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Presented by
Stephen R. Temple
Howard E. Whitney
Steen Research LLC
Steenresearch.com
U.S. Poultry, Proteins and Fats
Presentation
October 2015
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Cooking Fresh or Decaying ProteinCooking Fresh or Decaying Protein
Generates Odiferous and Toxic VaporsGenerates Odiferous and Toxic Vapors
ProblemProblem
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Common SenseCommon Sense
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Odor and ToxicityOdor and Toxicity
SourcesSources
Primary SourcesPrimary Sources Secondary SourcesSecondary Sources
Common SenseCommon Sense
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Innovations in Chemistry and Engineering
Primary SourcesPrimary Sources
 Infall BayInfall Bay
 Cooker and Hydrolyzer (Fugitive Odors)Cooker and Hydrolyzer (Fugitive Odors)
 Non-ConNon-Con
 Screw PressScrew Press
 CentrifugeCentrifuge
Odor and Toxicity SourcesOdor and Toxicity Sources
Common SenseCommon Sense
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Secondary SourcesSecondary Sources
 Cooker and HydrolyzerCooker and Hydrolyzer
CondensateCondensate
 Evaporator CondensateEvaporator Condensate
 W/W Bio ReactorsW/W Bio Reactors
 Aeration Ponds and BasinsAeration Ponds and Basins
 Milling RoomMilling Room
Odor and Toxicity SourcesOdor and Toxicity Sources
Common SenseCommon Sense
SCIENCESCIENCE
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Latin "scientia," meaning knowledge
Three Phases of Odor and ToxicityThree Phases of Odor and Toxicity
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ScienceScience
Nature of Odor and ToxicityNature of Odor and Toxicity
 Gas-Phase VOCsGas-Phase VOCs
 Aerosol Fats & OilsAerosol Fats & Oils
 Water Vapor and MistWater Vapor and Mist
 Solid ParticulatesSolid Particulates
 SmokeSmoke
STEEN RESEARCH, LLC
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Odor and Toxicity SourcesOdor and Toxicity Sources
ScienceScience
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Innovations in Chemistry and Engineering
GasesGases
ScienceScience
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Innovations in Chemistry and Engineering
ScienceScience
Ammonia
Trimethyl Amine
Methyl Pyrazine
Pyrrole
1-ethyl-1H-Pyrrole
Ethyl Pyrazine
Pyrazine
2,6-dimethyl-Pyrazine
1-methyl-1H-Pyrrole
2-methyl-Pyridine
2,5-dimethyl-1H-Pyrrole
3-methyl-Butenenitrile
3-methyl-Pyridine
Gases
Nitrogen Compounds
N,N-dimethyl-Benzamide
5-isopropyl-4-phenyl-3-hydroxy-
1,2,4-Triazole
Indole
Octanenitrile
3-Ethyl-2,5-dimethyl-1H pyrrole
5-butyl-3-methyl-1,2,3-8A-
tetrahydroindolizine
Acetamide
N,N-dibutyl-Formamide
Benzonitrile
2-Methyl-pyrrole
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Gases
Hydrogen Sulfide
Dimethyl Trisulfide
Dimethyl Disulfide
Carbonyl Sulfide
Thiophene
methyl-ethyl-Disulfide
Thiirane
Dimethyl Sulf
Methylthio Ethane
Carbon disulfide
2-methyl-Thiophene
3-Phenyl -Thiophene
Benzothiazole
3-(Methylthio)-1-propene
2-methyl-Thiazole
Sulfur Compounds
ScienceScience
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Gases
3-methyl-Butanal
2-methyl-Propanal
2-methyl-Butanal
Acetaldehyde
Aldehyde similar to 3-methyl-Butanal
Hexanal
Butanal
Benzaldehyde
Pentanal
Furfural
Heptanal
3-methylthio-Butyraldehyde
Propionaldehyde
Isobutyraldehyde
Isovaleraldehyde
3-Methyl-pentanal
2-methyl-2-Butenal
2-Dodecenal
Nonanal
1-Piperidinecarboxaldehyde
Heptanal
3-methylthio-Butyraldehyde
Propionaldehyde
Isobutyraldehyde
Isovaleraldehyde
3-Methyl-pentanal
Octanal
2-methyl-2-Butenal
2-Dodecenal
Nonanal
1-Piperidinecarboxaldehyde
Octanal
Aldehydes
ScienceScience
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Innovations in Chemistry and Engineering
Gases
Acetic acid
Propanoic acid
Isobutyric acid
Butyric acid
Isovaleric acid
2-Furancarboxylic acid
Valeric acid
4-Methyl-pentanoic acid
Caproic acid
1,2-Benzenedicarboxylic acid
2-Ethylhexanoic acid
Volatile Fatty Acids
Octanoic acid
Nonanoic acid
4-Carboxamidonicotinic acid
Decanoic acid
Pentadecanoic acid
Thiosulfuric acid
Benzoic acid
(Z)-9-Octadecenoic acid
(Z)-9-Octadecenoic acid
Hexanedioic acid
Heptanoic acid
ScienceScience
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Gases
Methyl Acetate
Propyl Acetate
Butyl Acetate
Ethyl Butanoate
Propyl Butanoate
Butyl Butanoate
Methyl Butanoate
4-Hydroxydodecanoic acid lactone
Ethyl 3-phenylpropionate
Esters
ScienceScience
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Innovations in Chemistry and Engineering
Gases
Acetone
2-Butanone
1-(2-furanyl)-Ethanone
2-Heptanone
Methyl Isobutyl Ketone (MIBK)
2-Pyrrolidinone
3-acetyl-4-hydroxy-2(5H)-Furanone
Piperidinone
1,6-Dioxacyclododecane-7,12-dione
1-Phenyl-ethanone
1-(Methoxy-3-pyranzinyl)-1-ethanone
2-Octanone
3-Hexanone
2-Nonanone
2-Decanone
Ketones
ScienceScience
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Innovations in Chemistry and Engineering
Gases
Methanol
Ethanol
Furfuryl Alcohol
1-Butanol
2-methyl-1-Propanol
1-Propanol
α,α-Dimethyl
benzenemethanol
1-Heptadecanol
2,5,8,11,14-
Pentaoxahexadecan-16-ol
Methylphloroglucinol
Heptanol
2-Ethyl-hexanol
1-Hexanol
2-Butoxy-Ethanol
2-Furanmethanol
Benzenemethanol
Benzeneethanol
1-Octanol
Alcohols
ScienceScience
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Innovations in Chemistry and Engineering
Gases
Oxygen Compounds
Furan
2-methyl-Furan
2,5-dimethyl-Furan
Tetrahydrofuran
2-Pentyl-Furan
3-Acetyl-6-methyl-2H-pyran-
2,4(3H)-dione
ScienceScience
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Innovations in Chemistry and Engineering
Gases
1,1-dichloro-2-Propanone
1-chloro-2-Butanone
Chloromethane
Chloroform (THM1)
Tetrachloroethene (PCE)
Dibromochloromethane (THM3)
Bromodichloromethane (THM2)
Carbon tetrachloride
1,2-Dimethyl-hydrazine dichloride
Chlorinated VOCs
ScienceScience
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Gases
2-methyl-Butane
Propylene
Toluene
Heptane
Benzene
Hexane
Ethylbenzene
2-Butene
1-Methyl-2-isopropyl benzene
Naphthalene
Trans-(-)-5-methyl-3-(1-methylethenyl)-cyclohexene
4-Vinyl-2-methoxy-phenol
p-Cresol
Methylnapthalene
Hydrocarbons
Phenol
2-Methyl-decane
2-methyl-1-Propene
Limonene
(1-Methylethenyl)-benzene
9-Octadecyne
Trans-caryophyllene
1,3,5,7-Cyclooctatetraene
Polynuclear Aromatics
ScienceScience
 Nitrogen CompoundsNitrogen Compounds
 Sulfur CompoundsSulfur Compounds
 AldehydesAldehydes
 Volatile Fatty AcidsVolatile Fatty Acids
 EstersEsters
 KetonesKetones
 AlcoholsAlcohols
 Oxygen CompoundsOxygen Compounds
 Chlorinated VOCsChlorinated VOCs
 HydrocarbonsHydrocarbons
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GasesGases
ScienceScience
VOCs Detected in
High Intensity Vapors
Water SolubilityWater Solubility
Compounds Affinity For WaterCompounds Affinity For Water
VolatilityVolatility
Compounds Affinity For AirCompounds Affinity For Air
AdsorptionAdsorption
Compounds Affinity For SolidsCompounds Affinity For Solids
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ScienceScience
Physical Properties
Gases
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Gases
ScienceScience
Water Solubility
Temperature Sensitive
Low Temp = High Solubility
Volatility
pH Sensitive
Alkaline pH Sulfur Compounds
Acidic pH Nitrogen Compounds
Neutral pH Oxygenated Compounds
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Gases
ScienceScience
AdsorptionAdsorption
Aerosolized Proteins, Fats Oils Greases,
Solid Particulates and Smoke
Contain:
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Gases
pH –Vapor SolubilitypH –Vapor Solubility
Hydrogen Sulfide HHydrogen Sulfide H22SS
vsvs
Ammonia NHAmmonia NH33
H2S
NH3
ScienceScience
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Innovations in Chemistry and Engineering
Liquid AerosolsLiquid Aerosols
ScienceScience
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ScienceScience
Liquid AerosolsLiquid Aerosols
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ScienceScience
SmokeSmoke
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ScienceScience
Solid ParticulateSolid Particulate
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ScienceScience
Solid ParticulateSolid Particulate
Science
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Odor VOCs Absorbed on ParticulatesOdor VOCs Absorbed on Particulates
BK
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ScienceScience
Multi-Phase FlowMulti-Phase Flow
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Engineering
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Innovations in Chemistry and Engineering
Engineering Constraints of Multi-Phase
Wet Gas Rendering Waste
EngineeringEngineering
 120- to 300-degrees F120- to 300-degrees F
 High Humidity and Aerosolized Water VaporHigh Humidity and Aerosolized Water Vapor
 Smoke and Solid ParticulatesSmoke and Solid Particulates
 Aerosolized Oils, Fats, Greases, Tallow, Proteins, etc.Aerosolized Oils, Fats, Greases, Tallow, Proteins, etc.
 Gas-Phase Ammonia, Hydrogen Sulfide, Complex of Odorous and Toxic OrganicsGas-Phase Ammonia, Hydrogen Sulfide, Complex of Odorous and Toxic Organics
 Non-Uniform and Variable Flow Density Patterns In Pipe NetworksNon-Uniform and Variable Flow Density Patterns In Pipe Networks
 Difficult to Quantify Total Mass FlowDifficult to Quantify Total Mass Flow
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Engineered Mass Reduction Methods:
Temperature Changes and Transfer to Water
EngineeringEngineering
 Air-Cooled Condensation (Non-Con isAir-Cooled Condensation (Non-Con is NOT TRUENOT TRUE))
 Spray Venturi Removal of large Particulates, Aerosols and Water Soluble GasesSpray Venturi Removal of large Particulates, Aerosols and Water Soluble Gases
 Advanced Condensation, Precipitation and Wilson Cloud Formation on CCNAdvanced Condensation, Precipitation and Wilson Cloud Formation on CCN
 Electrostatic Ionization of CCN-CloudElectrostatic Ionization of CCN-Cloud
 Packed Bed Wet Scrubbing For CCN-Cloud Condensation and Water SolublePacked Bed Wet Scrubbing For CCN-Cloud Condensation and Water Soluble
GasesGases
 Thermal Oxidation (TO/RTO/RCO/Boiler) For Complete VOC DestructionThermal Oxidation (TO/RTO/RCO/Boiler) For Complete VOC Destruction
Advanced Pre-TreatmentAdvanced Pre-Treatment
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Engineering
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Engineering
Advanced Pre-TreatmentAdvanced Pre-Treatment
Cloud Formation andCloud Formation and
EliminationElimination
PM 2.5PM 2.5
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Innovations in Chemistry and Engineering
PM 2.5
Micro-Particulate
Pollution
USEPA Mandated Testing
under National Ambient
Air 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 2.5
Fine ParticlesFine Particles
Combustion, gases toCombustion, gases to
particlesparticles
Sulfates/acidsSulfates/acids
NitrateNitrate
AmmoniumAmmonium
OrganicsOrganics
CarbonCarbon
MetalsMetals
WaterWater
SourcesSources::
Coal, oil, gasoline, diesel,Coal, oil, gasoline, diesel,
wood combustionwood combustion
Transformation of SOx,Transformation of SOx,
NOx, organic gasesNOx, organic gases
including biogenicsincluding biogenics
High temperature industrialHigh temperature industrial
processesprocesses
((thermal oxidizers,thermal oxidizers,
smelters, steel mills)smelters, steel mills)
ImpactsImpacts::
Children and Seniors mostChildren and Seniors most
at risk for prematureat risk for premature
death, heart attacks,death, heart attacks,
acute bronchitis andacute bronchitis and
aggravated asthma.aggravated asthma.
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PM 2.5
Who Does PM2.5 Effect?
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PM 2.5
How PM2.5 Gets into Lungs, Blood and Brain
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PM 2.5
 Air 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/25147109http://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/22544506http://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/21399501http://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/25341536http://www.ncbi.nlm.nih.gov/pubmed/25341536
 Toxicity beyond the Lung: Connecting PM2.5, Inflammation, and Diabetes
 http://www.ncbi.nlm.nih.gov/pubmed/25341536http://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/26220751http://www.ncbi.nlm.nih.gov/pubmed/26220751
Why Worry? Downwind Liability for:
But We Have a PermitBut We Have a Permit
The Third Circuit recently concluded that obtaining aThe Third Circuit recently concluded that obtaining a permit under the Clean Air Actpermit under the Clean Air Act
Does NOT ShieldDoes NOT Shield a company from liabilitya company from liability for damages caused by the plant?for damages caused by the plant?
The Supreme Court refused to take the case on appeal so the decisionThe Supreme Court refused to take the case on appeal so the decision
standsstands.. Bell v. Cheswick Generating StationBell v. Cheswick Generating Station, 734 F.3d 188, 190 (3d Cir. 2013), 734 F.3d 188, 190 (3d Cir. 2013) cert.cert.
denied sub nom.denied sub nom. GenOn Power Midwest, L.P. v. BellGenOn Power Midwest, L.P. v. Bell, 134 S. Ct. 2696, 189 L. Ed. 2d, 134 S. Ct. 2696, 189 L. Ed. 2d
739 (2014)739 (2014)
Why is this relevant? It is important because otherwise the company would argue thatWhy is this relevant? It is important because otherwise the company would argue that
the permit shielded it.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 onSo, 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 ofCo, 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 youthe permit. However under this third circuit ruling, the permit shield only protects you
against regulatory enforcement.against regulatory enforcement. It does not shield you from liability for harm to
people or property.
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PM 2.5
 Kills More thanKills More than
AIDS, malaria, breast cancer, and TBAIDS, malaria, breast cancer, and TB
 3 to 7 Million Deaths Each Year3 to 7 Million Deaths Each Year
 Rendering Creates PM2.5 byRendering Creates PM2.5 by
Burning Grease, HBurning Grease, H22S and NHS and NH33
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PM 2.5
 Filterable PMFilterable PM2.52.5
 Solid or liquid material at stack temperature andSolid or liquid material at stack temperature and
higher (measured at ~250higher (measured at ~250oo
to 1800to 1800oo
F)F)
 Stable in atmosphere and collected on ambientStable in atmosphere and collected on ambient
samplersampler
 Condensable PMCondensable PM2.52.5
 Vapor or gas at stack temperatureVapor or gas at stack temperature
 Condenses to liquid or solid at stack exitCondenses to liquid or solid at stack exit
 Stable in atmosphere and collected on ambientStable in atmosphere and collected on ambient
samplersampler
Components of Direct PMComponents of Direct PM2.52.5
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PM 2.5
How Filterable and Condensable PM2.5 are Sampled
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EngineeringEngineering
Case StudyCase Study
Title V Fresh Pork Processor
 New RTO Stack Test PM2.5 Emissions ~ 90-tpyNew RTO Stack Test PM2.5 Emissions ~ 90-tpy
 Violation of Air Permit (Violation of Air Permit (more than 12 times the
allowable discharge)
 Reduce PM2.5 Emissions or Production CapacityReduce PM2.5 Emissions or Production Capacity
Filterable and Condensable PM2.5 Sampling Results
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EngineeringEngineering
Case StudyCase Study
H2S + 2 O2 = H2SO4
H2SO4 + 2 NH3 = (NH4)2SO4
Formation of Ammonium Sulfate PM 2.5
By Thermal Oxidation of High Intensity Vapors
How PM2.5 is Formed in Animal Rendering
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EngineeringEngineering
Case StudyCase Study
Pre-Trial Conditions
Condensable Input to RTO = 1.92-lbs/hr
Condensable Output from RTO = 18.71-lbs/hr
~10-times PM2.5 Increase
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EngineeringEngineering
Case StudyCase Study
Reduce PM Generation Potential in
High Intensity Vapors
 Venturi Scrubber pH ControlVenturi Scrubber pH Control
 Venturi Scrubber Temperature ReductionVenturi Scrubber Temperature Reduction
 Increase Freshwater Makeup TDS ReductionIncrease Freshwater Makeup TDS Reduction
 Reduce Vacuum at Pickup PointsReduce Vacuum at Pickup Points
 Isolate Hair HydrolizerIsolate Hair Hydrolizer
 Reduce Air Cooled Condenser Temperature SetReduce Air Cooled Condenser Temperature Set
PointPoint
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EngineeringEngineering
Case StudyCase Study
Trial Results
Pre-Treated Vapor Condensable Output from RTO = 2.5-lbs/hr
~87% Reduction of Condensable PM2.5
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EngineeringEngineering
Case StudyCase Study
Solution
 Patent Pending TO/RTO and Boiler Pre-
Treatment Using Steen Research’s Super
Scrubber Technology
 Featuring Dual Scrubbing with RADOX
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Innovations in Chemistry and Engineering
EngineeringEngineering
Case StudyCase Study
Starve PM2.5 Precursors with RADOX Single or Dual Scrubbing
H2S + 2 O2 = H2SO4
H2SO4 + 2 NH3 = (NH4)2SO4
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Scrubber ChemistriesScrubber Chemistries
 Masking AgentsMasking Agents
 EnzymesEnzymes
 ScavengersScavengers
 Oxidizers (ClOxidizers (Cl22, ClO, ClO2,2, OO3,3, OHOH--
))
Masking Agents, Enzymes and ScavengersMasking Agents, Enzymes and Scavengers
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Engineering
Masking AgentsMasking Agents
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 Adds VOC’sAdds VOC’s
 EnvironmentalEnvironmental
SensitivitySensitivity
 No Feedback ControlNo Feedback Control
Based on LoadingBased on Loading
 High Water UseHigh Water Use
 Bio-FoulingBio-Fouling
Engineering
EnzymeEnzyme
withwith
Masking AgentMasking Agent
 Patent TextPatent Text ReNewReNew
http://www.google.com/patents/US20120219480http://www.google.com/patents/US20120219480
Minimal Reduction of H2S and NH3 compared to straight water w/o pHMinimal Reduction of H2S and NH3 compared to straight water w/o pH
modificationmodification
 Enzymes - Slow Reaction TimeEnzymes - Slow Reaction Time
 Masking AgentMasking Agent
 VOC GenerationVOC Generation
 Foaming (anti-foam agents spoil biodiesel use)Foaming (anti-foam agents spoil biodiesel use)
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Engineering
Triazine ScavingerTriazine Scavinger
 Old Oil Field TechnologyOld Oil Field Technology
 Nitrogen Loading to WWTNitrogen Loading to WWT
 No Loading Feedback ControlNo Loading Feedback Control
 High Water UseHigh Water Use
 Triazine → Thiadiazine, → DithiazineTriazine → Thiadiazine, → Dithiazine
 BioFouls to Insoluble PolymerBioFouls to Insoluble Polymer
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Engineering
OxidizersOxidizers
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Engineering
OHOH the Hydroxyl Radical and the 2the Hydroxyl Radical and the 2ndnd
strongest oxidizer known to man.strongest oxidizer known to man.
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Engineering
Relative Oxidation Of Reactive Species
Oxidizers
Bleach and Chlorine Dioxide ClOBleach and Chlorine Dioxide ClO22
 Weak, Temperature Sensitive OxidizerWeak, Temperature Sensitive Oxidizer
 Volatile at low temperatures (Like Bleach which flashes at a lowVolatile at low temperatures (Like Bleach which flashes at a low
temperature, 100 Degrees F, Chlorine dioxide flashes at 110 Degrees F)temperature, 100 Degrees F, Chlorine dioxide flashes at 110 Degrees F)
 When free chlorine interacts with proteins environmentally detrimentalWhen free chlorine interacts with proteins environmentally detrimental
compounds are such ascompounds are such as haloamines, and trihalomethaneshaloamines, and trihalomethanes, THM’s are, THM’s are
produced.produced. (THM’s are toxic and known carcinogens)(THM’s are toxic and known carcinogens)
 Addition of salts to the water systemAddition of salts to the water system
 Has a negative effect on waste waterHas a negative effect on waste water
biological systembiological system
ClO2 Engineering
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Purate 2-Part ClO2Purate 2-Part ClO2
 Low pHLow pH
 Insoluble about 110 FInsoluble about 110 F
 Acid Scrubbing onlyAcid Scrubbing only
 Toxic blow down to bio pondsToxic blow down to bio ponds
 Produces CarcinogenicProduces Carcinogenic
CompoundsCompounds THM’sTHM’s
 Extreme Fire HazardExtreme Fire Hazard
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Engineering
3-Part ClO23-Part ClO2
 Better pH rangeBetter pH range
 Insoluble about 110 FInsoluble about 110 F
 Toxic blow-down to bio pondsToxic blow-down to bio ponds
 High Salt LoadHigh Salt Load
 Produces CarcinogenicProduces Carcinogenic
CompoundsCompounds THM’sTHM’s
 Extreme Fire HazardExtreme Fire Hazard
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Engineering
Ozone OOzone O33
 Toxic GasToxic Gas
 Induces BioFoulingInduces BioFouling
 Low Solubility in Water Requires Over-Low Solubility in Water Requires Over-
DosingDosing
 Low Solubility Decreases More withLow Solubility Decreases More with
Increasing TemperatureIncreasing Temperature
 Low Solubility Decreases More withLow Solubility Decreases More with
Increasing pHIncreasing pH
 Increases VOC’s in air scrubberIncreases VOC’s in air scrubber
Gold Kist Ball Ground, GA Case studyGold Kist Ball Ground, GA Case study
O3
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Engineering
Ozone Solubility vs. TempOzone 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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Engineering
Ozone Solubility vs. pHOzone Solubility vs. pH
Engineering
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Engineering
Engineering
OZONE
OZONE
 Toxicity, CDC, OSA (Toxicity, CDC, OSA (Known CarcinogenKnown Carcinogen))
Does Ozone Cause Precancerous Changes in Cells?Does Ozone Cause Precancerous Changes in Cells?
http://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.abstractDetail/abstract/2314http://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.abstractDetail/abstract/2314
OzoneOzone
https://www.osha.gov/dts/chemicalsampling/data/CH_259300.htmlhttps://www.osha.gov/dts/chemicalsampling/data/CH_259300.html
Health EffectsHealth Effects
http://www.epa.gov/glo/health.htmlhttp://www.epa.gov/glo/health.html
 Destroys Packing And PlasticsDestroys Packing And Plastics
 Low Solubility (Low pH Only)Low Solubility (Low pH Only)
 Weak, Temperature SensitiveWeak, Temperature Sensitive
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Engineering
Fenton Radox ReactionFenton Radox Reaction
Hydroxyl Radical the second strongest oxidizer know to man.
Secondary Fenton chemistry reaction is the generation of peroxide free radical.
FeFe2+2+
+ H+ H22OO22 → Fe→ Fe3+3+
+ OH+ OH −−
++ OHOH
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Fe3+
+ H2O2 => Fe2+
+ H+
+ HOO0
The peroxide molecule formed in this reaction (HO2
0
) is a powerful free
radical which oxidizes organic compounds.
Engineering
Characteristic Radox ReactionCharacteristic Radox Reaction
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
 Highly ReactiveHighly Reactive
 Destroys All Odor Compounds, Toxic VOC’sDestroys All Odor Compounds, Toxic VOC’s
 Effective At Any pHEffective At Any pH
 Very High Solubility in Scrubber WaterVery High Solubility in Scrubber Water
 Not Toxic or CarcinogenicNot Toxic or Carcinogenic
 Effective at All TemperaturesEffective at All Temperatures
 No BioFouling, Keeps The Scrubber CleanNo BioFouling, Keeps The Scrubber Clean
 No Fire RiskNo Fire Risk
Engineering
Radox Full Scale Stack TestRadox Full Scale Stack Test
Case Study 1:Case Study 1:
High Intensity ScrubberHigh Intensity Scrubber
Scrubber pulled from the
cooker and presses.
Non-Methane Organic
Carbon (NMOC)
ermined using
US EPA Method 25A
Scrubber efficiency needed
to be better then 80 percent
removal.
Three continuous samples,
each 45 minutes in duration.
RUN 1 RUN 2 RUN 3 Average
Inlet
Flow Rate,
dsfm 523 519 520 521
acfm 565 559 560 561
Total Non-Methane Hydrocarbon,
ppm, as C1 1131 1035 1126 1097
lb/hr, as CH4 1.474 1.338 1.454 1.422
Outlet
Flow Rate,
dsfm 845 845 845 845
acfm 906 905 906 906
Total Non-Methane Hydrocarbon,
ppm, as C1 39.5 41.4 36.6 39.1
lb/hr, as CH4 0.0832 0.0872 0.0771 0.0825
DESTRUCTION EFFICIENCY, % 94.4 93.5 94.7 94.2
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Engineering
Radox USDA STUDYRadox USDA STUDY
Case Study 2:Case Study 2:
Feather Dryer AirFeather Dryer Air
ScrubberScrubber
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: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.”
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Engineering
OHOH the Hydroxyl Radical and the 2the Hydroxyl Radical and the 2ndnd
strongest oxidizer known to man.strongest oxidizer known to man.
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Engineering
Relative Oxidation Of Reactive Species
Oxidizers
Fenton Radox ReactionFenton Radox Reaction
Hydroxyl Radical the second strongest oxidizer know to man.
Secondary Fenton chemistry reaction is the generation of peroxide free radical.
FeFe2+2+
+ H+ H22OO22 → Fe→ Fe3+3+
+ OH+ OH −−
++ OHOH
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Fe3+
+ H2O2 => Fe2+
+ H+
+ HOO0
The peroxide molecule formed in this reaction (HO2
0
) is a powerful free
radical which oxidizes organic compounds.
Engineering
Characteristic Radox ReactionCharacteristic Radox Reaction
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
 Highly ReactiveHighly Reactive
 Destroys All Odor Compounds, Toxic VOC’sDestroys All Odor Compounds, Toxic VOC’s
 Effective At Any pHEffective At Any pH
 Very High Solubility in Scrubber WaterVery High Solubility in Scrubber Water
 Not Toxic or CarcinogenicNot Toxic or Carcinogenic
 Effective at All TemperaturesEffective at All Temperatures
 No BioFouling, Keeps The Scrubber CleanNo BioFouling, Keeps The Scrubber Clean
 No Fire RiskNo Fire Risk
Engineering
Radox Make-Down and ControlRadox Make-Down and Control
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
Engineering
Question and AnswersQuestion and Answers
STEEN RESEARCH, LLC
Innovations in Chemistry and Engineering
“Yes …I believe there’s a question there in the back.”

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Odor control pm2.5 talk-oct-2015 final

  • 1. Presented by Stephen R. Temple Howard E. Whitney Steen Research LLC Steenresearch.com U.S. Poultry, Proteins and Fats Presentation October 2015 STEEN RESEARCH, LLC Innovations in Chemistry and Engineering
  • 2. Cooking Fresh or Decaying ProteinCooking Fresh or Decaying Protein Generates Odiferous and Toxic VaporsGenerates Odiferous and Toxic Vapors ProblemProblem STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Common SenseCommon Sense
  • 3. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Odor and ToxicityOdor and Toxicity SourcesSources Primary SourcesPrimary Sources Secondary SourcesSecondary Sources Common SenseCommon Sense
  • 4. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Primary SourcesPrimary Sources  Infall BayInfall Bay  Cooker and Hydrolyzer (Fugitive Odors)Cooker and Hydrolyzer (Fugitive Odors)  Non-ConNon-Con  Screw PressScrew Press  CentrifugeCentrifuge Odor and Toxicity SourcesOdor and Toxicity Sources Common SenseCommon Sense
  • 5. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Secondary SourcesSecondary Sources  Cooker and HydrolyzerCooker and Hydrolyzer CondensateCondensate  Evaporator CondensateEvaporator Condensate  W/W Bio ReactorsW/W Bio Reactors  Aeration Ponds and BasinsAeration Ponds and Basins  Milling RoomMilling Room Odor and Toxicity SourcesOdor and Toxicity Sources Common SenseCommon Sense
  • 6. SCIENCESCIENCE STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Latin "scientia," meaning knowledge
  • 7. Three Phases of Odor and ToxicityThree Phases of Odor and Toxicity STEEN RESEARCH, LLC Innovations in Chemistry and Engineering ScienceScience
  • 8. Nature of Odor and ToxicityNature of Odor and Toxicity  Gas-Phase VOCsGas-Phase VOCs  Aerosol Fats & OilsAerosol Fats & Oils  Water Vapor and MistWater Vapor and Mist  Solid ParticulatesSolid Particulates  SmokeSmoke STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Odor and Toxicity SourcesOdor and Toxicity Sources ScienceScience
  • 9. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering GasesGases ScienceScience
  • 10. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering ScienceScience Ammonia Trimethyl Amine Methyl Pyrazine Pyrrole 1-ethyl-1H-Pyrrole Ethyl Pyrazine Pyrazine 2,6-dimethyl-Pyrazine 1-methyl-1H-Pyrrole 2-methyl-Pyridine 2,5-dimethyl-1H-Pyrrole 3-methyl-Butenenitrile 3-methyl-Pyridine Gases Nitrogen Compounds N,N-dimethyl-Benzamide 5-isopropyl-4-phenyl-3-hydroxy- 1,2,4-Triazole Indole Octanenitrile 3-Ethyl-2,5-dimethyl-1H pyrrole 5-butyl-3-methyl-1,2,3-8A- tetrahydroindolizine Acetamide N,N-dibutyl-Formamide Benzonitrile 2-Methyl-pyrrole
  • 11. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases Hydrogen Sulfide Dimethyl Trisulfide Dimethyl Disulfide Carbonyl Sulfide Thiophene methyl-ethyl-Disulfide Thiirane Dimethyl Sulf Methylthio Ethane Carbon disulfide 2-methyl-Thiophene 3-Phenyl -Thiophene Benzothiazole 3-(Methylthio)-1-propene 2-methyl-Thiazole Sulfur Compounds ScienceScience
  • 12. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases 3-methyl-Butanal 2-methyl-Propanal 2-methyl-Butanal Acetaldehyde Aldehyde similar to 3-methyl-Butanal Hexanal Butanal Benzaldehyde Pentanal Furfural Heptanal 3-methylthio-Butyraldehyde Propionaldehyde Isobutyraldehyde Isovaleraldehyde 3-Methyl-pentanal 2-methyl-2-Butenal 2-Dodecenal Nonanal 1-Piperidinecarboxaldehyde Heptanal 3-methylthio-Butyraldehyde Propionaldehyde Isobutyraldehyde Isovaleraldehyde 3-Methyl-pentanal Octanal 2-methyl-2-Butenal 2-Dodecenal Nonanal 1-Piperidinecarboxaldehyde Octanal Aldehydes ScienceScience
  • 13. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases Acetic acid Propanoic acid Isobutyric acid Butyric acid Isovaleric acid 2-Furancarboxylic acid Valeric acid 4-Methyl-pentanoic acid Caproic acid 1,2-Benzenedicarboxylic acid 2-Ethylhexanoic acid Volatile Fatty Acids Octanoic acid Nonanoic acid 4-Carboxamidonicotinic acid Decanoic acid Pentadecanoic acid Thiosulfuric acid Benzoic acid (Z)-9-Octadecenoic acid (Z)-9-Octadecenoic acid Hexanedioic acid Heptanoic acid ScienceScience
  • 14. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases Methyl Acetate Propyl Acetate Butyl Acetate Ethyl Butanoate Propyl Butanoate Butyl Butanoate Methyl Butanoate 4-Hydroxydodecanoic acid lactone Ethyl 3-phenylpropionate Esters ScienceScience
  • 15. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases Acetone 2-Butanone 1-(2-furanyl)-Ethanone 2-Heptanone Methyl Isobutyl Ketone (MIBK) 2-Pyrrolidinone 3-acetyl-4-hydroxy-2(5H)-Furanone Piperidinone 1,6-Dioxacyclododecane-7,12-dione 1-Phenyl-ethanone 1-(Methoxy-3-pyranzinyl)-1-ethanone 2-Octanone 3-Hexanone 2-Nonanone 2-Decanone Ketones ScienceScience
  • 16. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases Methanol Ethanol Furfuryl Alcohol 1-Butanol 2-methyl-1-Propanol 1-Propanol α,α-Dimethyl benzenemethanol 1-Heptadecanol 2,5,8,11,14- Pentaoxahexadecan-16-ol Methylphloroglucinol Heptanol 2-Ethyl-hexanol 1-Hexanol 2-Butoxy-Ethanol 2-Furanmethanol Benzenemethanol Benzeneethanol 1-Octanol Alcohols ScienceScience
  • 17. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases Oxygen Compounds Furan 2-methyl-Furan 2,5-dimethyl-Furan Tetrahydrofuran 2-Pentyl-Furan 3-Acetyl-6-methyl-2H-pyran- 2,4(3H)-dione ScienceScience
  • 18. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases 1,1-dichloro-2-Propanone 1-chloro-2-Butanone Chloromethane Chloroform (THM1) Tetrachloroethene (PCE) Dibromochloromethane (THM3) Bromodichloromethane (THM2) Carbon tetrachloride 1,2-Dimethyl-hydrazine dichloride Chlorinated VOCs ScienceScience
  • 19. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases 2-methyl-Butane Propylene Toluene Heptane Benzene Hexane Ethylbenzene 2-Butene 1-Methyl-2-isopropyl benzene Naphthalene Trans-(-)-5-methyl-3-(1-methylethenyl)-cyclohexene 4-Vinyl-2-methoxy-phenol p-Cresol Methylnapthalene Hydrocarbons Phenol 2-Methyl-decane 2-methyl-1-Propene Limonene (1-Methylethenyl)-benzene 9-Octadecyne Trans-caryophyllene 1,3,5,7-Cyclooctatetraene Polynuclear Aromatics ScienceScience
  • 20.  Nitrogen CompoundsNitrogen Compounds  Sulfur CompoundsSulfur Compounds  AldehydesAldehydes  Volatile Fatty AcidsVolatile Fatty Acids  EstersEsters  KetonesKetones  AlcoholsAlcohols  Oxygen CompoundsOxygen Compounds  Chlorinated VOCsChlorinated VOCs  HydrocarbonsHydrocarbons STEEN RESEARCH, LLC Innovations in Chemistry and Engineering GasesGases ScienceScience VOCs Detected in High Intensity Vapors
  • 21. Water SolubilityWater Solubility Compounds Affinity For WaterCompounds Affinity For Water VolatilityVolatility Compounds Affinity For AirCompounds Affinity For Air AdsorptionAdsorption Compounds Affinity For SolidsCompounds Affinity For Solids STEEN RESEARCH, LLC Innovations in Chemistry and Engineering ScienceScience Physical Properties Gases
  • 22. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases ScienceScience Water Solubility Temperature Sensitive Low Temp = High Solubility Volatility pH Sensitive Alkaline pH Sulfur Compounds Acidic pH Nitrogen Compounds Neutral pH Oxygenated Compounds
  • 23. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases ScienceScience AdsorptionAdsorption Aerosolized Proteins, Fats Oils Greases, Solid Particulates and Smoke Contain:
  • 24. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Gases pH –Vapor SolubilitypH –Vapor Solubility Hydrogen Sulfide HHydrogen Sulfide H22SS vsvs Ammonia NHAmmonia NH33 H2S NH3 ScienceScience
  • 25. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Liquid AerosolsLiquid Aerosols ScienceScience
  • 26. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering ScienceScience Liquid AerosolsLiquid Aerosols
  • 27. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering ScienceScience SmokeSmoke
  • 28. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering ScienceScience Solid ParticulateSolid Particulate
  • 29. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering ScienceScience Solid ParticulateSolid Particulate
  • 30. Science STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Odor VOCs Absorbed on ParticulatesOdor VOCs Absorbed on Particulates BK
  • 31. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering ScienceScience Multi-Phase FlowMulti-Phase Flow
  • 32. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 33. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering Constraints of Multi-Phase Wet Gas Rendering Waste EngineeringEngineering  120- to 300-degrees F120- to 300-degrees F  High Humidity and Aerosolized Water VaporHigh Humidity and Aerosolized Water Vapor  Smoke and Solid ParticulatesSmoke and Solid Particulates  Aerosolized Oils, Fats, Greases, Tallow, Proteins, etc.Aerosolized Oils, Fats, Greases, Tallow, Proteins, etc.  Gas-Phase Ammonia, Hydrogen Sulfide, Complex of Odorous and Toxic OrganicsGas-Phase Ammonia, Hydrogen Sulfide, Complex of Odorous and Toxic Organics  Non-Uniform and Variable Flow Density Patterns In Pipe NetworksNon-Uniform and Variable Flow Density Patterns In Pipe Networks  Difficult to Quantify Total Mass FlowDifficult to Quantify Total Mass Flow
  • 34. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineered Mass Reduction Methods: Temperature Changes and Transfer to Water EngineeringEngineering  Air-Cooled Condensation (Non-Con isAir-Cooled Condensation (Non-Con is NOT TRUENOT TRUE))  Spray Venturi Removal of large Particulates, Aerosols and Water Soluble GasesSpray Venturi Removal of large Particulates, Aerosols and Water Soluble Gases  Advanced Condensation, Precipitation and Wilson Cloud Formation on CCNAdvanced Condensation, Precipitation and Wilson Cloud Formation on CCN  Electrostatic Ionization of CCN-CloudElectrostatic Ionization of CCN-Cloud  Packed Bed Wet Scrubbing For CCN-Cloud Condensation and Water SolublePacked Bed Wet Scrubbing For CCN-Cloud Condensation and Water Soluble GasesGases  Thermal Oxidation (TO/RTO/RCO/Boiler) For Complete VOC DestructionThermal Oxidation (TO/RTO/RCO/Boiler) For Complete VOC Destruction
  • 35. Advanced Pre-TreatmentAdvanced Pre-Treatment STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 36. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering Advanced Pre-TreatmentAdvanced Pre-Treatment
  • 37. Cloud Formation andCloud Formation and EliminationElimination
  • 38. PM 2.5PM 2.5 STEEN RESEARCH, LLC Innovations in Chemistry and Engineering
  • 39. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering PM 2.5 Micro-Particulate Pollution USEPA Mandated Testing under National Ambient Air Quality Standards (NAAQS) and Prevention of Significant Deterioration (PSD) increments for the secondarily formed component of PM2.5
  • 40. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering PM 2.5
  • 41. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering PM 2.5 Fine ParticlesFine Particles Combustion, gases toCombustion, gases to particlesparticles Sulfates/acidsSulfates/acids NitrateNitrate AmmoniumAmmonium OrganicsOrganics CarbonCarbon MetalsMetals WaterWater SourcesSources:: Coal, oil, gasoline, diesel,Coal, oil, gasoline, diesel, wood combustionwood combustion Transformation of SOx,Transformation of SOx, NOx, organic gasesNOx, organic gases including biogenicsincluding biogenics High temperature industrialHigh temperature industrial processesprocesses ((thermal oxidizers,thermal oxidizers, smelters, steel mills)smelters, steel mills) ImpactsImpacts:: Children and Seniors mostChildren and Seniors most at risk for prematureat risk for premature death, heart attacks,death, heart attacks, acute bronchitis andacute bronchitis and aggravated asthma.aggravated asthma.
  • 42. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering PM 2.5 Who Does PM2.5 Effect?
  • 43. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering PM 2.5 How PM2.5 Gets into Lungs, Blood and Brain
  • 44. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering PM 2.5  Air 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/25147109http://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/22544506http://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/21399501http://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/25341536http://www.ncbi.nlm.nih.gov/pubmed/25341536  Toxicity beyond the Lung: Connecting PM2.5, Inflammation, and Diabetes  http://www.ncbi.nlm.nih.gov/pubmed/25341536http://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/26220751http://www.ncbi.nlm.nih.gov/pubmed/26220751 Why Worry? Downwind Liability for:
  • 45. But We Have a PermitBut We Have a Permit The Third Circuit recently concluded that obtaining aThe Third Circuit recently concluded that obtaining a permit under the Clean Air Actpermit under the Clean Air Act Does NOT ShieldDoes NOT Shield a company from liabilitya company from liability for damages caused by the plant?for damages caused by the plant? The Supreme Court refused to take the case on appeal so the decisionThe Supreme Court refused to take the case on appeal so the decision standsstands.. Bell v. Cheswick Generating StationBell v. Cheswick Generating Station, 734 F.3d 188, 190 (3d Cir. 2013), 734 F.3d 188, 190 (3d Cir. 2013) cert.cert. denied sub nom.denied sub nom. GenOn Power Midwest, L.P. v. BellGenOn Power Midwest, L.P. v. Bell, 134 S. Ct. 2696, 189 L. Ed. 2d, 134 S. Ct. 2696, 189 L. Ed. 2d 739 (2014)739 (2014) Why is this relevant? It is important because otherwise the company would argue thatWhy is this relevant? It is important because otherwise the company would argue that the permit shielded it.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 onSo, 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 ofCo, 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 youthe permit. However under this third circuit ruling, the permit shield only protects you against regulatory enforcement.against regulatory enforcement. It does not shield you from liability for harm to people or property.
  • 46. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering PM 2.5  Kills More thanKills More than AIDS, malaria, breast cancer, and TBAIDS, malaria, breast cancer, and TB  3 to 7 Million Deaths Each Year3 to 7 Million Deaths Each Year  Rendering Creates PM2.5 byRendering Creates PM2.5 by Burning Grease, HBurning Grease, H22S and NHS and NH33
  • 47. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering PM 2.5  Filterable PMFilterable PM2.52.5  Solid or liquid material at stack temperature andSolid or liquid material at stack temperature and higher (measured at ~250higher (measured at ~250oo to 1800to 1800oo F)F)  Stable in atmosphere and collected on ambientStable in atmosphere and collected on ambient samplersampler  Condensable PMCondensable PM2.52.5  Vapor or gas at stack temperatureVapor or gas at stack temperature  Condenses to liquid or solid at stack exitCondenses to liquid or solid at stack exit  Stable in atmosphere and collected on ambientStable in atmosphere and collected on ambient samplersampler Components of Direct PMComponents of Direct PM2.52.5
  • 48. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering PM 2.5 How Filterable and Condensable PM2.5 are Sampled
  • 49. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering EngineeringEngineering Case StudyCase Study Title V Fresh Pork Processor  New RTO Stack Test PM2.5 Emissions ~ 90-tpyNew RTO Stack Test PM2.5 Emissions ~ 90-tpy  Violation of Air Permit (Violation of Air Permit (more than 12 times the allowable discharge)  Reduce PM2.5 Emissions or Production CapacityReduce PM2.5 Emissions or Production Capacity Filterable and Condensable PM2.5 Sampling Results
  • 50. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering EngineeringEngineering Case StudyCase Study H2S + 2 O2 = H2SO4 H2SO4 + 2 NH3 = (NH4)2SO4 Formation of Ammonium Sulfate PM 2.5 By Thermal Oxidation of High Intensity Vapors How PM2.5 is Formed in Animal Rendering
  • 51. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering EngineeringEngineering Case StudyCase Study Pre-Trial Conditions Condensable Input to RTO = 1.92-lbs/hr Condensable Output from RTO = 18.71-lbs/hr ~10-times PM2.5 Increase
  • 52. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering EngineeringEngineering Case StudyCase Study Reduce PM Generation Potential in High Intensity Vapors  Venturi Scrubber pH ControlVenturi Scrubber pH Control  Venturi Scrubber Temperature ReductionVenturi Scrubber Temperature Reduction  Increase Freshwater Makeup TDS ReductionIncrease Freshwater Makeup TDS Reduction  Reduce Vacuum at Pickup PointsReduce Vacuum at Pickup Points  Isolate Hair HydrolizerIsolate Hair Hydrolizer  Reduce Air Cooled Condenser Temperature SetReduce Air Cooled Condenser Temperature Set PointPoint
  • 53. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering EngineeringEngineering Case StudyCase Study Trial Results Pre-Treated Vapor Condensable Output from RTO = 2.5-lbs/hr ~87% Reduction of Condensable PM2.5
  • 54. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering EngineeringEngineering Case StudyCase Study Solution  Patent Pending TO/RTO and Boiler Pre- Treatment Using Steen Research’s Super Scrubber Technology  Featuring Dual Scrubbing with RADOX
  • 55. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering EngineeringEngineering Case StudyCase Study Starve PM2.5 Precursors with RADOX Single or Dual Scrubbing H2S + 2 O2 = H2SO4 H2SO4 + 2 NH3 = (NH4)2SO4
  • 56. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering Scrubber ChemistriesScrubber Chemistries  Masking AgentsMasking Agents  EnzymesEnzymes  ScavengersScavengers  Oxidizers (ClOxidizers (Cl22, ClO, ClO2,2, OO3,3, OHOH-- ))
  • 57. Masking Agents, Enzymes and ScavengersMasking Agents, Enzymes and Scavengers STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 58. Masking AgentsMasking Agents STEEN RESEARCH, LLC Innovations in Chemistry and Engineering  Adds VOC’sAdds VOC’s  EnvironmentalEnvironmental SensitivitySensitivity  No Feedback ControlNo Feedback Control Based on LoadingBased on Loading  High Water UseHigh Water Use  Bio-FoulingBio-Fouling Engineering
  • 59. EnzymeEnzyme withwith Masking AgentMasking Agent  Patent TextPatent Text ReNewReNew http://www.google.com/patents/US20120219480http://www.google.com/patents/US20120219480 Minimal Reduction of H2S and NH3 compared to straight water w/o pHMinimal Reduction of H2S and NH3 compared to straight water w/o pH modificationmodification  Enzymes - Slow Reaction TimeEnzymes - Slow Reaction Time  Masking AgentMasking Agent  VOC GenerationVOC Generation  Foaming (anti-foam agents spoil biodiesel use)Foaming (anti-foam agents spoil biodiesel use) STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 60. Triazine ScavingerTriazine Scavinger  Old Oil Field TechnologyOld Oil Field Technology  Nitrogen Loading to WWTNitrogen Loading to WWT  No Loading Feedback ControlNo Loading Feedback Control  High Water UseHigh Water Use  Triazine → Thiadiazine, → DithiazineTriazine → Thiadiazine, → Dithiazine  BioFouls to Insoluble PolymerBioFouls to Insoluble Polymer STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 61. OxidizersOxidizers STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 62. OHOH the Hydroxyl Radical and the 2the Hydroxyl Radical and the 2ndnd strongest oxidizer known to man.strongest oxidizer known to man. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering Relative Oxidation Of Reactive Species Oxidizers
  • 63. Bleach and Chlorine Dioxide ClOBleach and Chlorine Dioxide ClO22  Weak, Temperature Sensitive OxidizerWeak, Temperature Sensitive Oxidizer  Volatile at low temperatures (Like Bleach which flashes at a lowVolatile at low temperatures (Like Bleach which flashes at a low temperature, 100 Degrees F, Chlorine dioxide flashes at 110 Degrees F)temperature, 100 Degrees F, Chlorine dioxide flashes at 110 Degrees F)  When free chlorine interacts with proteins environmentally detrimentalWhen free chlorine interacts with proteins environmentally detrimental compounds are such ascompounds are such as haloamines, and trihalomethaneshaloamines, and trihalomethanes, THM’s are, THM’s are produced.produced. (THM’s are toxic and known carcinogens)(THM’s are toxic and known carcinogens)  Addition of salts to the water systemAddition of salts to the water system  Has a negative effect on waste waterHas a negative effect on waste water biological systembiological system ClO2 Engineering STEEN RESEARCH, LLC Innovations in Chemistry and Engineering
  • 64. Purate 2-Part ClO2Purate 2-Part ClO2  Low pHLow pH  Insoluble about 110 FInsoluble about 110 F  Acid Scrubbing onlyAcid Scrubbing only  Toxic blow down to bio pondsToxic blow down to bio ponds  Produces CarcinogenicProduces Carcinogenic CompoundsCompounds THM’sTHM’s  Extreme Fire HazardExtreme Fire Hazard STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering 3-Part ClO23-Part ClO2  Better pH rangeBetter pH range  Insoluble about 110 FInsoluble about 110 F  Toxic blow-down to bio pondsToxic blow-down to bio ponds  High Salt LoadHigh Salt Load  Produces CarcinogenicProduces Carcinogenic CompoundsCompounds THM’sTHM’s  Extreme Fire HazardExtreme Fire Hazard
  • 65. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering Ozone OOzone O33  Toxic GasToxic Gas  Induces BioFoulingInduces BioFouling  Low Solubility in Water Requires Over-Low Solubility in Water Requires Over- DosingDosing  Low Solubility Decreases More withLow Solubility Decreases More with Increasing TemperatureIncreasing Temperature  Low Solubility Decreases More withLow Solubility Decreases More with Increasing pHIncreasing pH  Increases VOC’s in air scrubberIncreases VOC’s in air scrubber Gold Kist Ball Ground, GA Case studyGold Kist Ball Ground, GA Case study O3
  • 66. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering Ozone Solubility vs. TempOzone 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
  • 67. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering Ozone Solubility vs. pHOzone Solubility vs. pH Engineering
  • 68. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering Engineering OZONE
  • 69. OZONE  Toxicity, CDC, OSA (Toxicity, CDC, OSA (Known CarcinogenKnown Carcinogen)) Does Ozone Cause Precancerous Changes in Cells?Does Ozone Cause Precancerous Changes in Cells? http://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.abstractDetail/abstract/2314http://cfpub.epa.gov/ncer_abstracts/index.cfm/fuseaction/display.abstractDetail/abstract/2314 OzoneOzone https://www.osha.gov/dts/chemicalsampling/data/CH_259300.htmlhttps://www.osha.gov/dts/chemicalsampling/data/CH_259300.html Health EffectsHealth Effects http://www.epa.gov/glo/health.htmlhttp://www.epa.gov/glo/health.html  Destroys Packing And PlasticsDestroys Packing And Plastics  Low Solubility (Low pH Only)Low Solubility (Low pH Only)  Weak, Temperature SensitiveWeak, Temperature Sensitive STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 70. Fenton Radox ReactionFenton Radox Reaction Hydroxyl Radical the second strongest oxidizer know to man. Secondary Fenton chemistry reaction is the generation of peroxide free radical. FeFe2+2+ + H+ H22OO22 → Fe→ Fe3+3+ + OH+ OH −− ++ OHOH STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Fe3+ + H2O2 => Fe2+ + H+ + HOO0 The peroxide molecule formed in this reaction (HO2 0 ) is a powerful free radical which oxidizes organic compounds. Engineering
  • 71. Characteristic Radox ReactionCharacteristic Radox Reaction STEEN RESEARCH, LLC Innovations in Chemistry and Engineering  Highly ReactiveHighly Reactive  Destroys All Odor Compounds, Toxic VOC’sDestroys All Odor Compounds, Toxic VOC’s  Effective At Any pHEffective At Any pH  Very High Solubility in Scrubber WaterVery High Solubility in Scrubber Water  Not Toxic or CarcinogenicNot Toxic or Carcinogenic  Effective at All TemperaturesEffective at All Temperatures  No BioFouling, Keeps The Scrubber CleanNo BioFouling, Keeps The Scrubber Clean  No Fire RiskNo Fire Risk Engineering
  • 72. Radox Full Scale Stack TestRadox Full Scale Stack Test Case Study 1:Case Study 1: High Intensity ScrubberHigh Intensity Scrubber Scrubber pulled from the cooker and presses. Non-Methane Organic Carbon (NMOC) ermined using US EPA Method 25A Scrubber efficiency needed to be better then 80 percent removal. Three continuous samples, each 45 minutes in duration. RUN 1 RUN 2 RUN 3 Average Inlet Flow Rate, dsfm 523 519 520 521 acfm 565 559 560 561 Total Non-Methane Hydrocarbon, ppm, as C1 1131 1035 1126 1097 lb/hr, as CH4 1.474 1.338 1.454 1.422 Outlet Flow Rate, dsfm 845 845 845 845 acfm 906 905 906 906 Total Non-Methane Hydrocarbon, ppm, as C1 39.5 41.4 36.6 39.1 lb/hr, as CH4 0.0832 0.0872 0.0771 0.0825 DESTRUCTION EFFICIENCY, % 94.4 93.5 94.7 94.2 STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 73. Radox USDA STUDYRadox USDA STUDY Case Study 2:Case Study 2: Feather Dryer AirFeather Dryer Air ScrubberScrubber 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: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.” STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 74. OHOH the Hydroxyl Radical and the 2the Hydroxyl Radical and the 2ndnd strongest oxidizer known to man.strongest oxidizer known to man. STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering Relative Oxidation Of Reactive Species Oxidizers
  • 75. Fenton Radox ReactionFenton Radox Reaction Hydroxyl Radical the second strongest oxidizer know to man. Secondary Fenton chemistry reaction is the generation of peroxide free radical. FeFe2+2+ + H+ H22OO22 → Fe→ Fe3+3+ + OH+ OH −− ++ OHOH STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Fe3+ + H2O2 => Fe2+ + H+ + HOO0 The peroxide molecule formed in this reaction (HO2 0 ) is a powerful free radical which oxidizes organic compounds. Engineering
  • 76. Characteristic Radox ReactionCharacteristic Radox Reaction STEEN RESEARCH, LLC Innovations in Chemistry and Engineering  Highly ReactiveHighly Reactive  Destroys All Odor Compounds, Toxic VOC’sDestroys All Odor Compounds, Toxic VOC’s  Effective At Any pHEffective At Any pH  Very High Solubility in Scrubber WaterVery High Solubility in Scrubber Water  Not Toxic or CarcinogenicNot Toxic or Carcinogenic  Effective at All TemperaturesEffective at All Temperatures  No BioFouling, Keeps The Scrubber CleanNo BioFouling, Keeps The Scrubber Clean  No Fire RiskNo Fire Risk Engineering
  • 77. Radox Make-Down and ControlRadox Make-Down and Control STEEN RESEARCH, LLC Innovations in Chemistry and Engineering Engineering
  • 78. Question and AnswersQuestion and Answers STEEN RESEARCH, LLC Innovations in Chemistry and Engineering “Yes …I believe there’s a question there in the back.”

Editor's Notes

  1. 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