Post on 21-Dec-2015
April 13 2006 UI ECE Research Colloqiuim 1
Water Treatment Using Water Treatment Using Ultrasound-Induced Ultrasound-Induced
CavitationCavitation
Michael AndersonMichael AndersonMechanical Engineering
Center for Intelligent Systems Research
Greg MöllerGreg Möller Food Science and Toxicology
April 13 2006 UI ECE Research Colloqiuim 2
Experts consider options over sources of city water Associated Press, September 20, 2004
TWIN FALLS, Idaho – After years of drought and a declining Snake River Aquifer, experts are not ruling out any local lakes or even wastewater plant effluent as a source of city water.
Just five years ago, Twin Falls thought it had accumulated enough water sources to last for 50 years. Considering that diminishing supply, the city now finds itself pretty much starting over.
But since the first plan was devised, rounding up that water has become more complicated. The federal government recently said Twin Falls must lower naturally occurring arsenic levels in about 40 percent of its supply.
A committee is looking at a number of sources for water along the Snake River Canyon, including Devil's Corral, Rock Creek, seepage tunnels and wastewater treatment plant effluent. It's also working with state officials to change the use of certain water rights to purchase them.
April 13 2006 UI ECE Research Colloqiuim 3
Problem StatementProblem Statement
• Water quality and quantity is vitally linked to public health, environmental quality and economic opportunity.
• Many communities are now “development limited” due to limited water supply and limited wastewater discharge opportunity.
• New science suggests bioactive substances in human wastewater and other discharges are a direct threat.
April 13 2006 UI ECE Research Colloqiuim 4
Pump & ScreenPump & Screen
Primary SettlingPrimary Settling
SecondaryAeration
SecondaryAeration
ClarifiersClarifiers
Solids DigestionSolids Digestion
DisinfectionDisinfection
NPDES Permit to Pollute
NPDES Permit to Pollute
April 13 2006 UI ECE Research Colloqiuim 5
ChallengesChallenges• Pharmaceuticals, endocrine disrupting substances,
personal care products, and various pesticides and herbicides are found in many natural waters.– Wastewater discharge and non-point source pollution. – Micropollutants, PPCPs, PhAS, Biocidals.
• Concern about environmental and public health impact of these substances.
• Need for better science and technology.– Disposal and treatment options.– Detection of chemicals and biological impacts.– Green science and engineering.
April 13 2006 UI ECE Research Colloqiuim 6
Example: Antibiotic SoapExample: Antibiotic Soap
• Triclosan, the common antiseptic, was found in 57.6% of the United States water resources surveyed (USGS).
• A broad-spectrum antibacterial - antimicrobial agent classified as a Class III drug by the FDA.
• Bacteriostatic activity against a wide range of bacteria has lead to popular use in: – Personal care products, cosmetics, anti- microbial creams,
acne treatment, lotions and hand soaps, plastics, polymers and textiles.
• Linked to estrogenic effectsin fish.
O
OHCl Cl
Cl
April 13 2006 UI ECE Research Colloqiuim 7
Micropollutants in U.S. WatersMicropollutants in U.S. Waters
• USGS study tested U.S. waters for 95 chemicals ranging from perfumes to antidepressants.
• Of 139 streams tested, 80% had at least one of the chemicals and 50% had seven or more.
• Continual introduction “persistence”.• Threat to water reuse and to “captive”
aquatic biota.
April 13 2006 UI ECE Research Colloqiuim 8
ExcretionExcretion
• When we take medication, our bodies excrete the active chemicals with as much as 90% of the ingested drug still in a potent form.
April 13 2006 UI ECE Research Colloqiuim 9
Endocrine DisruptersEndocrine Disrupters
• Chemicals which interfere with endocrine system function.
• Endocrine system consists of glands and the hormones they produce. – Pituitary, thyroid, and adrenal glands, the female
ovaries and male testes.
Estradiol
April 13 2006 UI ECE Research Colloqiuim 10
Male-to-Female Sex ReversalMale-to-Female Sex Reversal
• Salmon: “a high incidence (84%) of a genetic marker for the Y chromosome in phenotypic females sampled from the wild... It appears likely that female salmon with a male genotype have been sex reversed, creating the potential for an abnormal YY genotype in the wild that would produce all-male offspring and alter sex ratios significantly.”
• High Incidence of a Male-Specific Genetic Marker in Phenotypic Female Chinook Salmon from the Columbia River. Nagler, JJ; Bouma, J; Thorgaard, GH; Dauble, DD Environmental Health Perspectives. Vol. 109, no. 1, pp. 67-69. Jan 2001
April 13 2006 UI ECE Research Colloqiuim 11
HypospadiasHypospadiasIncomplete Masculinization of the Reproductive Tract
• Paulozzi LJ, Erickson JD, Jackson RJ. 1997. Hypospadias trends in two U.S. surveillance systems. Pediatrics 100:831-834.
• Paulozzi LJ 1999. International trends in rates of hypospadias and cryptorchidism. Environmental Health Perspectives 107:297-302.
• Gray, LE, C Wolf, C Lambright, P Mann, M Price, RL Cooper and J Ostby. 1999. Administration of potentially antiandrogenic pesticides (procymidone, linuron, iprodione, chlozolinate, p,p'-DDE, and ketoconazole) and toxic substances (dibutyl- and diethylhexyl phthalate, PCB 169, and ethane dimethane sulphonate) during sexual differentiation produces diverse profiles of reproductive malformations in the male rat. Toxicology and Industrial Health. 15:94-118.
April 13 2006 UI ECE Research Colloqiuim 12
CavitationCavitation
• Oscillating pressure field (ultrasonic) or fluctuating pressure in shear layer of water jets (hydrodynamic) cause pre-existing microscopic bubble nuclei to grow explosively and then collapse violently.
April 13 2006 UI ECE Research Colloqiuim 13
11 22
33 44
Simulated Cavitation Bubble Simulated Cavitation Bubble DynamicsDynamics
• Sequence from high speed film of ~1cm cavitation bubble collapse.
• Note formation of high speed re-entrant jet (3,4)
April 13 2006 UI ECE Research Colloqiuim 14
Pressure Field Associated with Pressure Field Associated with Bubble CollapseBubble Collapse
Cavitational activity is directly proportional to the number density of particles present in the medium (Madanshetty and Apfel, 1991).
April 13 2006 UI ECE Research Colloqiuim 15
Ultrasonic Water Treatment:Ultrasonic Water Treatment:How Does It Work?How Does It Work?
•Acoustic waves in water can resonantly vibrate gas bubbles
•Resonant vibration can result in violent bubble collapse, causing temperatures and pressures as high as 5000K and 1700atm
•High pressures and temperatures cause chemical reactions among the gas in the bubble and water vapor, one of them the dissolution of water into H● and OH● (free radicals).
•Free radicals diffuse into the water and oxidize harmful chemicals.
April 13 2006 UI ECE Research Colloqiuim 16
New York Times, “Tiny Bubbles Implode With the Heat of a Star”,March 15 2005
How Hot?How Hot?
April 13 2006 UI ECE Research Colloqiuim 17
SonochemistrySonochemistry
• Free radicals are formed as a result of the cavitation microbubbles which are created during the negative pressure period of sound waves– Acoustic vs hydrodynamic
• Dissolved gas & nucleation sites needed– Ozone
• Milder operating conditions– Lower T, P
April 13 2006 UI ECE Research Colloqiuim 18
Postulated Reaction Postulated Reaction Mechanisms and LocationsMechanisms and Locations
• Within bubble.– Hydroxyl and other radical attack in gas phase.– Pyrolysis in gas phase.– Ion reactions.
• At or near bubble surface in liquid.– Hydroxyl and other radical attack in liquid phase. – Formation and reaction with supercritical water.
• In bulk liquid solution.– Hydroxyl and other radicals attack in liquid phase.
• Intermediate reactions and reaction products.
April 13 2006 UI ECE Research Colloqiuim 19
Mechanism of Cavitation OxidationMechanism of Cavitation OxidationAdvanced oxidation process
• Water dissociates under extreme physical conditions generated at cavitation bubble collapse.– Calculated up to ~5-10,000°K and 500-1200 atm
(sec lifetime).
• Forms free radicals:
H2O H + OH
H + H H2
OH + OH H2O2
OH + ORGANIC CO2 + H2O + …
April 13 2006 UI ECE Research Colloqiuim 20
Higher Frequency UltrasonicsHigher Frequency UltrasonicsMegasonics ~1MHz
• Current research is finding that for oxidations higher frequencies may lead to higher reaction rates.
• More, smaller, faster collapsing bubbles– Less OH radical recombination?
April 13 2006 UI ECE Research Colloqiuim 21
PPR
PR
RR og
21
2
3 2
2
2
22 422
31
ov
ov
oo
oo R
PR
PR
PR
Rayleigh-Plesset EquationRayleigh-Plesset Equation
April 13 2006 UI ECE Research Colloqiuim 22
Resonance Frequencies Resonance Frequencies Air Bubbles in Water Air Bubbles in Water
April 13 2006 UI ECE Research Colloqiuim 23
Moderate Vibration Moderate Vibration
Source: Leighton, “The Acoustic Bubble”, Academic Press, 1994
Ro= 2 mm, fo=1.7 kHzf = 10 kHzPA = 2.4 bar = 0.27 MPa
April 13 2006 UI ECE Research Colloqiuim 24
Stable Cavitation Stable Cavitation
Source: Leighton, “The Acoustic Bubble”, Academic Press, 1994
Ro= 0.10 mm, fo 10 kHzf = 10 kHzPA = 2.4 bar = 0.24 MPa
April 13 2006 UI ECE Research Colloqiuim 25
Stable Cavitation Stable Cavitation
Made by Tom Matula, Applied Physics Laboratory, University of Washington, available on Wikipedia
April 13 2006 UI ECE Research Colloqiuim 26
Transient Cavitation Transient Cavitation
Source: Leighton, “The Acoustic Bubble”, Academic Press, 1994
Ro = 60 m
Ro = 50 m
Ro = 10 m
Ro = 1 m
f = 10 kHzPA = 0.24 MPa
April 13 2006 UI ECE Research Colloqiuim 27
Spectra for Stable and Spectra for Stable and Transient Cavitation Transient Cavitation
Source: Frohly, et al.,JASA, 108(5), 2012-2020, 2000
April 13 2006 UI ECE Research Colloqiuim 28
Spectra for Stable and Spectra for Stable and Transient Cavitation Transient Cavitation
Source: Frohly, et al.,JASA, 108(5), 2012-2020, 2000
April 13 2006 UI ECE Research Colloqiuim 29
Spectra for Stable and Spectra for Stable and Transient Cavitation Transient Cavitation
Source: Frohly, et al.,JASA, 108(5), 2012-2020, 2000
April 13 2006 UI ECE Research Colloqiuim 30
0 0.2 0.4 0.6 0.8 1 1.20
2
4
6
8
10
12
14
16
18
RMS Pressure (MPa)
Bub
ble
Rad
ius
(m
)980 kHz
PRD
PB
PTC
713 mV672 mV
600 mV
521 mV
Effect of Pressure Amplitude onEffect of Pressure Amplitude onAcoustic Cavitation Acoustic Cavitation
April 13 2006 UI ECE Research Colloqiuim 31
State of the Art- Water TreatmentState of the Art- Water Treatment
Source: Destaillats, et al., “Ind. Eng. Chem. Res., 40, pp. 3855-3860, 2001
3096 J/Liter for ½ “removal” MO @ 67 W/Liter
April 13 2006 UI ECE Research Colloqiuim 32
Diffusion of Ultrasound in Tube Diffusion of Ultrasound in Tube ReactorReactor
Measurement PortsO-Ring Piston CollimatorMeasurement PortsO-Ring Piston Measurement PortsO-Ring Piston Collimator
Total Length of Tube = 120 cm
Tube Diameter = 9 cm
April 13 2006 UI ECE Research Colloqiuim 33
PZT TransducerCollimatorElectrode
PZT TransducerCollimatorElectrode
Copper Backing
Collimator to Diffuse Ultrasound Collimator to Diffuse Ultrasound
April 13 2006 UI ECE Research Colloqiuim 34
Pilot Scale Flow Ultrasonic CavitationPilot Scale Flow Ultrasonic Cavitation 5 Cell Apparatus and Filter Radiator Design
April 13 2006 UI ECE Research Colloqiuim 35
High Achievable Energy Densities High Achievable Energy Densities
April 13 2006 UI ECE Research Colloqiuim 36
Luminol Chemi-Lumeniscence Luminol Chemi-Lumeniscence
Measurement PortsO-Ring Piston CollimatorMeasurement PortsO-Ring Piston Measurement PortsO-Ring Piston Collimator
April 13 2006 UI ECE Research Colloqiuim 37
Ultrasound DistributionUltrasound Distribution
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8-3
-2
-1
0
+1
+2
+3
+4
RMS Pressure (MPa)
Loca
tion
Fro
m C
ente
r (c
m)
100% Drive
70% Drive
100% Drive= 100 Watts
= 15.1 W/Liter
70% Drive = 43 Watts
Length of Tube = 55 cm
Measurement 15 cm from transducer
April 13 2006 UI ECE Research Colloqiuim 38
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 510
-6
10-4
10-2
100
102
PZT Response Set 1 - 0.0068568 Watts - 0.47038 Volts RMS
Frequency(MHz)
Vol
tage
(V
)
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
10-5
100
Hydrophone Response Set 1 - 0.0033221 MPa
Frequency(MHz)
Pre
ssur
e (M
Pa)
1st Harmonic, A1
Ultraharmonics
Noise Level, NS
Fundamental, A0
Fundamental, B01st Harmonic, B
1Ultraharmonics
Noise Level, NH
Spectra at Low PowerSpectra at Low Power
April 13 2006 UI ECE Research Colloqiuim 39
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 510
-6
10-4
10-2
100
102
PZT Response Set 6 - 109.8652 Watts - 59.5413 Volts RMS
Frequency(MHz)
Vol
tage
(V
)
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
10-5
100
Hydrophone Response Set 6 - 0.66475 MPa
Frequency(MHz)
Pre
ssur
e (M
Pa)
Spectra at High PowerSpectra at High Power
April 13 2006 UI ECE Research Colloqiuim 40
Test ReactorTest ReactorSonochemical Measurements Sonochemical Measurements
Diameter = 7.5 cm
Length = 27 cm
Volume = 1.2 Liter
0.7 MPa at 95 WattsTypical = 80 Watts/Liter
April 13 2006 UI ECE Research Colloqiuim 41
Relative Oxidizing StrengthRelative Oxidizing Strength
Standard Potential (V)
Hydroxyl radical 2.80
Ozone 2.18
Chlorine 1.68
April 13 2006 UI ECE Research Colloqiuim 42
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8500
550
600
650
700
750
RMS Pressure (MPa)
Eh
(mV
)
Redox Potential: 18 MΩ-cm Water
April 13 2006 UI ECE Research Colloqiuim 43
0 50 100 150400
450
500
550
600
650
700
Time (Minutes)
Eh
(mV
)
20M Fe2+ 0.7 MPa
20M Fe2+ 0.4 MPa
Reagent Water 0.7 MPa
Reagent Water 0.4 MPa
20M Mn2+ 0.7 MPa
20M Mn2+ 0.4 MPa
Fe2+/Mn2+ Oxidation
April 13 2006 UI ECE Research Colloqiuim 44
0 10 20 30 40 50 60 70-0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
Time (Minutes)
Abs
orpt
ion
(AU
)0.2M KI 0.49 MPa
0.2M KI 0.23 MPa
0.2M KI 0.13 MPa
Potassium Iodide
April 13 2006 UI ECE Research Colloqiuim 45
0 10 20 30 40 50 60 70-0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
Time (Minutes)
Abs
orpt
ion
(AU
)0.2M KI 0.49 MPa
0.2M KI 0.23 MPa
0.2M KI 0.13 MPa
Potassium Iodide
Pressure Power k t 1/2 Eff
MPa W/l 103 min-1 min J/l for 1/20.13 17.61 0.07 9902 1743290.23 41.92 0.7 990 415070.49 56.17 6.3 110 6180
April 13 2006 UI ECE Research Colloqiuim 46
0 10 20 30 40 50 60 70-0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
Time (Minutes)
Abs
orpt
ion
(AU
)0.2M KI 0.49 MPa
0.2M KI 0.23 MPa
0.2M KI 0.13 MPa
Potassium Iodide
3096 J/Liter for ½ “removal” MO @ 67 W/Liter
Pressure Power k t 1/2 Eff
MPa W/l 103 min-1 min J/l for 1/20.13 17.61 0.07 9902 1743290.23 41.92 0.7 990 415070.49 56.17 6.3 110 6180
April 13 2006 UI ECE Research Colloqiuim 47
0 100 200 300 400 500 60010
-3
10-2
10-1
100
Time (Minutes)
Abs
orpt
ion
(AU
)0.64 MPa
0.45 MPa
0.31 MPa
Indigo Carmine Dye Bleaching
April 13 2006 UI ECE Research Colloqiuim 48
Observations/Conclusions
• 0.7 MPa achieved at 15 W/Liter in 3.5 Liter volume.
•Sonochemical activity caused by stable cavitation. Potential for increased performance with transient cavitation.
•At 0.7 MPa and 56 W/Liter, measured
6180 J/Liter for t1/2 KI in 1 Liter volume (possibility for 15 W/Liter with tube reactor).
•Compares with unknown pressure, 67
Watt/Liter, 3096 J/Liter for t1/2 MO in 45 Liter volume.
Measurement PortsO-Ring Piston CollimatorMeasurement PortsO-Ring Piston Measurement PortsO-Ring Piston Collimator
April 13 2006 UI ECE Research Colloqiuim 49
UI Intellectual PropertyUI Intellectual Property
• Parabolic transducer source (6,818,128)
• Radiator tube reactor array (6,911,153)
• Biphasic/triphasic US/ozone/metal-oxide catalytic water filter (patent pending)
April 13 2006 UI ECE Research Colloqiuim 50
April 13 2006 UI ECE Research Colloqiuim 51
0 100 200 300 400 500 60010
-3
10-2
10-1
100
Time (Minutes)
Abs
orpt
ion
(AU
)0.64 MPa
0.45 MPa
0.31 MPa
Indigo Carmine Dye Bleaching
Pressure Power k t 1/2 Eff
MPa W/l 103 min-1 min J/l for 1/20.31 77.13 0.91 761 275480.45 54.49 1.2 577 314760.64 56.17 2.8 248 19093
April 13 2006 UI ECE Research Colloqiuim 52
0 100 200 300 400 500 60010
-3
10-2
10-1
100
Time (Minutes)
Abs
orpt
ion
(AU
)0.64 MPa
0.45 MPa
0.31 MPa
Indigo Carmine Dye Bleaching
3096 J/Liter for ½ “removal” MO @ 67 W/Liter
Pressure Power k t 1/2 Eff
MPa W/l 103 min-1 min J/l for 1/20.31 77.13 0.91 761 275480.45 54.49 1.2 577 314760.64 56.17 2.8 248 19093
April 13 2006 UI ECE Research Colloqiuim 53
April 13 2006 UI ECE Research Colloqiuim 54
Sec # Pressure (Mpa) Power (Watts) W/L5.3.2 - Eh of DI Water at 980 kHz 0.16 25 20.96
0.3 43 36.050.41 62 51.980.71 94 78.8
5.3.2 Eh of Fe, Mn, and DI 0.7 95 79.640.4 59 49.46
5.3.3 Indigo Carmine Kinetics 0.64 92 77.130.45 65 54.490.31 43 36.05
5.3.4 Potassium Iodide 0.49 67 56.170.23 50 41.920.13 21 17.61
Acoustic Measurements Acoustic Measurements
April 13 2006 UI ECE Research Colloqiuim 55
Chemical and Engineering News, “Bubble Inferno”, 2005, 83, 10.
How Hot?How Hot?
April 13 2006 UI ECE Research Colloqiuim 56
Science, 2002, 295, 1868.
How Hot?How Hot?
April 13 2006 UI ECE Research Colloqiuim 57
Science News, 2005, 167, 147.
How Hot?How Hot?
April 13 2006 UI ECE Research Colloqiuim 58
0 5 10 15 20 25 30 350
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4H
ydro
phon
e F
unda
men
tal,
B0 (
MP
a)
Source Fundamental, A0 (Volts)
Amplitude of FundamentalAmplitude of Fundamental
April 13 2006 UI ECE Research Colloqiuim 59
0 5 10 15 20 25 300
0.05
0.1
0.15
0.2
0.25
Hyd
roph
one
1st
Har
mon
ic,
B 1 (M
Pa)
Source 1st Harmonic, A1 (Volts)
Amplitude of 1Amplitude of 1stst Harmonic Harmonic
April 13 2006 UI ECE Research Colloqiuim 60
Endocrine DisruptersEndocrine Disrupters
• Hormones are biochemicals.– Produced by endocrine glands.– Travel through the bloodstream and cause
responses in other parts of the body.
• Hormones of primary concern.– Estrogen, androgen
and thyroid hormones.
April 13 2006 UI ECE Research Colloqiuim 61
AntidepressantsAntidepressants• With the introduction of a host of new anti-depression
drugs in the late 80s, antidepressant prescriptions grew from 40 million in 1988 to more than 120 million in 1998.
• According to the CDC National Center for Health Statistics, more than 61 million new prescriptions for antidepressants were given by U.S. doctors in 2001.
April 13 2006 UI ECE Research Colloqiuim 62
Antidepressants in BiotaAntidepressants in Biota
• Prozac, Zoloft, Paxil and Celexa (selective serotonin reuptake inhibitors) are found in biota downstream of WWTPs (B. Brooks, Baylor U.)
• Levels of antidepressants as low as 1.5 ppb delays frog metamorphosis and cause development problems in fish (M. Black, U. GA).
April 13 2006 UI ECE Research Colloqiuim 63
Newton, Iowa WWTPNewton, Iowa WWTP
April 13 2006 UI ECE Research Colloqiuim 64
PharmaceuticalsPharmaceuticals
• Prescription drug sales in the U.S. have increased by 16.9% to $172 billion in 2003, plus $18 billon in over-the-counter medicines.
• The Union of Concerned Scientists estimates that in the U.S., 25 million pounds of antibiotics are fed to animals each year compared to 8 million pounds for people.