FMC Peracetic Acid

General Safety Review of 15/10 PAA and other formulations as used for Poultry (Spectrum), Direct Meat (Blitz), F&V Applications and VigorOx

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Agenda
Introduction to FMC Peroxygens Peracetic Acid Basics:

Chemistry Chemical and Physical Properties Stability Contamination Confinement Exposure

Peracetic Acid Hazards

Engineering Considerations Storage Transportation & Packaging Emergency Guidelines

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FMC North America Peroxygens

Tonawanda, NY Persulfates (Na, K, NH4) Peracetic Acid Metal Peroxides Prince George, BC H2O2

Mexico City H2O2 Persulfates

Bayport, TX H2O2

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FMC Peroxygen Leadership

Largest Persulfate Manufacturer Worldwide PAA Manufacture Since 1940s Leader in Peroxygen Handling:

Complete Internal Hazard Analysis Capability Complete Internal Corrosion Capability First US Supplier of Ultra High Purity Peroxide (<1 ppb metals) Engineering Consulting Expertise Peroxide Trial Equipment Auto Tank Gauging Capability On-Site Caros Acid Generation

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FMC Peracetic Acid Development History

1938 - First produced PAA at Buffalo 40% PAA - Chemical Synthesis for Pharmaceuticals 1986 - Joint development 15% PAA 1991 - Computer Controlled Manufacturing 1994 - Tonawanda Plant ISO 9002 Certification - GMP PAA Manufacture 1996 - Intermediate Bulk Container filling system - Analytical upgrades 1997 - SPC Implementation 1998 - Increased Acetic Acid bulk storage - New PAA control room 1999 - Development of Low Peroxide 15% PAA 2003 Launch all plastic Totes for 35% PAA 2004 New Reactor and Updated Controls 2004 Launch 1-Way Tote Offering

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Peracetic Acid Uses

Peracetic acid is used in the following applications:
Antimicrobial Chemical Synthesis Paper Machine Biocide Sanitizer/Disinfectant Sterilization

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What is Peracetic Acid?

O
H

C C
H H

O O

The peracetic acid molecule is simply an acetic acid molecule with an extra oxygen such that there is an O-O bond.

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PAA Equilibrium Chemistry

k forward

CH3COOH
Acetic Acid

+ H2O2
k reverse

CH3COOOH
Peracetic Acid

+ H 2O
Water

H
Heat

Hydrogen Peroxide

[PAA] [H2O] Keq = [HOAc] [H2O2] Rate of formation dependent on: Concentration and purity of starting materials Temperature Catalyst Rate of decomposition dependent on: Impurities; organic or inorganic Metals contamination leading to instability Storage Temperature

PKa: PAA HOAc

8.2 4.7

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PAA Equilibrium Chemistry (cont)

PAA active ingredient equilibrium is best illustrated on a triangular diagram:
Acetic Acid

Explosive Hazards Zone

NonExplosive Zone

H2O2

H2O

Any dilution of PAA with water shifts equilibrium and results in a new equilibrium along a line through the water apex point.

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Chemical Properties
TYPICAL COMPOSITIONS BY WEIGHT PERCENT
P e ra ce tic Acid (CH3 COOOH) Hydroge n P e roxide (H2 O 2 ) Ace tic Acid (CH3 COOH) S ulfuric Acid (H2 S O 4 ) Wa te r (Fre e ) To tal Ac tiv e Oxyg e n Othe r Orga nics Flas h Po int 15% , Re g ular 23% 16% 1% 45% 14.30% ND 155 F (68 C) 15% , Lo w Pe ro xide 10% 36% 1% 39% 7.90% ND 174 F (79 C)

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Physical Properties
Peracetic Acid
Appearance

15%, Low Peroxide

Odor

Specific Gravity at 20C Boiling Point

1.15

120 C (248 F) 19

Vapor Pressure (mm Hg, 25C)

Melting point

-49 F (-56 C) 2.9

pH 1% Solution

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Stability
All FMC peracetic acids are stabilized solutions.

Stabilizers reduce thermally induced decomposition and counteract catalytic decomposition induced by small amounts of metal ions. Recommended storage temperature is less than 30C (86F) to maintain product quality. PAA decomposition rate doubles for every 10C increase in temperature. Metal ions are catalytic to PAA decomposition; particularly active are the 1st row transition metals (e.g. Fe, Co, Ni, Cu, Zn, Cr, Mn). Both temperature and contamination can induce a self-accelerating decomposition of peracetic acid. This behavior is typical of peroxygen chemicals.

Temperature

Metal ions

Self-Accelerating Decomposition

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Conditions to Avoid

CONTAMINATION

CONFINEMENT

PERSONAL EXPOSURE

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Contamination
Stability is maintained by rigorous care in handling and storage. Stabilizer counteracts minute contaminant levels picked-up during handling. No amount of stabilizer will offset gross contamination! Contamination can cause rapid decomposition.

Potential contaminant sources include:

Heat Metals Incompatible Chemicals (e.g. alkalies, reducing agents, organics) Dust, dirt, etc.

Rapid decomposition is highly exothermic and Releases large volumes of oxygen which can over pressurize its container and/or equipment, and intensify a fire.

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Confinement
Peracetic Acid must not be confined because:

An inherent property of PAA is slow release of oxygen over time due to normal decomposition.
Recommended routine venting provisions include: Breather vents Pressure relief in piping Vented valves

PAA can release upwards of 100 times its volume in gas during rapid decomposition (e.g. caused by contamination).
Recommended emergency venting provisions include: Pressure relief valves Rupture disks Fusible plugs

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Equipment Considerations
FMC Engineering Services can assist in all design and engineering considerations for PAA feed systems. Only approved materials of construction can be used. Stainless steel equipment (304L or 316L SS) must be properly passivated prior to PAA service. Systems must be designed so PAA cannot be confined.

Pressure relief valves must be provided between valves in a piping system. Ball valves must be vented.

All PAA storage vessels must be provided with properly sized emergency relief vents.

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Equipment Considerations (contd)

Explosion-proof equipment is recommended for 15% PAA service. PAA vessels/containers must be provided with an adequate venting system to handle routine product transfers.

This system must be designed to prevent airborne contaminants from entering the PAA solution while minimizing employee exposure to fumes.

Provisions must be implemented to prevent backflow of process streams into PAA container and vice versa. A containment system must be provided in the event of a leak or spill. Safety shower and eyewash stations must be installed in the vicinity of PAA handling systems. A water source must be available wherever PAA is used.

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Materials of Construction Guidelines

15% PAA
Metals: Stainless Steel (type 304L, 316L only) Polymers: Polyethylene (HDPE/LLDPE)

Dilute PAA Solutions

Comment
Permitted exposure time dependent on Temp. & SA/V ratio. Passivation is required.

- limited exposure

Unpigmented only.

Teflon (PTFE) PVC (white, low carbon type) Polyethyle-ether-ketone (PEEK) Saran - short term exposure Embrittlement can occur with continued use.

- short term exposure

Use at ambient temperature only. Embrittlement can occur with continued use. Use at ambient temperature only. Embrittlement can occur with continued use. - short term exposure Use at ambient temperature only. Embrittlement can occur with continued use.

- short term exposure

Tygon

- short term exposure

Rubber: Synthetic (white only) Glass: Pyrex

Not recommended

- short term exposure

Colors will leach in to PAA solution over time.

Passivation required.

Material Compatibility must include evaluation of: Impact of PAA on material Impact of material on the PAA solution

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Storage
Adequate ventilation must be provided for PAA storage areas. To maintain product quality, store at or below 86F (30C). Do NOT store in direct sunlight. Do NOT store near reducing agents, combustibles, and other noncompatibles. Do NOT block vents on containers. Store containers upright. Maintain adequate spacing between pallets/IBCs. Wooden pallets are not recommended.
15% PAA
Applicable NFPA Code Associated Product Classification Electrical Rating NFPA 432 & 30 Class IV Organic Peroxide General Purpose

Refer to the appropriate NFPA code for spacing and sprinkler requirements.

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Transportation and Packaging

15% PAA
DOT Shipping Name
Organic peroxide Type F, Liquid, (with less than or equal to 18% peroxyacetic acid, stabilized)

DOT Labels

5.2 Organic Peroxide; Subrisk 8 (Corrosive) II 3109 30, 55 gal vented polyethylene drums; 330-gal LLDPE IBCs.

Packing Group UN Number Containers Available

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Exposure Hazards Active Ingredient

Proper handling and storage of PAA solutions minimize health hazards. Material Safety Data Sheets (MSDS) and the product label provide information concerning exposure, emergency first aid, as well as disposal of PAA solutions.

Eyes

Severely irritating. Acute exposure may cause irreversible eye damage, including blindness. Contact: Severely irritating, corrosive, acute exposure to liquid may cause severe burns. Absorption: Moderately hazardous; LD50 > 200 mg/kg for 17% PAA. Inhalation of vapors causes lacrimation and irritation of mucous membranes. TLV for peracetic acid has not been determined. The 8 hr TLV for acetic acid is 10 ppm and for hydrogen peroxide is 1 ppm. Slightly toxic; LD50 is between 50 and 500 mg/kg for 35% PAA.

Skin

Inhalation

Ingestion

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Personal Protective Equipment for A.I.

When handling PAA solutions, follow the MSDS and the following guidelines:

Eyes

Wear chemical type goggles or face shield whenever handling or mixing PAA solutions. Protect hands and arms with general purpose neoprene gloves. Cover feet and body with neoprene or rubber apron and footwear. Use in a well-ventilated area. If strong odors are detected, do not enter without self-contained breathing apparatus.

Skin

Inhalation

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Exposure Hazards At Use Concentrations

Eyes

Irritating. Acute exposure may cause eye damage. Contact: Irritating, corrosive, acute exposure to liquid may cause rash. Absorption: Not determined at <200 ppm level Studies indicate that at use concentrations will provide acetic acid and hydrogen peroxide levels < OSHA PEL limits for both substances. No inhalation hazards or irritations have been indicated during PAA used at <200 ppm when used in the field. Irritating to gastric tissue. LD50 not determined for at use concentrations of <200 ppm.

Skin

Inhalation

Ingestion

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PPE for At Use Concentrations of PAA

When handling PAA solutions, follow the MSDS and the following guidelines:

Eyes Avoid splash hazards and wash eyes if exposed, safety glasses are recommended for at use concentrations when splashing is an issue. Wear chemical type goggles or face shield whenever handling or mixing PAA concentrates. Skin Generally not found to be irritating at <200 ppm, wash with soap and water if irritation is noted. Experience has not shown this to be an issue. Inhalation Use in a well-ventilated area. Mild, vinegar like odor.

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First Aid Procedures

Refer also to Material Data Safety Sheets

Eyes

Wash immediately with copious amounts of water. Wash eyes for a minimum of 5 minutes with eyelids open. Contact a physician. Wash skin immediately with large amounts of water. Remove any contaminated clothing. Contact a physician. Remove subject to fresh air. Administer CPR and give oxygen if necessary. If swallowed, drink plenty of water immediately. Do not induce vomiting. Give milk of magnesia, chalk, or sodium bicarbonate. Call a physician immediately.

Skin

Inhalation

Ingestion

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Emergency Guidelines
Warm/Bulging Drum Release or Spill
Stop leak and dike spill if this can be done without risk. If container is punctured, move or roll drum so punctured area is above liquid level. Shut off or remove all ignition sources. Remove combustible or organic material from area. Flush all contacted surfaces with at least 20 volumes of water. Do not let undiluted material enter sewers or confined spaces. Any peracetic acid spill may be reportable under state or federal law. Can be neutralized with 7 lb bicarb per gal. 15/10 PAA or 0.8# bicarb/1# PAA 15/10 spilled Check residual with pH paper Call for assistance.

Disposal
Undiluted PAA must never be poured down drains or directly into sewers. Unused, undiluted PAA solutions that become waste material are classified as hazardous waste due to their low pH and oxidizing properties. An acceptable method for disposal of spilled material is to dilute with at least 20 volumes of water and allow the PAA solution to decompose followed by discharge into a suitable treatment system in accordance with all local, state, and federal rules and regulations. Call for assistance.

Do not move or agitate drum. Cool drum by external water spray. Move other drums away from warm or distended drum. Call for assistance.

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Fire Triangle
Peracetic acid itself has two of the three fire triangle components.

OXYGEN:
Sourced from PAA &/or H2O2

FUEL:
Sourced from HOAc &/or PAA

IGNITION SOURCE

Remember: Each PAA solution has a flash point and therefore is an NFPA combustible liquid which could supply fuel for a fire.

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Fire Fighting
WATER is the key word. Use ONLY water spray on all fires involving peracetic acid. Chemical fire extinguishers must not be used. Cool drums externally with water if exposed to fire. Wear self-contained breathing apparatus and full protective clothing. Wear full eye protection.

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Summary
PAA is a strong oxidizer with many useful applications; but it is also a hazardous chemical and must be treated with respect. Rapid PAA decomposition is highly exothermic and releases large volumes of O2 which can over pressurize equipment and intensify a fire. Hazards to avoid:

Contamination - by heat, metals, alkalis, organics and other incompatibles. Confinement - of normal & rapid decomposition O2 releases. Personal Contact - skin/eyes; fume inhalation; ingestion. Use only approved materials of construction. Stainless steel equipment must be passivated. Provide adequate routine venting & emergency pressure relief. Prevent introduction of external contaminants. Provide adequate ventilation system for product storage and transfer operations. Explosion-proof electrical for 15% PAA.

PAA Equipment Considerations:

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Summary (contd)
Safety shower/eyewash and water stations must be provided in the vicinity of PAA handling equipment and storage areas. PAA Storage Considerations: Store below 86F; out of direct sunlight Store away from flammables, combustibles & other non-compatibles. Never store on wooden pallets! Keep upright; dont block vents. Maintain proper container spacing, and provide adequate ventilation. Compliance with NFPA is mandatory. Wear proper PPE whenever handling PAA (i.e. goggles and/or face shield; neoprene gloves, apron & boots). SCBA gear must be worn for emergency response or whenever strong PAA fumes are detected. WATER is the key for direct personal contact, spills and fires involving PAA.

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Backups
General Process Safety and Information

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Proper Venting of PAA Valves

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Pressure Relief in PAA Piping Systems

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VigorOx Sanitizer Features & Benefits

Features
Broad Spectrum Efficacy (kills both gram- and gram+ bacteria) Non-Foaming No Rinse Broad pH Range Non-corrosive to SS

Benefits
Lowers bacteria count, extends shelf life of foods. Sanitizer contacts entire surface for more effective sanitation Saves time and water. Effective even if alkaline cleaning residual still present in equipment. Protects investment.

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VigorOx Sanitizer Value-In-Use

Extending Milk Shelf Life Using PAA vs. Hypochlorite Sanitizers

Case
Plant Baseline 100-200 PPM Chlorine Applied With Revised Procedures 100-200 PPM Chlorine Applied

Std. Error (Days) (Days at 7C)

9 0.51

Average Shelf-life

Range (Days)
5.9 - 16.6

20.4

2.98

7.3 - 30.6

With Revised Procedures 100-200 PPM Peracetic Acid Applied

33.9

4.12

21.3 - 53.0

Source: Ph.D. Dissertation May 4, 1994, Thomas J. Gruetzmacher; Identification and Control of Processing Variables that Affect the Quality and Safety of Fluid Milk; Graduate School of the University of Wisconsin-Madison.

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Peracetic Acid Biocide Functionality

Peracetic acid disrupts/oxidizes S-S and S-H chemical bonds within enzyme molecules. PAA is unaffected by and inactivates catalase enzyme. PAA penetrates bacteria spore walls (difficult - boiling sulfuric acid wont do it).
First, PAA Dislocates Cell Membrane Then, PAA Destroys Cells Internals

x x x x

Cell Wall

Enzymes in Cell

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Low Level Analysis

Analysis of VigorOx solutions in plant conditions can be completed using a test kit developed for the Food and Beverage Industry by LaMotte Company. The kit, #7191, uses two separate titrations. The first titration determines the concentration of hydrogen peroxide. The second titration determines the concentration of peracetic acid present. The kit comes with complete instructions, apparatus, and reagents for 50 tests. Reagent refills for 50 more tests are also available as product number R-7191. For additional information or to place an order, please contact:

LaMotte Company
PO Box 329 Chestertown, MD 21620 Phone: (800) 344-3100 or (410) 778-3100 FAX: (410) 778-6394
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Low Level Analysis

Analysis of part per million Peracetic solutions can be accomplished using a test kit developed by Chemetrics Company. The kit, #K7903, uses glass vacuvials with a colorometric comparator. The kit comes with complete instructions, apparatus, and reagents for 30 tests. Reagent refills for 30 more tests are also available as product number R-7903. For additional information or to place an order, please contact:

Chemetrics Company
4295 Calverton Rd. Calverton, VA 20138 Phone: (800) 356-3072 FAX: (540) 788-4856

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PAA Efficacy Against Common Organisms

Effective Concentrations of Antimicrobial Agents
Concentration of Antimicrobial (ppm) 1,200 1,000 800 600 400 200 0 L. monocytogenes S. aureus E. facium
Peracetic Acid
QUAT = Benzalkonium chloride 1. Concentration required for lethality in five minutes
2.

20C

5C

S. aureus L. monocytogenes
Active Chlorine QUAT

E. facium

Orth, R., and Mrozeck, H. Is the Control of Listeria, Campylobacter, and Yersinia a Disinfection Problem? Fleischwirtsch, 69 (10), 1575-1576

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VigorOx Ecological Data

Peracetic acid is not know n to be stable in the environm ent. It readily decom poses into w ater, oxygen, and acetic acid. T he decom position rate ranges from m inutes to days and is dependent upon existing concentrations of m icrobes, m etal ions, clays, and a variety of other com plexes (i.e. tem perature). A cute toxicity tests for 5% peracetic acid have been conducted w ith the follow ing aquatic organism s: B luegill sunfish ( Lepom is m acrochirus ), R ainbow trout ( O ncorynchus m ykiss ), the w ater flea ( D aphnia m agna ) and freshw ater green algae ( Selenastrum capricornutum P rintz ). T he 96-hour LC 50 values of for R ainbow trout and B luegill sunfish w ere 1.6 m g/L and 1.1 m g/L , respectively. T he E C 50 values for green algae and daphnia w ere 0.18 m g/L and 0.73 m g/L , respectively. Peracetic acid (5% ) is toxic to aquatic invertebrates and algae, and m oderately toxic to fish. D ue to the toxicity of 5% peracetic acid to aquatic organism s, effluent should not be discharged into lakes, ponds, estuaries, oceans or other w aters. S pecies B luegill sunfish R ainbow trout D aphnia m agna S elanastrum E xpo su re T im e 96 hours 96 hours 48 hours 120 hours L C 50 / E C 50 (m g/L ) L C 50 = 1.1 m g/L L C 50 = 1.6 m g/L E C 50 = 0.73 m g/L E C 50 = 0.18 m g/L N O E C (m g /L ) 0.47 m g/L 0.82 m g/L 0.56 m g/L 0.12 m g/L

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Peracetic Acid Physiological Data

Study Type
Eye Contact

Reference
FMC I95-2036 FMC I91-1195

Results
5% Peracetic Acid: Severely irritating (in-vitro) 0.15% Peracetic Acid: Mildly irritating, (rabbit) 5% Peracetic Acid: Corrosive (in-vitro) 0.15% Peracetic Acid: Non-irritating (rabbit) 17% Peracetic Acid: LD50 : Above 200 mg/Kg (rabbit) 0.15% Peracetic Acid: LD50 : Above 2000 mg/Kg (rat) 0.15% Peracetic Acid: Non-sensitizing (Guinea pig) LC50 : 524 mg/cum (mouse, 1 hour) 5% Peracetic Acid: LC50 : 4.08 mg/L (rat, 4 hour) 0.15% Peracetic Acid: LC50 : >7.669 mg/L (4 hour) 17% Peracetic Acid: LD50 : < 500 mg/Kg, > 50 mg/Kg (rat) 0.15% Peracetic Acid: LD50 : > 5000 mg/Kg (rat)

Skin Contact

FMC I95-2035 FMC I91-1194

Skin Absorption

FMC I83-721 FMC I91-1193

Skin Sensitization Inhalation

FMC I91-1191 JHEMI 20:54 1976 FMC I96-2138 FMC I91-1199

Ingestion

FMC I83-718 FMC I91-1192

JHEMI = Journal of Hygiene, Epidemiology, Microbiology and Immunology

5% Peracetic acid contains hydrogen peroxide. Chronic effects from overexposure to hydrogen peroxide include limited evidence of carcinogenicity to mice administered high concentrations in their drinking water (IARC Monograph 36, 1985). However, the International Agency for Research on Cancer concluded that hydrogen peroxide could not be classified as to its carcinogenicity to humans (Group III Carcinogen).

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PAA Stability
Self-accelerating decomposition Either induced by temperature or metal ions, peracetic acid can undergo a self-accelerating decomposition similar to other peroxygen chemicals. A generic example of a self-accelerating decomposition scenario is shown below. Temperature and time vary depending on the situation.
Generic Self- Accelerating Decomposition Example
200 175 150 125 100 75 50 25 0 0 2 4 6 8 10 12 Time 14 16 18 20 22 24

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Temperature