WaterTech 2015

Peracetic acid –

A new solution for

wastewater disinfection

Prepared by: Jean Paré, P. Eng.

Presentation Agenda

1.Peracetic Acid as Wastewater

Disinfectant

2.Process Implementation

3.Chemco/PeroxyChem Service

Overview

What is Peracetic Acid

The peracetic acid molecule is simply an acetic acid (vinegar) molecule with an extra

oxygen such that there is an O-O bond.

Peracetic acid is an equilibrium mixture of peracetic

acid, hydrogen peroxide, water and acetic acid

CH3COH + H2O2 CH3COOH + H2O

Acetic Acid Hydrogen Peracetic Acid Water

Peroxide

O O

The Peroxychem VigorOx WWT II is a 15% PAA / 23% H2O2

formulation which is formulated for maximum efficacy with maximum

safety.

VigorOx WWT II compositionComposition by weight percent

Peracetic Acid, 15 %

Hydrogen Peroxide, 23 %

Acetic Acid, 16 %

Water (free), 45 %

Stabilizer, <1 %

Other PAA don’t contain up to 23 % Hydrogen Peroxide = less active

VigorOx WWT II properties

Will maintain for a long period and saves time by eliminating the need for

repeated assay testing

Properties

Physical state Liquid

Odor pungent “vinegar” smell

Density 1.15 g/mL

Freezing point -56 ˚F

pH < 1 as is (2.9 for a 1 % solution)

Solubility completely soluble

Stability one year at temperatures below 84 ˚F

four months below 100 ˚F

NFPA • Flammability: flashpoint above 200 F

• Health: short exposure cause injury

• Reactivity: violent decomposition at high T

• Oxidizer

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OX

30 Years of PAA Microbial Control

1980 1990 2000 2010

Medical Device Sterilization

Surface Sanitization

VigorOx® LS&D

VigorOx® Citrus XA

Citrus Canker Control

Poultry Processing

Spectrum®

PAA 35 VigorOx® WWT II

Wastewater Disinfection

VigorOx® O&G

Oil Field Biocide

PMRA Canadian Approval For Disinfection of Sewage and Wastewater Effluents in

Treatment (since May 2014)Plants

Use VigorOx® WWT II to treat sewage and wastewater effluent related to

public and industrial wastewater treatment plants. VigorOx® WWT II may be

applied directly to the effluent or may be used with UV light.

• Add VigorOx® WWT II to effluent water at a concentration of 0.5 ppm to 4

ppm peroxyacetic acid.

• The maximum amount of peracetic acid that can be discharged is:

i. 0.09 * DF, where DF ≥ 12 and

DF = plant effluent discharge + receiving stream 7Q10

plant effluent discharge receiving stream; or

ii. 1 ppm if the 7Q10 is unknown or DF < 12.

• MEDDLCC has granted their authorization for its use in Quebec

Note: 7Q10 is the minimum average 7-day flow expected to occur once every

10 years for the receiving stream

Safety

Main Hazard

Exothermic Decomposition

• Over pressurization of tanks/lines

• Increase of T (evaporation of water

and then acetic acid)

•Trigger: contamination (+2 metals

such as iron, copper, nickel).

Safety Stanards

• Materials

• Pressure relief

• Containment

• Dilution

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OX

Classification

DOT

• Class 5.2 – Organic Peroxide

NFPA 30

• Class III A – combustible liquid,

cannot sustain a flame

NFPA 400

• Class IV – Organic Peroxide

NFPA 704

Safety

Safety risk profile is much lower than chlorine gas

• PAA is a liquid, leaks/spills are easily contained

• Spills easily handled – dilution and decomposition to

water/acetic

• Appropriate design of storage and handling equipment

• Appropriate use of PPE

Advancements in PAA

Wastewater Disinfection

• Peracetic Acid Background

• Why Consider VigorOx WWT II Peracetic Acid

– Data Sources

– Drivers for Conversion

– Disinfection Efficacy

• Process Implementation

• Conversion Path & Regulatory Involvement

Drivers for use of PAA

Chlorine

Toxicity

Need to add

dechlorination

High Operating CostChlorine

Safety

Chlorine

DBPs

Disinfection

Capacity

Need to replace

chlorination with UV

Need to upgrade system

or increase capacity

High Capital Cost

PAA can be the most economical disinfection alternative

New contact channel

New UV system

New chlorination system

VigorOx WWT II experience• Twenty VigorOx® WWT II wastewater disinfection applications over

the last two years.

Applications of VigorOx in wastewater have covered a

wide range of waters and climates

5 MGD

3yr

Full Scale

92 / 240 MGD

6 month

½ Full Scale

8/25 MGD

1 yr

Full Scale

15/45 MGD

5 yr

Full Scale

Efficacy

Effective Dose

Indicator Organism

Bacteria E-Coli

Fecal ColiformVirus

Poliovirus

Adenovirus

Demand

TSS

COD

BOD

Ammonia **

Contact Time Contact Tank

Flow ranges

PAA’s cost effectiveness depends on the effective dose (site-specific)

Efficacy – Indicator OrganismMatrix Organism

Inactivation

(log)Dose (mg/L)

Time

(minutes)Reference

Secondary effluent Total coliform 2 1.5 20 Zanetti et al., 2007

Secondary effluent Total coliform 2 2 16 Stampi et al. 2002

Secondary effluent Total coliform 3 2 27 Koivunen et al,. 2005

Secondary effluent Total coliform 4 1.5 20 Stampi et al., 2001

Secondary effluent Total coliform 4 3 15 Madoni et al., 1998

Secondary effluent Fecal coliform 3 2 16 Stampi et al. 2002

Secondary effluent E. coli 2 1.5 20 Zanetti et al., 2007

Secondary effluent E. coli 3 2 16 Stampi et al. 2002

Secondary effluent E. coli 4 1.5 20 Stampi et al., 2001

Secondary effluent E. coli 3 4 10 Dell’Erba et al., 2004

Secondary effluent Enterococci 4 3 15 Madoni et al., 1998

Secondary effluent Enterococci 2 2 16 Stampi et al. 2002

Secondary effluent Enterococci 4 1.5 20 Stampi et al., 2001

PAA’s efficacy against bacteria has been well documented

Efficacy – Indicator Organism

0

1

2

3

4

5

6

7

8

1 10 100 1,000 10,000 100,000

Bacteria, WW

MS2 phage, WW

Virus, DMW

Published PAA efficacy data demonstrate wide range of action

Ct (mg/L*min)

Log

Re

du

ctio

n

0

1

2

3

4

5

6

7

8

1 10 100 1,000 10,000 100,000

Efficacy – Indicator Organism

VigorOx proven effective against bacteria and viruses in WW

Ct (mg/L*min)

Log

Re

du

ctio

n

• Bacteria, WW (VigorOx)

Virus, WW (VigorOx)

ON1

ON1

ON1

ON1

ON1

TN1

CA1

MI1

CA3TN2TX2

FL1

WA1

MN1

IL1

TX1

FL2

MO1

Efficacy – Demand (TN2)

0

2

4

6

8

10

12

0 10 20 30 40 50

PA

A R

esid

ual

(mg

/L)

Contact Time (minute)

4 mg/L

7 mg/L

10 mg/L

DPAA = f (TSS, TOC, BOD, etc, etc)

The effluent’s PAA demand is driven by multiple quality parameters

Efficacy – Demand (TN1)

0

2

4

6

8

10

12

14

16

0 500 1000 1500 2000 2500 3000

Vig

orO

x d

em

an

d (

mg

/L)

Color (PtCo)

Max PAA demand: 14 ppm

Max Chlorine demand: 40 ppm

In some high-demand sites, Color correlated better than TSS or BOD

Efficacy – Contact Time (TX1)

VigorOx proved effective at contact times shorter than chlorine

VigorOx: 4.0 ppm @ 7.5 min

Chlor/Dechlor: 4.0 ppm @ 15 min

Efficacy – UV Synergies (NY1)

Comparison between:

• Log inactivation achieved with UV

only (blue)

• Log inactivation achieved with 50% of

the UV dose plus 1 ppm VigorOx at

30min contact time (red)

A 50% reduction in required UV dose

(potentially a 50% reduction in power

consumption) was observed.

VigorOx showed synergistic effect with UV, potentially reducing cost

and its impact on the environment

CorMix Study with MWH

• PAA concentration gradient post

outflow point

• Coupled with aquatic toxicity data,

can show impact of VigorOx WWT

on environment

• Residual decomposes quickly into

environmentally benign

compounds: water and vinegar

ConclusionsRecent field applications of VigorOx® WWT II (15% PAA) in municipal

wastewater disinfection demonstrate that PAA:

• Can achieve equivalent chlorine performance at lower doses

• Typically requires shorter contact times than chlorine (TX1, WA1)

• Will not generate TTHMs, Cyanide or NDMA (FL1, IL1, CA1)

• Is less toxic than chlorine and may not require quenching (FL1, ON1, TX1)

• Can be implemented with on-line residual monitoring and control (NY2)

• Can be as effective as chlorine against viruses (ON1)

• Can meet non-detect levels of Fecal Coliforms consistently (CA1, CA2)

• Can improve performance of existing UV systems (NY1, NY2)

PAA can enable compliance at the same or lower operating cost, and

avoiding additional capital expense.

The bottom line

• Provide effective wastewater disinfection

• Eliminate all issues associated with chlorine

– Safety in transportation/storage

– Toxicity to aquatic life

– Formation of DBPs

– Nitrification

• No capital cost

• Operating cost ≈ sodium hypo + bisulfite

Process Implementation

A complete solution

VigorOx

Chemical

Service

Process

Guarantee

Equipment

Peroxychem/Chemco provides chemistry, equipment and services for

a competitive operating cost.

Implementation – StorageTote Storage Considerations

• Containment required

• Never store on wooden pallets

• Do not store near reducing agents or

combustibles (20 ft minimum distance)

• Do not block vents

• Indoor Storage– Ventilation of 1 ft3/min/ft2

• NFPA classification– Class IV Organic Peroxide

– Does not support a flame

• Electrical– Intrinsically safe recommended for areas that

are not well ventilated

Safety Considerations: containment, materials, venting

Implementation – Storage Bulk

Safety Considerations: containment, materials, venting, connections

Bulk Storage Considerations

• Acceptable materials include:

– HDPE Linear (5yr max)

– Passivated SS-304L

• Containment required (double wall acceptable)

• Product shelf life ( C >15%)

• 1 year, T < 86 ˚F

• 4 months, T < 100 ˚F

• 1 month, T < 110 ˚F

• Free-lift emergency relief manway and conservation vent

• Avoid overflow lines

• Unique quick connect for fill line (avoid contamination)

• Consider all local codes and regulations

Implementation – Pumps

Safety considerations: redundancy, venting, containment, materials

Pump Skid Considerations

• Duty and Redundant

• Peristaltic, Diaphragm or Solenoid acceptable

• Off-gas valve required at pump head for

diaphragm and solenoid pumps

• Wetted Materials

– Passivated 304L SS

– Teflon®

– Santoprene™ (peristaltic pumps)

• Controller

– Flow-paced

– Compound loop

• Containment Required

Implementation – Piping

Safety considerations: venting, materials, flushing, flex connections

Piping Considerations

• Compatible wetted materials of construction (Teflon / 304SS)

• Vented ball valves

• Pressure relief valves to prevent PAA entrapment

• Dilution water / Flush line

• Flex Connections for Tanks / Totes / Pumps

• Gaskets

• GORE-TEX®

• Teflon

• Garlock Gylon® Style 3504

• Thread sealant

• White Teflon Tape (Do not use anti-galling tape)

• Fluorolube®

Implementation – Low T (IL1)

Low freezing point makes PAA ideal for cold weather applications

Freezing Point:

• VigorOx WWT II -56˚F(-49 ˚C)

• Sodium Hypochlorite -20˚F (-29 ˚C)

• Sodium Bisulfate 43˚F (+6 ˚C)

No heat-tracing required with PAA

Implementation – Control

New generation submersible probes validated for VigorOx

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

0.00 1.00 2.00 3.00 4.00 5.00

Pro

be

1 a

nd

Pro

be

2

VigorOx Concentration (mg/L as PAA)

On-line residual measurement makes

compound loop control possible for PAA

Capabilities – Piloting &Modeling

Conversion of

plug flow pilot

reactor to open

channel

rectangular

contact chamber

CFD Study with Drexel University

Figure from:

D. Santoro, et al

Int’l J. of Chem Reactor

Eng. Vol 3, 2005

Model the real time performance of VigorOx WWT II on-site

Capabilities – Lab Support

Microbiology Lab in Tonawanda, NY

Microbial Assessment

• E.Coli

• Fecal & Total Coliform

• Heterotrophic plate counts

• MS2 bacteriophage

Disinfection Kinetics (PAA, Cl2)

• Demand

• Decay

Water Quality

• pH, T, TOC, UVT, true and apparent color

PeroxyChem takes a scientific approach to

microbial control via peracetic acid

Hydrogen Peroxide

Peracetic Acid

Persulfates

PeroxyChem Locations

Headquarters

Philadelphia, PA

Research and Development

Tonawanda, NY

Production Plants

Bayport, TX Hydrogen Peroxide

Tonawanda, NY Persulfates, Peracetic Acid

Price George, BC, Canada Hydrogen Peroxide

Delfzil, Netherlands Hydrogen Peroxide

La Zaida, Spain Hydrogen Peroxide, Peracetic Acid

Rheinfelden, Germany Persulfates

About our Expertise,

Products and Services

• Training and Education: technical transfer session, health and safety training;

• Consulting and Technology Site Assessment: technology support and selection (chemical oxidation and reduction, co solvent-surfactant soil washing and enhanced bioremediation);

• Products supply, logistic and storage: nutrients, bacterial preparations strains, oxidants, reducing agents, catalysts, oxygen and hydrogen release compounds, co solvent-surfactant blends

• Laboratory Services and Analysis: Groundwater Parameter Analysis, Tracer Study, Soil and Groundwater Oxidant Demand Evaluation (SOD), Bench Scale Treatability testing in saturated and unsaturated conditions.

Questions?

Jean Paré, ing.

T:418-953-3480

Email: jean.pare@chemco-inc.com

Contact information

Chemco Inc.

124 Hambourg

Saint-Augustin-de-Desmaures, Qc

G3A2N4