Presented by

Stephen R. TempleHoward E. WhitneySteen Research LLCSteenresearch.com

U.S. Poultry, Proteins and FatsPresentationOctober 2015

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Cooking Fresh or Decaying Protein Generates Odiferous and Toxic Vapors ProblemCommon Sense

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Odor and Toxicity Sources Primary SourcesSecondary SourcesCommon Sense

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Primary SourcesInfall BayCooker and Hydrolyzer (Fugitive Odors)Non-Con Screw PressCentrifuge

Odor and Toxicity SourcesCommon Sense

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Secondary SourcesCooker and Hydrolyzer CondensateEvaporator CondensateW/W Bio ReactorsAeration Ponds and BasinsMilling Room

Odor and Toxicity SourcesCommon Sense

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SCIENCELatin "scientia," meaning knowledge

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Three Phases of Odor and ToxicityScience

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Nature of Odor and ToxicityGas-Phase VOCsAerosol Fats & OilsWater Vapor and MistSolid ParticulatesSmoke

Odor and Toxicity SourcesScience

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GasesScience

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ScienceAmmoniaTrimethyl AmineMethyl PyrazinePyrrole1-ethyl-1H-PyrroleEthyl PyrazinePyrazine2,6-dimethyl-Pyrazine1-methyl-1H-Pyrrole2-methyl-Pyridine2,5-dimethyl-1H-Pyrrole3-methyl-Butenenitrile3-methyl-PyridineGasesNitrogen CompoundsN,N-dimethyl-Benzamide5-isopropyl-4-phenyl-3-hydroxy-1,2,4-TriazoleIndoleOctanenitrile3-Ethyl-2,5-dimethyl-1H pyrrole5-butyl-3-methyl-1,2,3-8A-tetrahydroindolizineAcetamideN,N-dibutyl-FormamideBenzonitrile2-Methyl-pyrrole

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GasesHydrogen SulfideDimethyl TrisulfideDimethyl DisulfideCarbonyl SulfideThiophenemethyl-ethyl-DisulfideThiiraneDimethyl SulfMethylthio EthaneCarbon disulfide2-methyl-Thiophene3-Phenyl -ThiopheneBenzothiazole3-(Methylthio)-1-propene2-methyl-ThiazoleSulfur CompoundsScience

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Gases3-methyl-Butanal2-methyl-Propanal2-methyl-ButanalAcetaldehydeAldehyde similar to 3-methyl-ButanalHexanalButanalBenzaldehydePentanalFurfuralHeptanal3-methylthio-ButyraldehydePropionaldehydeIsobutyraldehydeIsovaleraldehyde3-Methyl-pentanal2-methyl-2-Butenal2-DodecenalNonanal1-PiperidinecarboxaldehydeHeptanal3-methylthio-ButyraldehydePropionaldehydeIsobutyraldehydeIsovaleraldehyde3-Methyl-pentanalOctanal2-methyl-2-Butenal2-DodecenalNonanal1-PiperidinecarboxaldehydeOctanalAldehydesScience

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GasesAcetic acidPropanoic acidIsobutyric acidButyric acidIsovaleric acid2-Furancarboxylic acidValeric acid4-Methyl-pentanoic acidCaproic acid1,2-Benzenedicarboxylic acid2-Ethylhexanoic acidVolatile Fatty AcidsOctanoic acidNonanoic acid4-Carboxamidonicotinic acidDecanoic acidPentadecanoic acidThiosulfuric acidBenzoic acid(Z)-9-Octadecenoic acid(Z)-9-Octadecenoic acidHexanedioic acidHeptanoic acidScience

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GasesMethyl AcetatePropyl AcetateButyl AcetateEthyl ButanoatePropyl ButanoateButyl ButanoateMethyl Butanoate4-Hydroxydodecanoic acid lactoneEthyl 3-phenylpropionateEstersScience

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GasesAcetone2-Butanone1-(2-furanyl)-Ethanone2-HeptanoneMethyl Isobutyl Ketone (MIBK)2-Pyrrolidinone3-acetyl-4-hydroxy-2(5H)-FuranonePiperidinone1,6-Dioxacyclododecane-7,12-dione1-Phenyl-ethanone1-(Methoxy-3-pyranzinyl)-1-ethanone2-Octanone3-Hexanone2-Nonanone2-DecanoneKetonesScience

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GasesMethanolEthanolFurfuryl Alcohol1-Butanol2-methyl-1-Propanol1-Propanol,-Dimethyl benzenemethanol1-Heptadecanol2,5,8,11,14-Pentaoxahexadecan-16-ol

MethylphloroglucinolHeptanol2-Ethyl-hexanol1-Hexanol2-Butoxy-Ethanol2-FuranmethanolBenzenemethanolBenzeneethanol1-OctanolAlcoholsScience

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GasesOxygen CompoundsFuran2-methyl-Furan2,5-dimethyl-FuranTetrahydrofuran2-Pentyl-Furan3-Acetyl-6-methyl-2H-pyran-2,4(3H)-dioneScience

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Gases1,1-dichloro-2-Propanone1-chloro-2-ButanoneChloromethaneChloroform (THM1)Tetrachloroethene (PCE)Dibromochloromethane (THM3)Bromodichloromethane (THM2)Carbon tetrachloride1,2-Dimethyl-hydrazine dichlorideChlorinated VOCsScience

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Gases2-methyl-ButanePropyleneTolueneHeptaneBenzeneHexaneEthylbenzene2-Butene1-Methyl-2-isopropyl benzeneNaphthaleneTrans-(-)-5-methyl-3-(1-methylethenyl)-cyclohexene4-Vinyl-2-methoxy-phenolp-CresolMethylnapthaleneHydrocarbonsPhenol2-Methyl-decane2-methyl-1-PropeneLimonene(1-Methylethenyl)-benzene9-OctadecyneTrans-caryophyllene1,3,5,7-CyclooctatetraenePolynuclear AromaticsScience

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Nitrogen Compounds Sulfur CompoundsAldehydesVolatile Fatty Acids

EstersKetonesAlcoholsOxygen CompoundsChlorinated VOCsHydrocarbons

GasesScienceVOCs Detected in High Intensity Vapors

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Water Solubility Compounds Affinity For Water

Volatility

Compounds Affinity For Air

Adsorption

Compounds Affinity For Solids

SciencePhysical PropertiesGases

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GasesScienceWater SolubilityTemperature SensitiveLow Temp = High SolubilityVolatilitypH SensitiveAlkaline pH Sulfur Compounds

Acidic pHNitrogen Compounds

Neutral pHOxygenated Compounds

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GasesScienceAdsorptionAerosolized Proteins, Fats Oils Greases, Solid Particulates and Smoke Contain:

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GasespH Vapor SolubilityHydrogen Sulfide H2S vs Ammonia NH3H2SNH3Science

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Liquid AerosolsScience

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ScienceLiquid Aerosols

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ScienceSmoke

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ScienceSolid Particulate

Spray Venturis are not designed to remove Smoke and Micro particulate and Micro Aerosols

Micro Particulate are known carcinogens

PM 10 EPA PM 2.5*

ScienceSolid Particulate

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ScienceOdor VOCs Absorbed on ParticulatesBK

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ScienceMulti-Phase Flow

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Engineering

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Engineering Constraints of Multi-Phase Wet Gas Rendering WasteEngineering

120- to 300-degrees F

High Humidity and Aerosolized Water Vapor

Smoke and Solid Particulates

Aerosolized Oils, Fats, Greases, Tallow, Proteins, etc.

Gas-Phase Ammonia, Hydrogen Sulfide, Complex of Odorous and Toxic Organics

Non-Uniform and Variable Flow Density Patterns In Pipe Networks

Difficult to Quantify Total Mass Flow

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Engineered Mass Reduction Methods:Temperature Changes and Transfer to WaterEngineering

Air-Cooled Condensation (Non-Con is NOT TRUE)

Spray Venturi Removal of large Particulates, Aerosols and Water Soluble Gases

Advanced Condensation, Precipitation and Wilson Cloud Formation on CCN

Electrostatic Ionization of CCN-Cloud

Packed Bed Wet Scrubbing For CCN-Cloud Condensation and Water Soluble Gases

Thermal Oxidation (TO/RTO/RCO/Boiler) For Complete VOC Destruction

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Advanced Pre-TreatmentEngineering

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EngineeringAdvanced Pre-Treatment

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Cloud Formation and Elimination

PM 2.5

PM 2.5Micro-Particulate Pollution

USEPA Mandated Testing under National AmbientAir Quality Standards (NAAQS) and Prevention of Significant Deterioration (PSD) increments for the secondarily formed component of PM2.5

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PM 2.5

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PM 2.5Fine ParticlesCombustion, gases to particlesSulfates/acidsNitrateAmmoniumOrganicsCarbonMetalsWaterSources:Coal, oil, gasoline, diesel, wood combustionTransformation of SOx, NOx, organic gases including biogenicsHigh temperature industrial processes (thermal oxidizers, smelters, steel mills)

Impacts:Children and Seniors most at risk for premature death, heart attacks, acute bronchitis and aggravated asthma.

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PM 2.5Who Does PM2.5 Effect?

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PM 2.5How PM2.5 Gets into Lungs, Blood and Brain

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PM 2.5Air pollution and children: neural and tight junction antibodies and combustion metals, the role of barrier breakdown and brain immunity in neurodegeneration.http://www.ncbi.nlm.nih.gov/pubmed/25147109

First trimester exposure to ambient air pollution, pregnancy complications and adverse birth outcomes in Allegheny County, PA.http://www.ncbi.nlm.nih.gov/pubmed/22544506

Fine particulate air pollution (PM2.5) and the risk of acute ischemic stroke.http://www.ncbi.nlm.nih.gov/pubmed/21399501

Relationship between fine particulate air pollution and ischaemic heart disease morbidity and mortality.http://www.ncbi.nlm.nih.gov/pubmed/25341536

Toxicity beyond the Lung: Connecting PM2.5, Inflammation, and Diabeteshttp://www.ncbi.nlm.nih.gov/pubmed/25341536

Exposure to fine airborne particulate matters induces hepatic fibrosis in murine models.http://www.ncbi.nlm.nih.gov/pubmed/26220751

Why Worry? Downwind Liability for:

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But We Have a PermitThe Third Circuit recently concluded that obtaining apermit under the Clean Air Act Does NOT Shield a company from liabilityfor damages caused by the plant?The Supreme Court refused to take the case on appeal so the decision stands.Bell v. Cheswick Generating Station, 734 F.3d 188, 190 (3d Cir. 2013)cert. denied sub nom.GenOn Power Midwest, L.P. v. Bell, 134 S. Ct. 2696, 189 L. Ed. 2d 739 (2014)Why is this relevant? It is important because otherwise the company would argue that the permit shielded it. The permit shield allows a company to hide from Regulatory Liability for unknown discharges if it has a permit. So, for example, If I have a permit that has limits for NOx, CO2, SO2, and is quiet on Co, cobalt, there is an assumption that even if I discharge Co I am not in violation of the permit. However under this third circuit ruling, the permit shield only protects you against regulatory enforcement. It does not shield you from liability for harm to people or property.

PM 2.5Kills More than

AIDS, malaria, breast cancer, and TB

3 to 7 Million Deaths Each Year

Rendering Creates PM2.5 by

Burning Grease, H2S and NH3

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PM 2.5Filterable PM2.5Solid or liquid material at stack temperature and higher (measured at ~250o to 1800o F)Stable in atmosphere and collected on ambient samplerCondensable PM2.5Vapor or gas at stack temperatureCondenses to liquid or solid at stack exitStable in atmosphere and collected on ambient sampler

Components of Direct PM2.5

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PM 2.5How Filterable and Condensable PM2.5 are Sampled

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EngineeringCase StudyTitle V Fresh Pork ProcessorNew RTO Stack Test PM2.5 Emissions ~ 90-tpy

Violation of Air Permit (more than 12 times the allowable discharge)

Reduce PM2.5 Emissions or Production Capacity

Filterable and Condensable PM2.5 Sampling Results

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EngineeringCase Study

H2S + 2 O2 = H2SO4

H2SO4 + 2 NH3 = (NH4)2SO4Formation of Ammonium Sulfate PM 2.5By Thermal Oxidation of High Intensity VaporsHow PM2.5 is Formed in Animal Rendering

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EngineeringCase StudyPre-Trial ConditionsCondensable Input to RTO = 1.92-lbs/hrCondensable Output from RTO = 18.71-lbs/hr~10-times PM2.5 Increase

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EngineeringCase StudyReduce PM Generation Potential in High Intensity VaporsVenturi Scrubber pH Control Venturi Scrubber Temperature ReductionIncrease Freshwater Makeup TDS ReductionReduce Vacuum at Pickup PointsIsolate Hair HydrolizerReduce Air Cooled Condenser Temperature Set Point

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EngineeringCase StudyTrial ResultsPre-Treated Vapor Condensable Output from RTO = 2.5-lbs/hr~87% Reduction of Condensable PM2.5

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EngineeringCase StudySolutionPatent Pending TO/RTO and Boiler Pre-Treatment Using Steen Researchs Super Scrubber Technology

Featuring Dual Scrubbing with RADOX

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EngineeringCase StudyStarve PM2.5 Precursors with RADOX Single or Dual ScrubbingH2S + 2 O2 = H2SO4

H2SO4 + 2 NH3 = (NH4)2SO4

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EngineeringScrubber ChemistriesMasking Agents

Enzymes

Scavengers

Oxidizers (Cl2, ClO2, O3, OH-)

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Masking Agents, Enzymes and Scavengers

Engineering

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Masking AgentsAdds VOCs

Environmental Sensitivity

No Feedback Control Based on Loading

High Water Use

Bio-Fouling

Engineering

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Enzyme with Masking AgentPatent Text ReNew

http://www.google.com/patents/US20120219480Minimal Reduction of H2S and NH3 compared to straight water w/o pH modification

Enzymes - Slow Reaction Time

Masking Agent

VOC Generation

Foaming (anti-foam agents spoil biodiesel use)

Engineering

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Triazine Scavinger Old Oil Field Technology

Nitrogen Loading to WWT

No Loading Feedback Control

High Water Use

Triazine Thiadiazine, Dithiazine

BioFouls to Insoluble Polymer

Engineering

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OxidizersEngineering

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OH the Hydroxyl Radical and the 2nd strongest oxidizer known to man.EngineeringRelative Oxidation Of Reactive Species Oxidizers

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Bleach and Chlorine Dioxide ClO2Weak, Temperature Sensitive Oxidizer

Volatile at low temperatures (Like Bleach which flashes at a low temperature, 100 Degrees F, Chlorine dioxide flashes at 110 Degrees F)

When free chlorine interacts with proteins environmentally detrimental compounds are such as haloamines, and trihalomethanes, THMs are produced. (THMs are toxic and known carcinogens)

Addition of salts to the water system

Has a negative effect on waste water

biological system

ClO2Engineering

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Purate 2-Part ClO2Low pH

Insoluble about 110 F

Acid Scrubbing only

Toxic blow down to bio ponds

Produces Carcinogenic Compounds THMs

Extreme Fire Hazard

Engineering3-Part ClO2Better pH range

Insoluble about 110 F

Toxic blow-down to bio ponds

High Salt Load

Produces Carcinogenic Compounds THMs

Extreme Fire Hazard

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EngineeringOzone O3

Toxic GasInduces BioFoulingLow Solubility in Water Requires Over-DosingLow Solubility Decreases More with Increasing Temperature

Low Solubility Decreases More with Increasing pHIncreases VOCs in air scrubber

Gold Kist Ball Ground, GA Case study O3

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EngineeringOzone Solubility vs. Temp The chart above shows ozone solubility vs. temperature for different ozone concentrations. The water pressure is at atmospheric (0 PSIG).(35 Degrees C = 95 Degrees F)Engineering

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EngineeringOzone Solubility vs. pH

Engineering

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EngineeringEngineeringOZONE

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OZONEToxicity, CDC, OSA (Known Carcinogen)

Does Ozone Cause Precancerous Changes in Cells? http://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.abstractDetail/abstract/2314Ozone https://www.osha.gov/dts/chemicalsampling/data/CH_259300.html Health Effectshttp://www.epa.gov/glo/health.html

Destroys Packing And Plastics

Low Solubility (Low pH Only)

Weak, Temperature Sensitive

Engineering

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Fenton Radox ReactionHydroxyl Radical the second strongest oxidizer know to man.Secondary Fenton chemistry reaction is the generation of peroxide free radical. Fe2+ + H2O2 Fe3+ + OH + OHFe3+ + H2O2 => Fe2+ + H+ + HOO0The peroxide molecule formed in this reaction (HO20) is a powerful free radical which oxidizes organic compounds.Engineering

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Characteristic Radox ReactionHighly Reactive

Destroys All Odor Compounds, Toxic VOCs

Effective At Any pH

Very High Solubility in Scrubber Water

Not Toxic or Carcinogenic

Effective at All Temperatures

No BioFouling, Keeps The Scrubber Clean

No Fire Risk

Engineering

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Radox Full Scale Stack Test Case Study 1: High Intensity Scrubber

Scrubber pulled from the cooker and presses.

Non-Methane Organic Carbon (NMOC) determined using US EPA Method 25A

Scrubber efficiency needed to be better then 80 percent removal.

Three continuous samples,each 45 minutes in duration. Engineering

RUN 1RUN 2RUN 3AverageInletFlow Rate, dsfm523519520521 acfm565559560561Total Non-Methane Hydrocarbon, ppm, as C11131103511261097 lb/hr, as CH41.4741.3381.4541.422

OutletFlow Rate, dsfm845845845845 acfm906905906906Total Non-Methane Hydrocarbon,

ppm, as C139.541.436.639.1 lb/hr, as CH40.08320.08720.07710.0825

DESTRUCTION EFFICIENCY, %94.493.594.794.2

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Radox USDA STUDYCase Study 2:Feather Dryer Air Scrubber

100 K SCFM Packed Bed Air Scrubber

USDA Compared ClO2 to RADOX-23 Fenton Treatment System

Gas chromatography ("GC") and mass spectrometry ("MS") was used to determine destruction efficiency

Results From USDA Study:

Samples from Radox-treated air streams had (1) 42 % higher concentration of carbon dioxide (CO2); (2) 69 % lower concentrations of the highly aldehyde compounds, and (3) 52 % lower total VOC when compared to untreated, or ClO2-treated samples.

The RADOX treatment reduced the total perceived odor intensity by 74 while the ClO2 treatment did not significantly alter the odor intensity.

"The RADOX catalyst was shown to be significantly more effective than chlorine dioxide (ClO2) for reducing the concentration of malodorous VOC and total VOC emitted from poultry rendering.

The concentration of highly malodorous aldehyde compounds, which were responsible for a majority of the poultry rendering odor, were not changed by the ClO2 treatment.Additionally, there was a 5-fold higher concentration of indole in the ClO2 samples when compared to RADOX-treated samples.

Engineering

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OH the Hydroxyl Radical and the 2nd strongest oxidizer known to man.EngineeringRelative Oxidation Of Reactive Species Oxidizers

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Fenton Radox ReactionHydroxyl Radical the second strongest oxidizer know to man.Secondary Fenton chemistry reaction is the generation of peroxide free radical. Fe2+ + H2O2 Fe3+ + OH + OHFe3+ + H2O2 => Fe2+ + H+ + HOO0The peroxide molecule formed in this reaction (HO20) is a powerful free radical which oxidizes organic compounds.Engineering

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Characteristic Radox ReactionHighly Reactive

Destroys All Odor Compounds, Toxic VOCs

Effective At Any pH

Very High Solubility in Scrubber Water

Not Toxic or Carcinogenic

Effective at All Temperatures

No BioFouling, Keeps The Scrubber Clean

No Fire Risk

Engineering

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Radox Make-Down and ControlEngineering

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Question and AnswersYes I believe theres a question there in the back.

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*Spray Venturis are not designed to remove Smoke and Micro particulate and Micro Aerosols

Micro Particulate are known carcinogens

PM 10 EPA PM 2.5*

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