae

control• Can be blended with silica for waste

water treatment• Acid Alum – contains free Sulfuric Acid

Aluminum Chloride 4% Al• Polymerized into Poly-Aluminum

Chloride (PACL) 5% to 13% AL• PACL is an INORGANIC POLYMER• PACL – minimal pH and alkalinity

reduction – 8.3 pH or lower for good results

• Blended w/ polymers• Reduces sludge up to 90%• Generally works better in colder water

than Alum• Blended with Copper Sulfate / algae

control • Many different varieties / manufactures• Very corrosive to metals / Stainless Steel

Iron (Ferric) CoagulantsIron (Ferric) Coagulants Slight HazardSlight Hazard

Ferric Sulfate• pH & Alkalinity reduction• pH range < 9.5• Sludge disposal easier• Stains surfaces red• Good for cold water• Ferrous Sulfate – Odor

Control in WW only• Can be blended with

polymers

Ferric Chloride• pH & Alkalinity reduction• pH range <9.5• Extremely corrosive

(liquid sand paper)• Stains surfaces red• Good in cold water• Ferrous Chloride (Chlorite

reduction for surface plants using CLO2)

ORGANIC POLYMERSORGANIC POLYMERSRefined from Crude Oil – Non Hazardous- Refined from Crude Oil – Non Hazardous- Slipping HazardSlipping Hazard

Polydiallydimethlammonium Chloride (Poly-Dadmac)

• Short Chain Positive (cationic) polymers – low – medium – high (molecular weights) (single monomer)• 10% – 20% – 40% solids – price & dose• Most common for surface water treatment and primary clarifiers in WW• Can be used as both coagulant and flocculent• Used in alum & ferric blends• Good for color removal

Epi-Dadmac

• Cousin of the Poly-Dadmac – same in molecular weights & cationic charge (double monomer)• Can perform much better than Poly - Dadmac in some waters – coagulant & flocculent• Good for color removal• Used in coagulant blends also

Emulsion Polymers / True Flocculent

• Primarily used for WW Belt pressing – very long chain• Comes in dry and liquid form – many different types• Three charges – Anionic (negative -) Cationic (positive + ) & Non-Ionic (Both + & -)• Used in surface water treatment as flocculent – (NSF Certified) mostly up-flow clarifiers @ 0.2 -1.0 mg/L

Charge NeutralizationCharge NeutralizationSuspended Colloidal Particles

No Coagulant AddedNeutralized Colloidal Particles (NCP)

After the Addition of Coagulant

Uncharged Particles are free to collide and aggregate

-ve

-ve -ve

-ve

-ve -ve-ve

-ve

NCPNCPNCP

NCPNCP

NCP

NCP

NCPNCP

NCPNCP

NCP

NCP

NCP

NCP

NCP

NCP

NCPNCP

NCP

NCPNCP

NCP

NCP

Charged Particles repel each other

Sodium AluminatesSodium AluminatesSlightly Hazardous Slightly Hazardous

• Made using Caustic Soda instead of Sulfuric Acid or Hydrochloric Acid

• Only known use for water treatment is in 0 alkalinity low pH waters (Minnesota)

• Raises pH & alkalinity during coagulation• Primarily used in the wet end paper mill

process

BENTONITE CLAYBENTONITE CLAYNon-Hazardous Non-Hazardous

• Used to provide heavier floc in surface water plants with low turbidity raw water

• Primarily used in Up-Flow Clarifiers• Drilling mud for the oil field• Some Bentonite Clay comes with (dry)

emulsion polymer mixed in for larger floc formation

CONTROLERS’CONTROLERS’pH - Alkalinity, Odors, Corrosion, AlgaepH - Alkalinity, Odors, Corrosion, Algae

• Caustic Soda – Sodium Hydroxide (pH - Alk)• Caustic Potash – rare for pH (cold weather) (blend of soda ash)• Lime – Calcium Hydroxide – pH – Alkalinity - softening• Soda Ash – Calcium Carbonate (alkalinity & pH)• Baking Soda – Calcium Bicarbonate (rare for alkalinity)• Ammonia – Anhydrous, Aqueous, & L.A.S. (DBP Control)• Nitrates: Sodium & Calcium (WW Odor Control)• Magnesium Hydroxide: (WW Odor Control)• Activated Carbon – PAC (odor T.O.C. reduction) GAC• Hydrogen Peroxide – bio-film – odor control W&WW - oxidation• Copper Sulfate – algae control / coagulation Marine Hazard• Phosphates – corrosion control – sequestration (pb,Mn,fe,cu)• Carbon Dioxide – pH adjustment – softening – pH reduction

CAUSTIC SODACAUSTIC SODANaOH – Sodium Hydroxide - NaOH – Sodium Hydroxide - Corrosion / Fe & Mn ControlCorrosion / Fe & Mn Control

VERY HAZARDOUS VERY HAZARDOUS

• IF YOU GET CAUSTIC IN YOUR EYES IT CAN BLIND YOU

• Bi-product of Chlorine manufacturing• Raise pH - alkalinity for corrosion control• Cleaning Filter Media• Raise pH to bring Iron & Manganese out of

solution in surface and ground waters• Used to Make Bleach / combined w/ Chlorine &

water• Caution - Calcium Carbonate deposits

AmmoniaAmmoniaTTHM ControlTTHM Control

Anhydrous Ammonia: Inhalation Hazard is used in water treatment with chlorine to form Chloramines a gentler disinfectant which does not form TTHM’s

Ammonium Hydroxide comes in a ~20% solution must be kept below 80F – used in power plants to convert Nitrites to nitrogen (Urea – DEF fluid)

Liquid Ammonium Sulfate (L.A.S.) NON-HAZARDOUS is a safer method of chloramination, more stable residuals in distribution <4F freeze point. Comes in a 10% by weight solution

NITRATES / WW Odor & Corrosion NITRATES / WW Odor & Corrosion Control – NON HAZARDOUSControl – NON HAZARDOUSAmmonium Nitrate Very Hazardous – fertilizer - OK City BombingAmmonium Nitrate Very Hazardous – fertilizer - OK City Bombing

• Aerobic bacteria energy source to eliminate anaerobic bacteria from forming hydrogen sulfide

• Calcium Nitrate – hydrogen sulfide control – used in lift stations with force mains with a DT time of greater than 5 hours (Hydrogen Peroxide best for less than 5 hours)

• Sodium Nitrate – Same as above, higher dose, can be blended with oxidant (Sodium Chlorite) to reduce foams

• Fairly expensive – less than ½ the cost of infrastructure replacement in the long run (~10 years)

Magnesium HydroxideMagnesium Hydroxide Odor &Odor & Corrosion Control WW – NON HAZARDOUSCorrosion Control WW – NON HAZARDOUS

• Added at lift stations and WWTP to raise alkalinity sewer pH to maximum ~ 8.2-8.5

• 8.2-5 pH prevents hydrogen sulfide from gassing off and in solution at splash points

• Difficult to maintain / constant agitation to keep Magnesium in solution on site

• Fairly expensive but non hazardous• Long term use in lift stations will create cement like

sediment that must be eventually removed w/ Jack Hammer….

Lime / Calcium HydroxideLime / Calcium Hydroxide• Raises pH – +Calcium for stability in potable water• Softening Potable Water – pH to 9.5+• Coagulation aid in low alkalinity waters (post

coagulant)• Increases Alkalinity (CaCO3) 1 to 1• Used for Waste Water Sludge Treatment (B to A)

exothermic reaction (heats up to ~ 120F) when added at high doses in sludges

• Dry Quick Lime / Slake Lime and slurries available

Soda AshSoda Ash(Sodium Carbonate)(Sodium Carbonate)

NON-HAZARDOUSNON-HAZARDOUS

• Excellent for raising Alkalinity• Used in low alkalinity <10 mg/L - low pH

waters normally used during flood events• Expensive• Dry & 15% Liquid Solution• Baking Soda (Sodium Bi-Carbonate)– rarely

used for particular alkalinity water chemistry - + carbonate alkalinity

CARCARBONBONSS• Granular Activated Carbon (GAC) Non Hazardous Filters –

Organics (odor & TOC) Absorption – Used for Biological Filters potable & WW treatment

• P.A.C. (Powder Activated Carbon) – Inhalation Hazard• Odor Control (surface water) – 4 hours contact time optimal• T.O.C. reduction (fire w/ fire)• Coagulant Aid (heavier floc in low turbs)• 3 Types: Lignite Coal (GAC/anthracite filters), Bituminous

(Mines), and Wood Based are the 3 different types

COPPER SULFATECOPPER SULFATECorrosive – Marine HazardCorrosive – Marine Hazard

• Used to control Algae growth in lakes, reservoirs, ponds, clarifiers, UV Panels WW Plants

• Often blended with Coagulants to control algae growth rates in Water Plant Clarifiers and recycle ponds = reduced odors and better filter / clarifier cleaning

• Can be blended with lime slurry to make a paste for clarifier walls for algae control

• Comes in dry and 25% solutions (Regulated by EPA) • Kills Algae / Disrupts algae photosynthesis (Co to O) =

robs oxygen in water = fish kill – max use in ponds w/ fish = 0.3 mg/L (dry basis) 4 hours contact time required

Poly PhosphatesPoly Phosphates Corrosion Inhibitors / Fe,Pb,Cu,& Mn SequesteringCorrosion Inhibitors / Fe,Pb,Cu,& Mn Sequestering

• Poly-Ortho’s – Most common in Drinking Water• Polys’ = sequestering of Fe & Mn Well & Surface • Ortho = corrosion control (lead & copper leaching from

pipes) the type used depends on system circumstances • Zinc Ortho (Acidic)– Zinc is regulated in industrial waste

water into streams not rivers • Tetra Sodium Pyrophosphate – Drinking Water / Cooling

Towers• Sodium Hexametaphosphate – Boiler Water - Drinking• Sodium Tripolyphosphate – Water Treatment /Cleaners• Mono (pure ortho) – Water treatment• Corrosion Control – allow lower pH’s in distribution vs

caustic or lime use costs• Waste Water Plant affected = ~ 1.0 mg/L of phosphate in

sewer water- strict permit limits on phosphate can eliminate use by water systems

Carbon Dioxide / GasCarbon Dioxide / GasHazardous – No Odor – Must have CO2 MonitorsHazardous – No Odor – Must have CO2 Monitors

• Reduction of pH after softening• pH reduction of raw water without reducing

alkalinity for enhanced TOC reduction• Increases Carbonate Alkalinity • Expensive Infrastructure and Dangerous

Sodium FluorideSodium FluorideVery Corrosive – Kills BacteriaVery Corrosive – Kills Bacteria

Fluorine (element base)Fluorine (element base)

• Water treatment additive for dental cavity control - @ .7 mg/L target for potable water

• Most surface waters have ~ 0.2 to 0.4 natural Calcium Fluoride content

• Some well waters contain 3-4 mg/L and it must be blended or removed with treatment (expensive-Activated Alumina media) – stained teeth (Panhandle and W. Texas)

• Oil field down hole injection to disrupt strata to increase oil flow / Bi-product of Aluminum smelting.

CITRIC ACID (50%)CITRIC ACID (50%)USED FOR CLEANING

MEMBRANES Made using Limes (fruit)Crop success can affect

pricing

Chelating Copper Sulfate

ANY QUESTIONS?ANY QUESTIONS?Hope you can retain everything discussed

MOST IMPRORTANTLY ALWAYS be SAFETY conscience when handling ANY TYPE OF CHEMICALS WHERE ALL PPE PROTECTION AND NEVER FORGET YOUR EYES… WHERE THOSE SAFETY GLASSESTHANKS FOR YOUR TIME!SAFE DRIVE HOME