Per Acetic

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FMC Peracetic AcidFMC Peracetic Acid

General Safety Review of 15/10 PAA and otherformulations as used

for Poultry (Spectrum®), Direct Meat (Blitz®),F&V Applications and VigorOx®


� Introduction to FMC Peroxygens� Peracetic Acid Basics:

» Chemistry» Chemical and Physical Properties» Stability

� Peracetic Acid Hazards» Contamination» Confinement» Exposure

� Engineering Considerations� Storage� Transportation & Packaging� Emergency Guidelines

Agenda


FMC North America Peroxygens

Bayport, TXH2O2

Mexico CityH2O2

Persulfates

Tonawanda, NYPersulfates (Na, K, NH4)Peracetic AcidMetal Peroxides

Prince George, BCH2O2

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FMC Peroxygen Leadership

� Largest Persulfate Manufacturer Worldwide

� PAA Manufacture Since 1940’s

� 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 Caro’s Acid Generation


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


Peracetic Acid Uses

Peracetic acid is used in the following applications:

Antimicrobial

Chemical Synthesis

Paper Machine Biocide

Sanitizer/Disinfectant

Sterilization


What is Peracetic Acid?

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

OH

C H

C

H OH O


PAA Equilibrium Chemistry

k forward

� CH3COOH + H2O2 CH3COOOH + H2O + ∆Hk reverse

Acetic Acid Hydrogen Peracetic Acid Water HeatPeroxide

[PAA] [H2O] PKa:Keq = PAA 8.2

[HOAc] [H2O2] HOAc 4.7

� 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


PAA Equilibrium Chemistry (con’t)

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

H2O2 H2O

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

Non-Explosive

ZoneExplosiveHazardsZone


Chemical Properties

TYPICAL COMPOSITIONS BY WEIGHT PERCENT

Pe race tic Acid(CH3COOOH)

15%,Re gular

15%,Low

Peroxide

Hydrogen Pe roxide (H2O2) 23% 10%

Ace tic Acid (CH3COOH) 16% 36%

Sulfuric Acid (H2SO4) 1% 1%

Wa te r (Free ) 45% 39%

Total Ac tive Oxyge n 14.30% 7.90%

Othe r Organics ND ND

Flas h Point 155 F(68 C)

174 F(79 C)


Physical Properties

Specific Gravityat 20C

1.15

120 C(248 F)

Vapor Pressure(mm Hg, 25C)

-49 F(-56 C)

pH 1% Solution 2.9

PeraceticAcid

15%,Low

PeroxideAppearance ⇒

Odor ⇒

Boiling Point

Melting point

19


Stability

� All FMC peracetic acids are stabilized solutions.» Stabilizers reduce thermally induced decomposition and counteract

catalytic decomposition induced by small amounts of metal ions.

� Temperature» Recommended storage temperature is less than 30ºC (86ºF) to maintain

product quality.

» PAA decomposition rate doubles for every 10ºC increase intemperature.

� Metal ions» Metal ions are catalytic to PAA decomposition; particularly active are

the 1st row transition metals (e.g. Fe, Co, Ni, Cu, Zn, Cr, Mn).

� Self-Accelerating Decomposition» Both temperature and contamination can induce a self-accelerating

decomposition of peracetic acid. This behavior is typical of peroxygenchemicals.


Conditions to Avoid

PERSONALEXPOSURE

CONTAMINATION CONFINEMENT


Contamination

� Stability is maintained by rigorous care in handling andstorage.

� Stabilizer counteracts minute contaminant levels picked-upduring 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.


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 duringrapid decomposition (e.g. caused by contamination).

� Recommended “emergency” venting provisions include:− Pressure relief valves− Rupture disks− Fusible plugs


Equipment Considerations

FMC Engineering Services can assist in all design andengineering 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 pipingsystem.

» Ball valves must be vented.

� All PAA storage vessels must be provided with properly sizedemergency relief vents.


Equipment Considerations (cont’d)

� 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 processstreams into PAA container and vice versa.

� A containment system must be provided in the event of a leak orspill.

� Safety shower and eyewash stations must be installed in thevicinity of PAA handling systems.

A water source must be available wherever PAA is used.


Materials of Construction Guidelines

15% PAA Dilute PAA Solutions CommentMetals:• Stainless Steel

(type 304L, 316L only)√ - limited exposure √ Permitted exposure time dependent on Temp. &

SA/V ratio. Passivation is required.

Polymers:• Polyethylene (HDPE/LLDPE) √ √ Unpigmented only.

• Teflon (PTFE) √ √

• PVC(white, low carbon type)

√ - short term exposure √ Embrittlement can occur with continued use.

• Polyethyle-ether-ketone(PEEK)

√ - short term exposure √ Use at ambient temperature only. Embrittlementcan occur with continued use.

• Saran √ - short term exposure √ Use at ambient temperature only. Embrittlementcan occur with continued use.

• Tygon √ - short term exposure √ - short term exposure Use at ambient temperature only. Embrittlementcan occur with continued use.

Rubber:• Synthetic (white only) Not recommended √ - short term exposure Colors will leach in to PAA solution over time.

Glass:• Pyrex √ √ Passivation required.

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


Storage

� Adequate ventilation must be provided for PAA storage areas.� To maintain product quality, store at or below 86ºF (30ºC).� Do NOT store in direct sunlight.� Do NOT store near reducing agents, combustibles, and other non-

compatibles.� Do NOT block vents on containers. Store containers upright.� Maintain adequate spacing between pallets/IBCs.� Wooden pallets are not recommended.

15% PAAApplicable NFPACode

NFPA 432 & 30

Associated ProductClassification

Class IVOrganicPeroxide

Electrical Rating General Purpose

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


Transportation and Packaging

15% PAADOT Shipping Name Organic peroxide Type F,

Liquid, (with less than orequal to 18% peroxyaceticacid, stabilized)

DOT Labels 5.2 Organic Peroxide;Subrisk 8 (Corrosive)

Packing Group II

UN Number 3109

Containers Available 30, 55 gal ventedpolyethylene drums;330-gal LLDPE IBCs.


Exposure Hazards Active Ingredient

� Eyes» Severely irritating. Acute exposure may cause irreversible eye damage,

including blindness.

� Skin» Contact: Severely irritating, corrosive, acute exposure to liquid may cause

severe burns.» Absorption: Moderately hazardous; LD50 > 200 mg/kg for 17% PAA.

� Inhalation» Inhalation of vapors causes lacrimation and irritation of mucous membranes.

TLV for peracetic acid has not been determined. The 8 hr TLV for acetic acidis 10 ppm and for hydrogen peroxide is 1 ppm.

� Ingestion» Slightly toxic; LD50 is between 50 and 500 mg/kg for 35% PAA.

Proper handling and storage of PAA solutions minimize health hazards. Material Safety DataSheets (MSDS) and the product label provide information concerning exposure, emergency

first aid, as well as disposal of PAA solutions.


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

Personal Protective Equipment for A.I.

� Eyes» Wear chemical type goggles or face shield whenever handling or

mixing PAA solutions.

� Skin» Protect hands and arms with general purpose neoprene gloves.» Cover feet and body with neoprene or rubber apron and footwear.

� Inhalation» Use in a well-ventilated area.» If strong odors are detected, do not enter without self-contained

breathing apparatus.


Exposure Hazards At Use Concentrations

� Eyes» Irritating. Acute exposure may cause eye damage.

� Skin» Contact: Irritating, corrosive, acute exposure to liquid may cause rash.» Absorption: Not determined at <200 ppm level

� Inhalation» 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.

� Ingestion» Irritating to gastric tissue. LD50 not determined for at use concentrations

of <200 ppm.


PPE for At Use Concentrations of PAA

� 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 andwater if irritation is noted.

» Experience has not shown this to be an issue.� Inhalation

» Use in a well-ventilated area.» Mild, vinegar like odor.

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


First Aid Procedures

� Eyes» Wash immediately with copious amounts of water. Wash eyes for

a minimum of 5 minutes with eyelids open. Contact a physician.

� Skin» Wash skin immediately with large amounts of water. Remove any

contaminated clothing. Contact a physician.

� Inhalation» Remove subject to fresh air. Administer CPR and give oxygen if

necessary.

� Ingestion» If swallowed, drink plenty of water immediately. Do not induce

vomiting. Give milk of magnesia, chalk, or sodium bicarbonate.Call a physician immediately.

Refer also to Material Data Safety Sheets


Emergency Guidelines

Warm/Bulging Drum

� Do not move or agitatedrum.

� Cool drum by external waterspray.

� Move other drums awayfrom warm or distendeddrum.

� Call for assistance.

Release or Spill

� Stop leak and dike spill if this canbe done without risk. If containeris punctured, move or roll drumso punctured area is above liquidlevel.

� Shut off or remove all ignitionsources.

� Remove combustible or organicmaterial from area.

� Flush all contacted surfaces withat least 20 volumes of water.

� Do not let undiluted material entersewers or confined spaces. Anyperacetic acid spill may bereportable under state or federallaw.

� Can be neutralized with 7 lbbicarb 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 bepoured down drains or directlyinto sewers.

� Unused, undiluted PAA solutionsthat become waste material areclassified as hazardous wastedue to their low pH and oxidizingproperties.

� An acceptable method fordisposal of spilled material is todilute with at least 20 volumes ofwater and allow the PAAsolution to decompose followedby discharge into a suitabletreatment system in accordancewith all local, state, and federalrules and regulations.

� Call for assistance.


Fire Triangle

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 anNFPA “combustible liquid” which could supply fuel for a fire.

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


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.


Summary

� PAA is a strong oxidizer with many useful applications; but it is also ahazardous chemical and must be treated with respect.

� Rapid PAA decomposition is highly exothermic and releases large volumesof 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.

� PAA Equipment Considerations:» 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.


Summary (cont’d)

� Safety shower/eyewash and water stations must be provided in the vicinityof PAA handling equipment and storage areas.

� PAA Storage Considerations:» Store below 86ºF; out of direct sunlight» Store away from flammables, combustibles & other non-compatibles.» Never store on wooden pallets!» Keep upright; don’t 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 emergencyresponse or whenever strong PAA fumes are detected.

� WATER is the key for direct personal contact, spills and fires involvingPAA.


Backups

General Process Safety and Information


Proper Venting of PAA Valves


Pressure Relief in PAA Piping Systems


VigorOx Sanitizer Features & Benefits

� Broad Spectrum Efficacy (killsboth gram- and gram+ bacteria)

� Non-Foaming

� No Rinse

� Broad pH Range

� Non-corrosive to SS

� Lowers bacteria count, extendsshelf life of foods.

� Sanitizer contacts entire surface formore effective sanitation

� Saves time and water.

� Effective even if alkaline cleaningresidual still present in equipment.

� Protects investment.

Features Benefits


VigorOx Sanitizer Value-In-UseExtending Milk Shelf Life Using PAA vs. Hypochlorite Sanitizers

Plant Baseline100-200 PPMChlorine Applied

9 0.51 5.9 - 16.6

With Revised Procedures100-200 PPMChlorine Applied

20.4 2.98 7.3 - 30.6

With Revised Procedures100-200 PPMPeracetic Acid Applied

33.9 4.12 21.3 - 53.0

CaseAverageShelf-life

(Days at 7C)Std. Error

(Days)Range(Days)

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

Wisconsin-Madison.


� Peracetic acid disrupts/oxidizes S-S and S-H chemicalbonds within enzyme molecules.

� PAA is unaffected by and inactivates catalase enzyme.

� PAA penetrates bacteria spore walls (difficult - boilingsulfuric acid won’t do it).

First, PAA Dislocates Cell Membrane Then, PAA Destroys Cells Internals

Cell Wall

x

Enzymes inCell

xx

x

x

Peracetic Acid Biocide Functionality


Low Level Analysis

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

LaMotte CompanyPO Box 329Chestertown, MD 21620

Phone: (800) 344-3100 or (410) 778-3100FAX: (410) 778-6394


Low Level Analysis

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

Chemetrics Company4295 Calverton Rd.Calverton, VA 20138

Phone: (800) 356-3072FAX: (540) 788-4856


PAA Efficacy Against Common Organisms

Effective Concentrations of Antimicrobial Agents

QUAT = Benzalkonium chloride

L. monocytogenesS. aureus

E. facium

0

200

400

600

800

1,000

1,200

Concentration of Antimicrobial (ppm)

Peracetic Acid Active Chlorine QUAT

20C 5C

1. Concentration required for lethality in five minutes

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

L. monocytogenesS. aureus

E. facium


VigorOx Ecological Data

Peracetic acid is not know n to be stable in the environm ent. It readily decom poses into w ater, oxygen, andacetic acid. The decom position rate ranges from m inutes to days and is dependent upon existingconcentrations 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:Bluegill sunfish (Lepom is m acrochirus), R ainbow trout (O ncorynchus m ykiss), the w ater flea (D aphniam agna) and freshw ater green algae (Selenastrum capricornutum Printz). The 96-hour LC 50 values of forRainbow trout and B luegill sunfish w ere 1.6 m g/L and 1.1 m g/L, respectively. The EC 50 values for greenalgae and daphnia w ere 0.18 m g/L and 0.73 m g/L , respectively. Peracetic acid (5% ) is toxic to aquaticinvertebrates and algae, and m oderately toxic to fish. D ue to the toxicity of 5% peracetic acid to aquaticorganism s, effluent should not be discharged into lakes, ponds, estuaries, oceans or other w aters.

Species Exposure Tim e L C 50/ EC 50 (m g/L ) N O E C (m g/L)B luegill sunfish 96 hours LC 50 = 1.1 m g/L 0.47 m g/LR ainbow trout 96 hours LC 50 = 1.6 m g/L 0.82 m g/LD aphnia m agna 48 hours EC 50 = 0.73 m g/L 0.56 m g/LSelanastrum 120 hours EC 50 = 0.18 m g/L 0.12 m g/L


Peracetic Acid Physiological Data

Study Type Reference Results

Eye Contact FMC I95-2036

FMC I91-1195

5% Peracetic Acid: Severely irritating (in-vitro)

0.15% Peracetic Acid: Mildly irritating, (rabbit)

Skin Contact FMC I95-2035

FMC I91-1194

5% Peracetic Acid: Corrosive (in-vitro)

0.15% Peracetic Acid: Non-irritating (rabbit)

Skin Absorption FMC I83-721

FMC I91-1193

17% Peracetic Acid: LD50 : Above 200 mg/Kg (rabbit)

0.15% Peracetic Acid: LD50 : Above 2000 mg/Kg (rat)

Skin Sensitization FMC I91-1191 0.15% Peracetic Acid: Non-sensitizing (Guinea pig)

Inhalation JHEMI∗ 20:54 1976

FMC I96-2138

FMC I91-1199

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)

Ingestion FMC I83-718FMC I91-1192

17% Peracetic Acid: LD50 : < 500 mg/Kg, > 50 mg/Kg (rat)0.15% Peracetic Acid: LD50 : > 5000 mg/Kg (rat)

∗JHEMI = Journal of Hygiene, Epidemiology, Microbiology and Immunology

5% Peracetic acid contains hydrogen peroxide. Chronic effects from overexposure to hydrogen peroxide include limitedevidence 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 beclassified as to its carcinogenicity to humans (Group III Carcinogen).


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.

0

25

50

75

100

125

150

175

200

0 2 4 6 8 10 12 14 16 18 20 22 24

Time

Tem

pera

ture

Generic SelfGeneric Self-- Accelerating Decomposition ExampleAccelerating Decomposition Example

Per Acetic

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