Application of Submerged Hydrodynamic Cavitating Jets ... · Application of Submerged Hydrodynamic...
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Application of Submerged HydrodynamicCavitating Jets (DynaJets®) to Oxidation Of
Organic Compounds in Water
Greg Loraine
November 17, 2010
AOT 16Dynaflow, Inc.
10621-J Iron Bridge RoadJessup, MD
www.dynaflow-inc.com
www.dynaflow-inc.com AOT 16 11-17-10
Outline
Cavitation and Formationof Free Radicals
Acoustic (Ultrasonic)Cavitation vs.Hydrodynamic Cavitation
Hydrodynamic CavitatingJets
Oxidation / Reduction inWater
Applications
Conclusions
Underwater explosion from6000 V spark.Collapse is analogousto cavitation
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CavitationCavitation
Bubble nuclei in waterexpand & collapse whenthe local pressure changesvery quickly.
Collapsing bubblesproduce tremendouspressures & temperaturesin localized area (~5,200K, ~200 Atm).
Water vapor dissociatesinto OH• and H•
H2O → OH• + H•
Volatile compounds canalso dissociate intoradicalsCCl4 → Cl• + Cl3C
•
Pressure
Radius of Bubble
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Reaction Location
Inside collapsing bubbleor at interface
Volatile compounds enterthe expanding bubble anddecompose duringcollapse
OH• and H• concentrationshighest in center, decreasetoward bubble wall
Hydrophobic compoundspartition to air-waterinterface
Local depletion of startingcompound and build up ofproducts
Co
nce
ntr
atio
n
OH• H•
Parent
Products Products
Collapsing Bubble
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Hydrodynamic & Ultrasonic CavitationHydrodynamic & Ultrasonic Cavitation
Ultrasonic (US) cavitation produced bymechanical vibration in a liquidlocalized at the face of the probe.
US- high intensity, localized cavitation,energy intensive, scaling up difficult
Hydrodynamic Cavitation (HD) isproduced by motion of fluid.
Large pressure fluctuations in shearlayer of the liquid cause cavitation.
HD – wider area of cavitation, 1/10 –1/100 energy required, easy to scale
US
HD
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DYNAJETS® Cavitating Jets
Specially designed nozzles intensifycavitation and generate cavitation atlower pump pressures
This is achieved through:
– Passive acoustic excitation
– Swirling the flow
Both enhance vorticity and reducepressure in the vortices
SSTRATOTRATOJJETET®® DDYNAYNASSWIRLWIRL®®
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Hydrodynamic Cavitation for Oxidation
Hydrodynamic cavitation can be 10 – 100 times moreenergy efficient than acoustic cavitation
No addition of oxidizer
Optical opacity or particulates are no problem
Other than nozzle no special equipment required
DYNAJETS®
– Cavitation at lower pressures
– Lower pressures lower electrical requirements
Hydraulic Energy = Flow Rate x Pressure change xtime
– Cavitation in wider area
– Easier to scale up than US
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0
0.2
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0.6
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1
0 10 20 30 40Time, Hours
C/C
0P
-Nit
rop
he
no
l
DYNAJETS®
ULTRASONIC
Note Much More Rapid Concentration
Drop with the DYNAJETS ® .
0.01
0.1
1
10
0 5 10 15 20 25 30 35
Time, Hours
Ox
ida
tio
nE
ffic
en
cy
,m
g/M
J
Note High Oxidation Efficency and Short
Oxidation Time for DYNAJETS ® .
DYNAJETS®
ULTRASONIC
Energy: Acoustic & Hydrodynamic
25 ppm p-Nitrophenol
Hydrodynamic cavitation can be 10 – 100 times more energyefficient than acoustic cavitation*
*K.Kalumuck, G. Chahine, J. Fluids Eng., 122,(2000) 465.S. Majumdar, P. S. Kumar, A. Pandit, Ultra. Sonochem., 5 (1998) 113.
K. Jyoti, A. Pandit, Water Res., 38 (2004), 2249.
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Applications of DYNAJETS®
Oxidation
– Chlorinated solvents
– Toluene, Acetone
– Pesticides: Malathion, Carbaryl, 2,4-D
– Pharmaceuticals and Personal CareProducts
Disinfection
– Water
– Wastewater
– Storm water
Recovery of Cellular Matter – Algae
Pretreatment of lignocellulose biomass
Biodiesel production
Pump
Reaction Chamber
Dual JetDYNASWIRL® Nozzle
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Selectivity of HD Cavitation Oxidation
Volatile (high vapor pressure) can be oxidized easily
pH can be used to adjust degree of ionization of weakacids and bases
Hydrophobic compounds (high octanol-water partitioncoefficient log KOW) oxidize faster than hydrophiliccompounds
Reaction intermediates are formed in regions of highradical concentrations, lower by-product concentrations
Operating parameters (pump pressure, jet velocity, etc.),and nozzle design can be varied to improve oxidationperformance
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Volatile Compounds: Mineralization of Chloroform
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0 50 100 150 200Time [min]
TO
Cp
pm
2-Jet DYNASWIRL® 65 psi, Chloroform = 344 mg/LVapor Pressure = 160 mm Hg @ 20 C
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0
0.5
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1.5
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Oxidation Time (mins)
To
lue
ne
(pp
m)
Oxidation of Toluene
DYNASWIRL® 30 psiToluene:Vapor Pressure= 28.4 mmHg @25 CLog KOW=2.69
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0.5
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1
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Oxidation Time (mins.)
Me
thy
lO
ran
ge
[C]/
[C]0
pH=2.7
pH=2.5
pH=2.4
Hydrophobicity: pH effects & Methyl Orange
Decoloration of acid dye, Methyl Orange –pKa = 3.44
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pH
Mo
leF
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[MO-H]
[MO-]
DYNASWIRL® dual jet 30 psi
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0.7
0.75
0.8
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0.9
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1
1.05
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Oxidation Time (mins.)
[C]/
[C]0
Dimethyl methylphosphonate
Malathion
Solubility Effects: DMMP and Malathion
DMMP – dimethyl methylphosphonate,sol = >100g/L, log KOW=-1.88 Vp = <0.1 mmHg
Malathion – organophosphate pesticideSol = 145 mg/L, log KOW=2.89, Vp = 3x10-6 mmHg
Dual Jet DYNASWIRL® at 30 psi
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Malathion Oxidation Products
2.93 4.93 6.93 8.93 10.93 12.93 14.93 16.93 18.93 20.93 22.93Time0
100
%
msw30-cl-120 1: Scan EI+TIC
5.16e912.34;99
4.71
127
20.63127
P
OS
O SP
OS
O SP
OS
O SP
OS
P
OS
O S
P
S
OCH2O SOH P
S
OCH2O SP
S
OCH2O SP
S
OCH2O SP
S
OP
S
OCH2O SOH
O
OO
O
CH2CH3
CH2CH3
CH2CH3
O
OO
O
CH2CH3
CH2CH3
O
OOO
OO
CH2CH3
CH2CH3
CH2CH3
O
OO
O
CH2CH3
CH2CH3
CH2CH3
O
OO
O
CH2CH3
CH2CH3
O
OOO
OO
CH2CH3
CH2CH3
CH2CH3
P
O
S
O SP
O
S
O SP
O
S
O SP
O
S
P
O
S
O S
O
OO
O
OH
CH2CH3
O
OOO
OO
OH
CH2CH3
Int. Std–Tributyl phosphate
Malathion
O
OO CH2CH3CH2CH3
OH
OH
O
OOO CH2CH3CH2CH3
OH
OH
CH2CH3
O
OO
OH
O
OOO
OH
P
O
S
CH2O SOH P
O
S
CH2O SP
O
S
CH2O SP
O
S
CH2O SP
O
S
P
O
S
CH2O SOH
P
O
S
O SP
O
S
O SP
O
S
O SP
O
S
P
O
S
O S
GC/MS data from Malathion oxidation: Dual Jet DYNASWIRL® at 30 psi
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Oxidation Time (mins)
[C]/
[Ma
l]0
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[C]/
[Ma
l]0
DYNASWIRL® duo jet, 30 psi
Mass Balance Of Malathion Oxidation
Mass Balance
Malathion
Diethyl Fumarate
Hydroxydimethyl Phosphorodithioic Acid
Dimethyl Phosphorodithioic Acid
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Selective Oxidation of Mixtures: log KOW
7 pharmaceuticals and personal care products weremixed in wastewater treatment plant effluent
Mixture oxidized using DYNASWIRL® nozzle at60 psi for 30 minutes
Mixture had a range of log KOW values 1.4 – 5.9
More hydrophobic compounds reacted faster
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Oxidation of Mixture of PPCP in Wastewater
0.600
0.700
0.800
0.900
1.000
1.100
0 5 10 15 20 25 30
Time (mins.)
C/C
0
Chloroxylenol
Tris (2-chloroethyl)Phosphate
Galaxolide
Mus k Ketone
Oxybenzone
Triclosan
Ibuprofen
DYNASWIRL® nozzle at 60 psi
1.44 3.97
3.79
4.31
4.76
5.9
5.9
Log KOW
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Log KOW and Reaction Extent
In a mixture more hydrophobic compounds react faster
y = 0.0523x - 0.0536
R2 = 0.7922
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log Kow
(1-C
/C0)
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Increasing Reaction Rates
Nozzle design
Pressure drop through the nozzle affects thequality of cavitation and oxidation efficiency
Tweeking the system can increase reactionefficiency
DYNASWIRL® nozzle
20 psi 100 psi
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Chloramphenicol antibiotic used in aquaculture and veterinary applications
Removal of Chloramphenicol using centerbody CaviJet at 45 and 65 psi
Initial concentrations = 27 mg/l, and total volume 11 liters
Effects of Operating Pressure
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Cycles
Ch
lora
mp
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ol[C
]/[C
] 0 65 psi
45 psi
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Oxidation with DYNASWIRL®Initial conc = 30 mg/L, Volume = 10 L.
Effect of Pressure Drop on Removal Rate
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Oxidation Time (minutes)
Ch
lora
mp
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nic
olm
g/L
30 psi
90 psi
60 psi
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Chloramphenicol Removal per kilowatt-hour
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kJ
Ch
lora
mp
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ol[C
]/[C
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CaviJet 45 psi
DynaSwirl 30 psi
DynaSwirl 60 psi
DynaSwirl 90 psi
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Conclusions
Cavitation initiated reactions are similar regardless of howthe cavitation is initiated
Hydrodynamic cavitation can be more energy efficient andeasier to scale up than ultrasonic devices
Selective removal of volatile and hydrophobic compoundscan be accomplished
Selective removal by pH adjustment
Oxidation rates have non-linear dependence on pumppressure
Nozzle geometry can effect oxidation rates
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Collaboration
www.dynaflow-inc.com, technology descriptionsand papers
Testing, design, and production services
Collaborative research
– Feasibility studies
– Small business STTR
– Grant proposal writing
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Acknowledgements & Contact InformationAcknowledgements & Contact Information
DYNAFLOW, INC.www.dynaflow-inc.com
10621-J Iron Bridge Road, Jessup, MD20794. USA
Dr. Greg LoraineSr. Research Scientist
(301) 604-3688
Dr. Georges L. ChahinePresident
(301) [email protected]
Business POC: Dr. Jin-Keun ChoiPrincipal Research Scientist
(301) [email protected]
US Environmental ProtectionAgency
NASA
Office Naval Research
NOAA
NIEHS
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Oxidation of As (III) to As(V)
UV/H2O2 & UV/TiO2 data Yoon and Lee 2005
4.60.173DYNAJETS®
17.40.004UV/TiO2
310.004UV/H2O2
kW/1000 galPump Power kWLamp Power kWAOP
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Disinfection Efficiency: E coli & BDisinfection Efficiency: E coli & B subtilissubtilis
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
1.E+08
0 20 40 60 80 100 120
Disinfection Time (mins)
CF
U/m
l
E. coli
B. subtilis
Same conditions - DYNASWIRL® nozzle at 2.1 bar
Effects of nozzle geometry, and nozzle pressure were investigatedusing E. coli and B. subtilis.