Analysis of Chemical Reactions in Pulsed Streamer Discharges

221 Pages·2015·1.11 MB·English

by  Mayank Sahni

Florida State University Libraries
Electronic Theses, Treatises and Dissertations The Graduate School
2006
Analysis of Chemical Reactions in Pulsed
Streamer Discharges: An Experimental
Study
Mayank Sahni
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THE FLORIDA STATE UNIVERSITY

COLLEGE OF ENGINEERING

ANALYSIS OF CHEMICAL REACTIONS IN PULSED STREAMER DISCHARGES:
AN EXPERIMENTAL STUDY

BY
MAYANK SAHNI

A Dissertation submitted to the
Department of Chemical Engineering
in partial fulfillment of the
requirements for the degree of
Doctor of Philosophy

Degree Awarded:
Spring Semester, 2006

Copyright © 2006
Mayank Sahni
All Rights Reserved
The members of the committee approve the dissertation of Mayank Sahni defended on
January 9, 2006.

______________________
Bruce R. Locke
Professor Directing Dissertation

______________________
Peter Fajer
Outside Committee Member

______________________
Rufina Alamo
Committee Member

______________________
Ravindran Chella
Committee Member

The office of Graduate Studies has verified and approved the above named committee
members.

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To my Parents

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ACKNOWLEDGMENTS

I thank my thesis advisor Dr Bruce R. Locke, for his motivation, patience and
guidance throughout the course of my PhD. His interest in this work and his style of
advising has motivated me to put in my best effort. I would also like to thank my
committee members Dr Peter Fajer, Dr Ravi Chella and Dr Rufina Alamo for serving on
my committee. Thanks also to Dr Igor Alabugin and Dr Louis Kischenbaum for their
help at critical junctures of my PhD. Helpful discussions with Dr Petr Lukes and Dr Olga
Federova are gratefully acknowledged. I would like to thank Mr Wright Finney for his
suggestions both inside and outside the laboratory.
I would like to acknowledge the support of the Department of Chemical
Engineering, FAMU-FSU College of Engineering, Florida State University Graduate
Student Fellowship, U.S. Department of Defense Small Business Innovative Research,
and the Florida Department of Environmental Protection.
I also thank Dr. Pavel Šunka, Dr. Martin Člupek, and Dr. Vaclav Babicky at the
Institute of Plasma Physics, Czech Academy of Sciences for their hospitality during my
visit.
I would like to thank all my past and present corona group colleagues for several
great years both inside and outside the lab. I owe a great deal to ‘my boss’ Dr. Michael
Kirkpatrick for all his help throughout the course of my PhD. Friends in Tallahassee have
contributed in making my stay here comfortable and exciting. A special thanks is due to
Ms. Jyoti Kolhe for her tremendous help in all facets of my PhD work.
I would like to thank my family, my grandparents, my parents and my sister for
their encouragement and motivation for pursuing my PhD.

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TABLE OF CONTENTS
List of Tables…………………………………………………………………... x
List of Figures………………………………………………………………….. xii
Abstract………………………………………………………………………… xviii

I. INTRODUCTION AND LITERATURE REVIEW………………… 1
1.1 What are Plasmas?……………………………………………… 1

1.2 Various types of electrical discharges and their uses …………... 1

1.3 Liquid phase electrical discharges ……………………………... 3

1.4 Gas phase electrical discharges………………………………… 7

1.5 New Reactor configurations……………………………………. 11

1.6 Comparison of pulsed streamer discharges with other AOP……. 13

1.7 Objectives of this research………….…………………………... 16

II. DEGRADATION OF CHEMICAL WARFARE AGENT SIMULANTS
USING GAS-LIQUID PULSED STREAMER DISCHARGES……. 18

2.1 Introduction…….……………………………………………….. 18

2.2 Experimental techniques and methods …………………………. 21

2.2.1 Materials ……………………………………..……........ 21

2.2.2 Pulsed generation network……………………………… 21

2.2.3 Reactor Configurations ………………………………… 22

2.2.4 Analytical techniques and procedures …………………. 24
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2.2.5 Properties of the simulants chosen…..…………………. 26

2.3 Results and Discussion ………………………………………… 28

2.3.1 Effect of reactor configuration on the degradation of
H agent simulant (no additives in solution)…..………… 28

2.3.2 Effect of reactor configuration on the degradation of H
agent stimulant (ferrous salts in solution (Fenton’s
case))….………………………………………………... 32

2.3.3 Comparison of the ion chromatography data on the
degradation of H agent stimulant in various reactor
configurations…..……………………………………… 36

2.3.4 Energy yields of degradation of the H agent stimulant… 36

2.3.5 Effect of additives in solution (zeolites and platinum
coated activated carbon) on the degradation of the
H agent simulant …..…………………………………… 41

2.3.6 Degradation of G agent simulant in reference and series
configurations (no additives in solution)………………. 46

2.3.7 Degradation of G agent simulant in reference and
series configurations (ferrous salts in solution (Fenton’s
reactions)) ……………………………………………... 48

2.3.8 Comparison of the ion chromatography and energy
efficiency data on the degradation of G agent stimulant
in various reactor configurations………………………. 49

2.4 Conclusions……………………………………………........ …. 50

III. DEGRADATION OF AQUEOUS PHASE POLYCHLORINATED
BIPHENYLS (PCB) USING PULSED CORONA DISCHARGES … 53

3.1 Introduction ………………………………………………….. 54

3.2 Experimental Techniques…………………………………….. 55

3.2.1 Materials and Methods ……………………………..... 55

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3.2.2 Pulse Generating Network ………………………......... 56

3.2.3 Reactor Configuration ………….…………………........ 56

3.3 Results and Discussion ………………………………………… 58

3.3.1 Comparison of experimentally obseved and model
simulated degradation of TCB in the reference
configuration………….................................................... 59

3.3.2 TCB degradation in the Series configuration ………….. 62

3.3.3 Effect of high voltage electrodes on the degradation of
TCB………….................................................................. 68

3.3.4 Effect of additives (zeolytes) on the degradation of TCB... 70

3.3.5 Effect of hydroxyl radical scavenger (methanol) on the
degradation of TCB ……………………......................... 72

3.3.6 Effect of salts in solution on the degradation of TCB….. 74

3.3.7 Effect of initial pH of solution on the degradation of TCB.. 75

3.3.8 Comparison of degradation of PCB congeners with
different number of chlorine substituents…………….... 76

3.4 Conclusions ……………………………………………............ 79

IV. QUANTIFICATION OF HYDROXYL RADICALS PRODUCED
IN PULSED ELECTRICAL DISCHARGE REACTORS………. 80

4.1 Introduction …………………………………………………….. 80

4.2 Experimental Procedures……………………………………….. 83

4.2.1 Chemical and Materials..……………………………….. 83

4.2.2 Formaldehyde quantification using HPLC…................... 84

4.2.3 Quantification of 2-hydroxyterephthalic acid (HTA)…... 84

4.2.4 Quantification of hydrogen peroxide (H O ).................... 84
2 2

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4.2.5 Quantification of ozone (O )..………………………….. 84
3

4.2.6 Power Supply and Reactor Configuration….................... 85

4.2.7 Reaction mechanisms and byproducts of probes….......... 88

4.3 Results and Discussion…………………………………………. 90

4.3.1 Effect of input power on the hydroxyl radical
production rate………………………………………… 90

4.3.2 Effect of reactor configuration on the hydroxyl radical
production rate ..……………………………………….. 101

4.3.3 Effect of gas composition on the hydroxyl radical
production rate ..……………………………………….. 110

4.3.4 Effect of initial conductivity of the solution on the
hydroxyl radical production rate ……………………… 114

4.3.5 Effect of initial pH of solution on the hydroxyl radical
production rate …………….………………………….. 121

4.3.6 Effect of solution temperature on the hydroxyl radical
production rate……..…………………………………. 124

4.3.7 Effect of high voltage electrode material on the
hydroxyl radical production rate……………………….. 126

4.3.8 Effect of adding reactive species scavengers to the
solution on the hydroxyl radical production rate………. 128

4.3.9 Effect of additives such as zeolytes to the solution on
the hydroxyl radical production rate…………………… 130

4.4 Conclusions…………………………………………………….. 133

V. QUANTIFICATION OF REDUCTIVE SPECIES PRODUCED BY HIGH
VOLTAGE ELECTRICAL DISCHARGES IN WATER…………. 134

5.1 Introduction…………………………………………………….. 134

5.2 Experimental methods…………………………………………… 139

5.3 Results …………………………………………………………... 143
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a) Reductive Species Quantification using TNM as the reductive species probe

5.3.1 Effect of initial concentration of probe (TNM) on the
production of reductive species………………............... 143

5.3.2 Effect of initial power (applied voltage) on the
formation and degradation of NF-……………..………. 143

5.3.3 Effect of initial conductivity of solution on the
production of reductive species……………………….. 146

5.3.4 Effect of scavengers of solution on the production of
reductive species………………………………………. 151

5.3.5 Effect of bubbling different gases into solution on the
production of reductive species……………………….. 160

b) Reductive Species Quantification using NBT as the reductive species probe

5.3.6 Effect of input power (applied voltage) on the
production of reductive species ……………………….. 161

5.3.7 Comparison of the production rate of reductive and
oxidative species……………………………………….. 165

5.3.8 Experiments with NBT as probe with TNM as
scavenger in solution…………………………………… 167

5.4 Conclusions……………………………….................................. 169

VI. SUMMARY AND CONCLUSIONS…………………………………. 170
VII. FUTURE WORK………………………………………………………. 178

APPENDIX ….………………………………………………………………….. 181
REFERENCES………………………………………………………………….. 182
BIOGRAPHICAL SKETCH……………………………………………………. 199
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