Escolar Documentos
Profissional Documentos
Cultura Documentos
Capacitance INCREASED!
Werner v. Siemens Poggendorfs Annalen der Chemie und Physik 102, 66 (1857) Ozone Production in an Atmospheric-Pressure Dielectric Barrier Discharge
H.E. Wagner, R. Brandenburg, et. al. The barrier discharge: basic properties and applications to surface treatment. Vacuum. 71 p417-436 (2003).
B. Eliasson and U. Kogelschatz. IEEE Transactions Plasma Science. Vol. 19 Issue 6, 1063-1077 (1991)
Single dielectric
Double dielectric
B. Eliasson and U. Kogelschatz. IEEE Transactions Plasma Science. Vol. 19 Issue 6, 1063-1077 (1991)
H.E. Wagner, R. Brandenburg, et. al. The barrier discharge: basic properties and applications to surface treatment. Vacuum. 71: 417-436 (2003).
Streamer Propagation in 1 bar Air A.A. Kulikovsky, IEEE Trans. Plasma Sci. 25 439-446 (1997).
1mm
n e 1mm
=109
cm-3 1012
1010 cm-3
1014
1013
Peak current
Gap
ne=109cm-3
ne=1014 cm-3
Dielectric-Barrier Discharges
Electric Field Breakdown Electrons & Ions
Plasma Chemistry Discharge Physics
Ozone Generation
Surface Treatment
Pollution Control
Excimer Formation
CO2 Lasers
Hydrogenation of CO2
Excimer Lamps
Plasma Displays
Generation of Ozone
Dielectric Barrier Discharge
3 O2 2 O3 X Y Z
O2
O2 O2 O e [ O O2 O3 O3 O2 e O2 O O2 O3 O2 O2
O3+ O2
Heat
Heat
X Power source [ Discharge gap Y High voltage electrode \ Grounded electrode Z Glass, Ceramic or Enamel Dielectric
Most powerful commercial oxidizing agent Unstable - must be generated and used onsite Limited solubility in water, but more so than oxygen Leaves a dissolved residual which ultimately converts back to oxygen
Generation of Ozone
Generation of Ozone
Advantages of Enamel Dielectrics Proven, Patented Design Simplicity
Generation of Ozone
Generation of Ozone
Oxygen
Off-Gas Blower
10-12% O3
LOX
LOX Tank
Ozone Generators
Vaporizers
Start-Up Date
1986 2003 2003 2004 2005 2007 2007 2008 2009
Los Angeles, CA Fairfax, VA Corbalis MWD, CA Mills Fairfax Co., VA Griffith MWD, CA Jensen Indianapolis, IN Belmont AWT Indianapolis, IN Southport AWT MWD, CA Diemer MWD, CA Weymouth
Ozonia North America - Potable Water Summary Total Number of Installations: 90 Total Installed Production: > 265,000 lbs/day
Revision -B
Disinfectant: Kills by cell lysing or causing the cell wall to rupture Attacks all bacteria virus, cysts and spores in varying degrees
Micro-organism / DNA
Capsule Cell wall Adenine Thymine Cytosine Guanine
Growth possible
NO GROWTH
0.004 0.008 0.012 0.016 0.020
O3 mg/l
0.05 - 0.25 0.4 1.0 0.1 0.75 1.5 5.0 1.0 3.0 3.0 10.0 5.0 15.0+
Contact time
sec. min. 5 10 min. 4 minutes 5 10 min. 5 10 min. 10 30 min. 15 30 min.
Applications of Ozone
Wastewater Treatment
Disinfection of Secondary and Tertiary Effluents Color Reduction TOC Oxidation (Industrial) Oxidation of Odor Causing Compounds Oxidation of Endocrine Disruptors (EDCs) and Pharmaceutically Active Compounds (PACs)
Applications of Ozone
What are Endocrine Disruptors (EDCs) and Pharmaceutically Active Compounds (PACs)?
EDCs and PACs are Naturally and Synthetic compounds that may affect the balance or normal functions in animals and humans
Applications of Ozone
Examples of Endocrine Disruptors
1000s of compounds that may be Investigated as EDCs Some examples are: Synthetic Hormones Naturally Occurring Estrogens Health and Beauty Aids Solvents Pesticides Surfactants Plastics Fungicides
Microchip manufacturing
Experimental Setup
Front view of the two units after the redesign and reworking of the gas, water and instruments connections.
Experimental Setup
Top view of the two experimental units. Spectroscope (not shown) is to the left of the DBD. The units were different with respect to their electrodes: one had only the electrode coated with the dielectric (singlecoated), the other one had the electrode and the anode coated with the dielectric (double-coated).
Generation of Ozone
Spectroscopy
Plasma
IR spectra in pure oxygen (black curve) and at approximately 10wt% N2 admixture (red line). N2O5 peaks appear at 1245 cm-1 and at 1725 cm-1.
IR spectra of several methane variations. The green curve envelopes all of the methane peaks at 1325 cm-1, recorded at smaller methane admixtures. Simultaneously, the N2O5 peaks disappear as the methane peaks appear.
N2O5 Formation
p=2 bara, cwt=20C, q=3.5kW/m2, f=1450Hz
4.5 4.0 NOx content [ppmV] @ 3wt% N2 Blending 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 5 7 9 11 ozone conc. [wt%] 13 15 17 N2O5 AT95 N2O AT95 N2O5 IGS N2O IGS N2O5 LG N2O LG
Amount of formed N2O5 and N2O as a function of ozone concentration at 3 wt% of nitrogen admixture and for various electrode arrangements.
3.0E+06
2.5E+06
11 3
Intensity, a.u. 2.0E+06
12
2 1.5E+06
4 15 6 8 10 16 14 17
1.0E+06
1
5.0E+05
13
0.0E+00 280
300
320
340
360
380
400
420
440
460
480
500
520
540
560
580
600
620
640
660
680
700
720
740
760
780
800
820
840
860
Wavelength, nm
1.00E+04
Intensity (a.u.)
8.00E+03
6.00E+03
4.00E+03
2.00E+03
O*(777)
0.00E+00 200
250
300
350
400
450
500
550
600
650
700
750
800
850
Wavelength, nm
Intensities in 3 wt%N2+O2 plasma
Dry Air O2 N2
e-
O2
O2*
N
O2
O3
N2*
O3
NO
NO O3 N* O2
NO2
O3
NO2
N NO2
NO3
NO2
N2O N2O4
NO3
N2O5
Modeling of plasma chemistry incl. the NxOy chemistry up to N2O5, for different Oxygen Nitrogen mixtures, varying power deposition scenarios and initial ozone background concentrations (up to 15%) previously done.
With N2 present less oxygen atoms are formed. However, the difference in intensity is very small.
2.0E+03
1.0E+04
wit h
HO 2
Picture of an amorphous-crystalline N2O5 structure captured at the Orlando Skylake water plant in 2006.
Oxygen N2 O2
e-
e-CH4 O
O2
O2*
N
O2
O3
N2 *
OH
NO
NO O3 N* O2
O3
NO2
NO2
O3
NO2
N NO2
NO3
NO2
HNO3
N2 O
N2O4
NO3
N2O5
b).
Outlet
c).
d).
Inlet
Inlet
Electrode of the ozone generator after: *several hours in CH8/O2 and up to 2 wt% of methane (a, b, c) *three hours in CH8/O2+traces of N2 and up to 1 wt% of methane (d) Visible change of discharge character at about 1/3 length of electrode (a, d)
deposition
vaporization by sputtering
Inlet Outlet
Inlet
irreversible process above a N2 threshold (??) << 1000ppm N2 @ any CH4 concentration (60ppm??)
Formation
Summary
The mechanisms of formed NOx by-products follows the same principles as the air fed ozone generators; the amount of formed N2O5 is found to depend on just three parameters: ozone concentration nitrogen admixture cooling water temperature ( = gas temperature) The conversion of methane to OH and H2O is found to depend on: dissociation by electron impact ( microdischarge) energy distribution of electrons in the microdischarges ( discharge gap)
Scientific Approach
Theoretical
P = 4 f C D,i
i =1 n
Experimental
c [wt%] f [Hz]
where i : n : Upeak : Umin, i : f : C D,i i : : : i slice amount of slices per cylinder [] peak voltage [V] minimum voltage i th slice [V] frequency [Hz] capacitance of dielectrics i slice [F]
th th
q [kW/m2]
18.0 efficiency [%] 15.0 12.0 9.0 6.0 3.0 3.9 0.0 10.7 17.6 24.4 8.2 6.4 4.6 2.8 1.0 power density [kW/m2]
Outer grounded electrode (left picture) and the dielectric covered inner electrodes (right).
Reference Arrangement
Inlet
Gas flow direction
Outlet
Optimized Arrangement
Inlet
Gas flow direction
Outlet
O3
Conclusions
Fundamentals of ozone synthesis in a DBD plasma: Highly filamented DBD discharges are best-suited for the production of ozone concentrations in the range of 6 to 14 wt%. The preferred characteristic of the microdischarges are Townsend-like, at reduced electric fields E/n around 190 Townsend. Detrimental side-effects, induced by by-products, can be avoided by a proper design of the electrode arrangement. The phenomenon is related to the diffusion rates of formed by-product clusters.
Conclusions
Benefits from DBD Plasma Tailoring: Reduced power consumption of up to 10% improvement Increased ozone concentrations of up to 14% now achievable Improved neutralization and conditioning of detrimental by-products Reduced system capital and operational cost!!!
Ackownledgements
This research was partly funded and done in collaboration with the Degremont Technologies R&D Spectroscopic and analytical equipment was purchased through a grant for the National Aeronautics and Space Administration (NASA) for enhancement of student research. This research was funded in part by the American Chemical Societys Petroleum Research Fund.
This research was funded in part by the Electro-Energetic Physics Program of the U.S. Air Force Office of Scientific Research (AFOSR).
Questions???
Thank You!
For more information:
Prof. Jose L. Lopez, PhD Saint Peters College Department of Applied Science and Technology Physics Division, Gannon Hall Telephone: (201) 761-6352 Email: joselopez@spc.edu