U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
PB80-180037
OZONE FOR INDUSTRIAL WATER AND WASTEWATER
TREATMENT AN ANNOTATED BIBLIOGRAPHY
RIP G, RICE, ET AL
INTERNATIONAL OZONE ASSOCIATON
CLEVELAND, OHIO
MAY 1980
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EPA 600/2-80-142
May 1980
OZONE FOR INDUSTRIAL WATER AND WASTEWATER TREATMENT
An Annotated Bibliography
by
Rip G. Rice
Jacobs Engineering Group
Washington, D.C. 20005
and
Myron E. Browning
Allied Chemical Company
Syracuse, New York 13209
Grant No. R-803357
to
International Ozone Associaton
Cleveland, Ohio 44167
Project Officer
Fred M. Pfeffer
Source Management Branch
Robert S. Kerr Environmental Research Laboratory
Ada, Oklahoma 74820
ROBERT S. KERR ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
ADA, OKLAHOMA 74820
REPRODUCED BY
NATIONAL TECHNICAL
INFORMATION SERVICE
IIS DEPARTMENT OF COMMERCE
SPRINGFIELD, VA 22161
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TECHNICAL REPORT DATA
(Please read /attractions on the reverse before completing)
1 REPORT NO
EPA-600/2-80-142
3. RECIPI
ENTJS ACCESSION-NO
PB80 180037
4 TITLE AND SUBTITLE
Ozone for Industrial Water and Wastewater
Treatment, An Annotated Bibliography
5 REPORT DATE
l"ay 19GO issuine date.
6. PERFORMING ORGANIZATION CODE
Jacobs Engrg. Group
Uflchinomn n r ?nnns
and Myron E. Browning
Allied Chemical Co.
Syracuse MV 11900
8. PERFORMING ORGANIZATION REPORT NO
9 PERFORMING ORGANIZATION NAME AND ADDRESS
International Ozone Association
Cleveland, Ohio 44167
10 PROGRAM ELEMENT NO.
C33B1B
11 CONTRACT/GRANT NO
Grant No. R-803357
12 SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Robert S. Kerr Environmental Research Laboratory
P. 0. Box 1198
Ada, Oklahoma 74820
13. TYPE OF REPORT AND PERIOD COVERED
Final Report/7-1974 to 7-1977
14 SPONSORING AGENCY CODE
600/15
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The project explored the technology of ozonation applicable to industrial water
and wastewater treatment. The final report documents existing equipment, extent
of application and practical usage, contract systems, monitoring and detection
devices, general and specific economics, and most recent acceptable procedures.
17
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Industrial waste treatment, oxidation
ozonization, activated carbon, activated
sludge process, wastewater, waste treat-
ment
Industrial wastewater
treatment; biological
activated carbon.
NTIS 68/D
13 DISTRIBUTION STATEMENT
Release to Public
19 SECURITY CLASS (ThisReport/
Unclassified
21 NO OF PAGES
199
20 SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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DISCLAIMER
This report has been reviewed by the Robert S. Kerr Environmental
Research Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents necessarily reflect
the views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
n
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FOREWORD
The Environmental Protection Agency was established to coordinate adminis-
tration of the major Federal programs designed to protect the quality of our
environment .
An important part of the Agency's effort involves the search for informa-
tion about environmental problems, management techniques and new technologies
through which optimum use of the Nation 'a land and water resources can be
assured and the threat pollution poses to the welfare of the American people
can be minimized. EPA's Office of Research and Development conducts this
search through a nationwide network of research facilities.
As one of these facilities, the Robert S. Kerr Environmental Research
Laboratory is responsible for the management of programs to: (a) investigate
the nature, transport, fate and management of pollutants in ground water;
(b) develop and demonstrate methods for treating wastewaters with soil and
other natural systems; (c) develop and demonstrate pollution control technol-
ogies for irrigation return flows; (d) develop and demonstrate pollution con-
trol technologies for animal production wastes; (e) develop and demonstrate
technologies to prevent, control, or abate pollution from the petroleum refin-
ing and petrochemical industries; and (f) develop and demonstrate technologies
to manage pollution resulting from combinations of industrial wastewaters or
industrial/municipal wastewaters .
Increasing concern over the presence of toxic or nonbiodegradable com-
ponents in treated effluents has dictated that research be performed to
establish technologies for removal or conversion of those compounds to elimi-
nate them from industrial wastewaters prior to discharge. Application of
innovative technology, such as ozonation, to control undesirable contaminants
in wastewater streams is of paramount interest as a potential treatment
methodology to protect the environment.
~~J O.
W. C. Galegar
Director
Robert S. Kerr Environmental Research Laboratory
iii
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ABSTRACT
This research project and technology transfer effort was initiated in
response to growing national concern about the discharge of industrial
chemicals and by-products from industrial processing plants into the environ-
ment. The technology of oxidation of these chemicals by means of ozone, a
very powerful oxidant, offers promise for being able to eliminate some of
these chemicals from industrial wastewaters prior to discharge. Therefore
this program was initiated to survey the published ozone literature and
assess how ozone has been used in the past to cope with specific industrial
water and wastewater problems.
In the Literature Survey, which is a separate EPA report, there is
included a section on the fundamental principles of ozone technology, which
describes the generation of ozone on commercial scale, the various methods of
contacting ozone with aqueous solutions and methods of analysis for ozone
from the point of view of process controls.
Industries are grouped into 20 individual categories which are discussed
separately as to the known uses of ozone in treating waters and wastewaters
in each category. More than 500 published articles were reviewed. Some of
these articles were abstracted, and these abstracts have been assembled in
this companion report.
Abstracts are grouped according to their industrial categories, which
are arranged alphabetically. A list of Literature Cited is given for each
industrial category, and the cited articles are arranged alphabetically with
respect to the last name of the senior author. Each article cited has been
given a 2-letter category code and a number. For example, AQ-12 means the
Aquaculture category, reference number 12.
An asterisk following the reference cited indicates that an abstract of
that reference is included in this Annotated Bibliography.
iv
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CONTENTS
Foreword 11 i
Abstract 1v
Tables yii
Abbreviations and Symbols viii
Acknowledgements ix
1. Introduction 1
2. Aquaculture
Literature cited 2
Abstracts 5
3. Biofouling Control
Literature cited 16
Abstracts 17
4. Cyanides and Cyanates
Literature cited 18
Abstracts 20
5. Electroplating
Literature cited 25
Abstracts 27
6. Food & Kindred Products and Brewing
Literature cited 40
Abstracts 41
7. Hospital Wastewaters
Literature cited 50
Abstracts 53
8. Inorganics
Literature cited 59
Abstracts 60
9. Iron & Steel
Literature cited 62
Abstracts 63
10. Leather Tanneries
Literature cited 70
Abstracts 70
11. Mining
Literature cited 72
Abstracts 73
12. Organic Chemicals
Literature cited 75
Abstracts 81
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13. Petroleum Refineries
Literature cited 98
Abstracts 100
14. Pharmaceuticals
Literature cited Ill
15. Phenols
Literature cited 112
Abstracts 114
16. Photoprocessing
Literature cited 134
Abstracts 135
17. Plastics & Resins
Literature cited 147
Abstracts 147
18. Pulp & Paper
Literature cited 150
Abstracts 155
19. Soaps & Detergents
Literature cited 173
Abstracts 174
20. Textiles
Literature cited 177
Abstracts 179
VI
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TABLES
Number £§2!
1 Effects of Ozonation of Gymnodinium breve Toxin on Mice and Killfish 8
2 Depuration of Clams in Ozonized Seawater 11
3 Effects of Ozonized Seawater on Spawned, Fertilized Meiotic and
Cleaving Oyster Eggs 12
4 Cost Comparisons of Treating Cyanide Wastewaters by a Variety of
Techniques 34
5 Ozone Treatment of Severodonetsk Chemical Works, Biologically Treated
Wastewaters 88
6 Ozone Treatment of Shchekino Chemical Works, Biologically Treated
Wastewaters 88
7 Treatment of Sewage of a Varnish Plant by Gassing With Ozone (20 mg 0~
in Air) for 30 Minutes at 19°C J94
8 Wastewater Discharge of a Paint & Varnish Plant Treated 25 Minutes
With Ozonized Air 95
9 Wastewater From the Canal Near the Outlet of a Paint & Vanish
Manufacturing Plant, Pretreated by Precipitation and Treated with
Ozone (30 Minutes) and Chlorine 96
10 Laboratory Data Obtained by Ozonation of Refinery Wastewater . . . .106
11 Ozonation of Refinery Wastewaters at Sarnia, Ontario, Canada .... 108
12 Ozonation of Phenols 124
13 Effects of Ozonation of Phenols on Solution CODs 123
14 Effect of pH on Ozonation of a 30 mg/1 Solution of Phenol 125
15 Ozonation of Phenol, o-Cresol and p-Cresol 128
16 Ozonation of Phenolic Wastes to 99% Removal 128
17 Ozonation of Synthetic Photoprocessing Effluents (Sample Volume =
3 Liters) 136
18 Ozonation of Photoprocessing Chemicals 137
19 Ozonation of Spent Photographic Ferrocyanide Bleach Solutions. ... 144
VII
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LIST OF ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS MeOH
mg/1
AcH -- acetaldehyde min
APHA -- American Public Health MM
Association MUST
bbl -- barrel
BOD -- biochemical oxygen demand nm
BOD-5 — 5-day BOD NMR
BPTCA -- best practicable control
technology currently NSSC
available
BuOH -- butyl alcohol (butanol) OAV
cfm -- cubic feet per minute OD
cm -- centimeters PAC
COD -- chemical oxygen demand
cP -- centipoise ppb
cu ft -- cubic feet ppm
DO -- dissolved oxygen PSIG
EDTA -- ethylenediaminetetra- P.V.
acetic acid PVC
Et — ethyl RFI
EtOAc -- ethyl acetate RO
EtOH -- ethyl alcohol (ethanol) RPM
GAC -- granular activated carbon SCFH
gal -- gallon scfm
g/hr -- grams per hour sec
gpm -- gallons per minute sq m/hr
gpd -- gallons per day SS
HCHO — formaldehyde std 1/min
HCOOH -- formic acid TDS
hr -- hour TLC
hp -- horsepower TOC
Hz -- hertz UF
I ~ imperial US
ID — inside diameter UV
Igpm — imperial gallons/minute v •
in -- inch, inches wh/g
IR -- infrared yr
kg/sq cm — kilograms/square cm
KHz -- kilohertz SYMBOLS
kw -- kilowatt
kwh -- kilowatt-hour [ ]
M -- molar u
Me -- methyl
methyl alcohol, methanol
milligrams per liter
minute
million
mobile unit, self
transportable
nanometer
nuclear magnetic
resonance
neutral sulfite semi-
chemical
oxygen absorption value
outside diameter
powdered activated
carbon
parts per billion
parts per million
pounds per sq in guage
permanganate value
polyvinyl chloride
refractory index scale
reverse osmosis
revolutions per minute
standard cu ft/hr
standard cu ft/min
second
square meters per hour
.suspended solids
standard liters/minute
total dissolved solids
thin layer chromatography
total organic carbon
ultrafiltration
ultrasonics
ultraviolet
volt
watt hours/gram
year
concentration of
micron
vm
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ACKNOWLEDGEMENTS
The authors are grateful for the assistance of many people whose efforts
were essential to the accomplishment of this work. First, we thank the State
of Connecticut, Department of Environmental Protection for their financial
contribution in support of this program.
For the gathering and abstracting of the many articles cited, we are
appreciative of the efforts of Dr. Archibald G. Hill, William J. Geist, Jane
Tofel, James King, Dr. Stanley Padegimas, John Graumann, Teresa Czaposs and
Barbara Cowley-Durst.
We also thank Dr. Walter J. Blogoslawski of the National Marine Fisheries
Service for critically reviewing those sections of this report dealing with
aquaculture and biofouling, Dr. L. Joseph Bollyky of Bollyky Associates for
reviewing the sections dealing with cyanides and cyanates as well as electro-
plating, and Captain Barry W. Peterman of the Army Medical Bioengineering
Research & Development Laboratories for reviewing the section on hospital
wastewaters.
IX
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INTRODUCTION
Although ozone has been used to treat drinking water at the city of Nice
since 1906, and today there are more than 1,000 water treatment plants in
Europe alone employing ozone for many different water treatment purposes
(Miller ejt al_., 1978), industrial wastewater treatment with ozone is still,
relatively speaking, in its infancy.
Current water pollution problems with industrial wastewater discharges
have prompted renewed interest in the use of powerful oxidants, including
ozone, for treating these wastewaters for recycle and reuse, or prior to
discharge to the environment.
In addition, where halogenated oxidants such as chlorine and hypochlo-
rite are currently used to treat municipal and industrial wastewaters,
toxicities of these halogenated wastewaters to indigenous aquatic life also
have prompted studies on alternative treatment techniques, including ozonation.
In recognition of the potentials for ozone to alleviate certain industrial
wastewater pollution problems, the U.S. Environmental Protection Agency,
Office of Research & Development, funded a grant (R-803357-01-3) to the
International Ozone Institute to conduct a state-of-the-art review of the
published literature dealing with the use of ozone. This report will summarize
the results of that survey.
This survey is not an exhaustive review of the published literature, in
that only the more readily available articles were obtained. In addition,
much of the Russian, Japanese and German literature could not be translated
due to limitations of time and funding. Nevertheless, some 430 published
articles were reviewed and abstracted. Abstracts of the more pertinent
articles have been compiled in this companion report.
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LITERATURE CITED -- AQUACULTURE (AQ)
AQ-01 Anonymous, 1972, "Use of Ozone in Sea Water for Cleansing Shell-
fish", Effluent and Water Treatment Journal, 12:260-262.
AQ-02 Blogoslawski, W.J., 1977, "Ozone as a disinfectant in mariculture",
in Proc. Third Meeting of the I.C.E.S. Working Group on Mariculture,
Brest, France, May 10-13. Actes de Collogues de C.N.E.X.O. 4:371-
381.
AQ-03 Benoit, R.G. & N.A. Matlin, 1966, "Control of Saprolegnia on Eggs
of Rainbow Trout (Salmo gairdneri) with Ozone", Trans. Am. Fish
Soc. 95(4):430-432.
AQ-04* Blogoslawski, W.J., C. Brown, E.W. Rhodes & M. Broadhurst, 1975,
"Ozone Disinfection of a Seawater Supply System." in Proc. First
Intl. Symp. on Ozone for Water & Wastewater Treatment, R.G. Rice &
M.E. Browning, Editors, Intl. Ozone Assoc., Cleveland, Ohio, p.
674-687.
AQ-05 Blogoslawski, W.J., F.P. Thurberg & M.A. Dawson, 1973, "Ozone
Inactivation of a Gymnodim'um breve Toxin." Water Research 7:1701-
1703.
AQ-06* Blogoslawski, W.J., F.P. Thurberg, M.A. Dawson & M.J. Beckage,
1975, "Field Studies on Ozone Inactivation of a Gymnodim'um breve
Toxin", Environmental Letters, 9(2):209-215.
AQ-07 Blogoslawski, W.J., L. Farrell, R. Garceau & P. Derrig, 1976,
"Production of Oxidants in Ozonized Seawater", in Proc. Sec. Intl.
Symp. on Ozone Techno!., R.G. Rice, P. Pichet & M.-A. Vincent,
editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 671-681.
AQ-08 Blogoslawski, W.J. & M.E. Stewart, 1977, "Marine Applications of
Ozone Water Treatment", in Forum on Ozone Disinfection, E.G.
Fochtman, R.G. Rice & M.E. Browning, editors, Intl. Ozone Assoc.,
Cleveland, Ohio, p. 266-276.
AQ-09 Blogoslawski, W.J. & M.E. Stewart, 1978, "Paralytic Shellfish
Poison in Spisula solidissima; Anatomical Location and Ozone
Detoxification", Marine Biology, in press.
AQ-10* Burkstaller, J. & R.E. Speece, 1970, "Survey of Treatment and
Recycle of Used Fish Hatchery Water." New Mexico State Univ. Engr.
Exptl. Sta., Technical Rept. #64, June.
AQ-11 Ciambrone, D.F., 1975, "Ozone Treated Sewage for Oyster Culture",
in Aquatic Applications of Ozone, W.J. Blogoslawski & R.G. Rice,
editors. Intl. Ozone Assoc., Cleveland, Ohio, p. 81-86.
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AQ-12 Combs, T.J. & W.J. Blogoslawski, 1975, "Effects of Ozone on a
Marine-Occurring Yeast, Sporobolomyces", in Aquatic Applications of
Ozone. W.J. Blogoslawski & R.G. Rice, editor?. Intl. Ozone Assoc.,
Cleveland, Ohio, p. 43-49.
AQ-13 Crecelius, E.A., 1977, "The Production of Bromine and Bromate in
Seawater by Ozonization", presented at Symp. on Advanced Ozone
Technology, Toronto, Ontario, Canada, Nov. Intl. Ozone Assoc.,
Cleveland, Ohio.
AQ-14 Dawson, M.A., F. Thurberg, W.J. Blogoslawski, J. Sasner, Jr. & M.
Ikawa, 1974, "Inactivation of Paralytic Shellfish Poison by Ozone
Treatment", Proc. Food-Drugs from the Sea Conf., Marine Technology
Soc., p. 152-157.
AQ-15* DeManche, J.M., P.L. Donaghay, W.P. Breese & L.F. Small, 1975,
"Residual Toxicity of Ozonized Seawater to Oyster Larvae." Oregon
State Univ., Sea Grant College Prog. Pub. #ORESU-T-75-003, November,
5 pp.
AQ-16 Edwards, H.B., 1974, "Closed Raceway System for Mariculture", 1974,
Presented at World Mariculture Soc. Meeting.
AQ-17 Edwards, H.B., 1975, "A New Concept for Aquaculture Closed Raceway
Systems", Presented at World Mariculture Society, Seattle, Washington,
Jan. 30.
AQ-18 Eppley, R.W., E.H. Renger & P.M. Williams, 1976, "Chlorine Reactions
With Seawater Constituents and the Inhibition of Photosynthesis of
Natural Marine Phytoplankton", Estuarine & Coastal Marine Sci.
4:147-161.
AQ-19* Fauvel, Y., 1963, "Use of Ozone as a Sterilizing Agent in Seawater
for the Depuration of Shellfish", Intl. Comm. for Scientific
Exploration of the Mediterranean Ocean, Reports and Verbal Proceedings
17(3):701-706.
AQ-20 Fauvel, Y., 1964, "Nouvelles observations sur 1'utilisation de
1'ozone comme agent stirilisateur de 1'eau de mer pour 1'epuration
des coquillages", Comrn. Int. Explor. Sci. Mer MSdit., Symp. Pollut.
Mar. par Microorgan. Prod. P§trol. 293-298.
AQ-21 Fauvel, Y., 1967, "1'Epuration des Coquillages", Rev. trav. Inst.
PSches marit., 31(1).
AQ-22 Fauvel, Y., 1977, "Utilisation de L'Ozone en Ostreiculture et dans
les Industries Connexes", Presented at 3rd Intl. Symp. on Ozone
Technol., Paris, France, May. Intl. Ozone Assoc., Cleveland, Ohio.
AQ-23 Frese, R., 1974, "Ozonisierung odor Biologische Filterung. Eine
Vergleichende Studie mit Einbeziehung der Erfahrungen am Kieler
Aquarium". Diplomarbeit Christian Albrecht. Univ. Kiel, 58 p.
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AQ-24 Giese, A. & E. Christensen, 1965, "Effects of Ozone on Organisms",
Physio!. Zool. 27(2):101-115.
AQ-25 Haraguchi, T., U. Simidu & K. Also, 1969, "Preserving Effect of
Ozone to Fish", Bull. Japanese Soc. Sci. Fisheries, 35(9).
AQ-26 Helz, G.R., R.Y. Hsu & R.M. Block, 1978, "Bromoform Production by
Oxidative Biocides in Marine Waters", in Ozone/Chlorine Dioxide
Oxidation Products of Organic Materials, R.G. Rice & J.A. Cotruvo,
editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 68-76.
AQ-27 Honn, K. & W. Chavin, 1976, "Utility of Ozone Treatment in the
Maintenance of Water Quality in a Closed Marine System", Marine
Biol. 34:201-209.
AQ-28 Ingols, R.S., 1978, "Ozonation of Seawater", in Ozone/Chlorine
Dioxide Oxidation Products of Organic Materials. R.G. Rice & J.A.
Cotruvo, editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 77-81.
AQ-29 Macalady, D.L., J.H. Carpenter & C.A. Moore, 1977. "Sunlight-
Induced Bromate Formation in Chlorinated Seawater", Science 195:1335-
1337.
AQ-30* MacLean, S.A., A.C. Longwell & W.J. Blogoslawski, 1973, "Effects of
Ozone-treated Seawater on the Spawned, Fertilized, Meiotic and
Cleaving Eggs of the Commercial American Oyster." Mutation Rsch.
21:283-285.
AQ-31 Murphy, W.K., 1975, "The Use of Ozone in Recycled Oceanarium Water",
in Aquatic Applications of Ozone, W.J. Blogoslawski & R.G. Rice,
editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 87-95.
AQ-32 Pichet, P. & C. Hurtubise, 1975, "Reactions of Ozone in Artificial
Seawater", in Proc. Sec. Intl. Symp. on Ozone Technol., R.G. Rice,
P. Pichet & M.-A. Vincent, editors, Intl. Ozone Assoc., Cleveland,
Ohio, p. 665-681.
AQ-33 Rosenlund, B.D., 1975, "Disinfection of Hatchery Influent By Ozona-
tion and the Effects of Ozonated Water on Rainbow Trout", in
Aquatic Applications ojf Ozone, W.J. Blogoslawski & R.G. Rice,
editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 59-69.
AQ-34* Salmon, J., A. Salmon, J. Le Gall & D. Loir, 1937, "A Depuration
Station for Shellfish Using Ozonized Seawater." Ann. Hyg. 15:581-
584.
AQ-35* Salmon, J., J. Le Gall & A. Salmon, 1937, "Preliminary Note on
Several Experiments of Purifying Edible Marine Molluscs by Ozonized
Seawater", Ann. Hyg. Publique, Industrielle et Sociale 15:44-50.
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AQ-36 Sander, E. & H. Rosenthal, 1975, "Application of Ozone in Water
Treatment For Home Aquaria, Public Aquaria and for Aquaculture
Purposes", in Aquatic Applications of Ozone. W.J. Blogoslawski &
R.G. Rice, editors, Intl. Ozone Assoc., Cleveland, Ohio', p. 103-
114.
AQ-37 Spotte, S.H., 1970, Fish and Invertebrate Culture: Water Management
jn_ Closed Systems. Wiley-Tnterscience Publishers, Inc., New York,
N.Y., 145 p.
AQ-38 Stewart, M.E. & W.J. Blogoslawski, 1977, "Detoxification of Marine
Poisons By Ozone Gas", Presented at 3rd Intl. Symp. on Ozone
Technol., Paris, France, May. Intl. Ozone Assoc., Cleveland, Ohio.
AQ-39 Stopka, K., 1975, "European and Canadian Experiences with Ozone in
Controlled Closed Circuit Fresh & Salt Water Systems", in Aquatic
Applications of Ozone, W.J. Blogoslawski & R.G. Rice, editors,
Intl. Ozone Assoc., Cleveland, Ohio, p. 170-176.
AQ-40 Tchakhotine, S., 1937, "The Destructive Action of Ozone on Sperm",
Compt. rend, de Soc. de Biologie 126:1154-1156.
AQ-41 Thompson, G.E., 1976, "Ozone Applications in Manitoba, Canada", in
Proc. Sec. Intl. Symp. on Ozone Technology, R.G. Rice, P. Pichet &
M.-A. Vincent, editors, Intl. Ozone Assoc., Cleveland, Ohio, p.
682-693.
AQ-42 Thurberg, P.P., 1975, "Inactivation of Red-Tide Toxins by Ozone
Treatment", in Aquatic Applications of Ozone. W.J. Blogoslawski &
R.G. Rice, editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 50-58.
AQ-43* Violle, H., 1929, "Sterilization of Seawater with Ozone: Application
of this Method to the Purification of Contaminated Shellfish", Rev.
Hyg. et de Med. Preventive 51:42-46.
AQ-04
Title: "Ozone Disinfection Of A Seawater Supply System"
Authors; W.J. Blogoslawski, C. Brown, E.W. Rhodes & M. Broadhurst
Source; Proc. First Intl. Symposium on Ozone for Water & Wastewater Treatment,
R. G. Rice & M. E. Browning, Editors, Intl. Ozone Assoc., Cleveland,
Ohio (1975), p. 674-687.
Describes a 13,000 gpd pilot scale seawater disinfection system at the
Mil ford, Connecticut Laboratory of the National Marine Fisheries Service. It
was designed to eliminate fouling associated with piping volumes of seawater
and reduce the possibility of marine microorganisms pathogenic to fish,
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molluscs, and crustaceans. In addition, the process demonstrated the ability
of aeration to reduce the toxicity of phytoplankton metabolites during midsummer
bloom of Long Island Sound "red tides".
System Description: Raw seawater is gravity delivered to a magnetic drive
centrifugal pump and lifted through a 1.7 cu ft vertical packed column contain-
ing 8 x 12 mesh coconut shell activated carbon (Calgon Corp., Type PCB).
After prefiltration, the water is passed through 2 static mixing columns
(Kenics Corp. Model 37-56-092) in vertical series with a total of 24 PVC
mixing elements. Ozone gas in compressed air is introduced counter-currently
at the base of the mixing column by a 6 g/hr capacity ozone generator (PCI
Ozone Corp.) at a flow of 20 SCFH. (The concentration of ozone in the air
feed gas is not given, therefore, ozone dosage and ozone utilization cannot
be calculated with certainty.)
Ozonized seawater then is pumped up through 3 parallel column filters
containing 10.2 cu ft of 6 x 16 mesh coconut shell activated carbon. Treated
water is passed through 2 10-micron mesh nylon filter bags and stored in a
750 gal fiberglass-lined holding tank. Water production is controlled by
float switches located in the storage tank. When the system is not treating
water the carbon columns are automatically back-flushed with well water at 45
PSIG. The cumulative backwashing time amounts to 11 or 12 hrs/day. Dissolved
ozone is determined from samples taken prior to carbon filtration by an
amperometric ozone analyzer (Fisher & Porter, Model 17L-2000). No ozone is
found 1n the effluent from the carbon columns. Water quality is monitored by
total plate counts taken weekly. Samples of the raw and ozonized water are
plated on marine agar and incubated for 5 days at 18°C.
Plate counts were taken over 1 yr of normal operation to monitor disinfec-
tion efficiency. Entering bacterial concentrations were 105 to 103/ml.
Counts in the ozonized seawater were at least 2 to 3 log numbers less than in
the raw water. At a dissolved ozone concentration of 0.5 to 0.56 mg/1, no
microorganisms were observed on inoculated agar plates. This residual ozone
concentration was obtained at a 7 gpm flow and 30 sec residence time in the
ozone reactor (20°C). If the generator was producing at its maximum rate (6
g/hr), then the ozone dosage required to attain the residual of 0.5 to 0.56
mg/1 was 3.77 mg/1. However, ozone utilization cannot be calculated, since
the amount of ozone in contactor off-gases was not determined.
During the pilot study, marine fish, crustaceans and molluscs freshly
captured from Long Island Sound were held in flow-through 250 gal tanks
containing either raw or ozonized water. In groups without water treatment,
fish developed whitish lesions near the fins or tail characteristic of the
salt water aquaria disease "fin rot". Mortality ranged from 78 to 100% over
a 90 day test period. No fin rot or necrotic lesions were noticed, and
limited mortality occurred in fish held in ozone treated water.
Ozonized water prevented fertilized oyster eggs from developing into
normal larvae. In a 68-hr test only 44.2% of the eggs developed normally in
ozonized water. Toxicity cannot be caused by residual ozone due to its short
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half-life and because dissolved ozone Is destroyed upon passage of the treated
water through activated carbon. Therefore it is concluded that toxic activity
is caused by some oxidation product (organic or inorganic).
The ozone contactors, associated piping and after-filters have remained
free of fouling organisms. Non-ozonized seawater pipes become heavily
fouled over a 3 day period. This indicates a potential for ozone to control
biological fouling.
AQ-06
Title: "Ozone Inactivation Of A Gymnodinium breve Toxin"
Authors: W.J. Blogoslawski, P.P. Thurberg & M.A. Dawson
Source: Water Research 7:1701-1703 (1973).
Discusses the ability of ozone to inactivate toxic metabolites of the
Florida red tide dinoflagellate, Gymnodinium breve.
Crude toxic material was obtained by ether extraction of Gymnodinium
breve cultures. The toxic powder was suspended in mammalian saline and
injected intraperitoneally (i.p.) into 19 to 21 g white mice. A similar
preparation was suspended in seawater and injected i.p. into 6 to 10 g killi-
fish. Mouse dosage was 6.0 mg toxin in 0.4 ml saline, and the fish dosage
was 6.0 mg in 0.2 ml saline. After data were obtained on the toxicity of the
sample, the material was ozonized.
Three ml samples (toxin suspended in appropriate saline) were placed in
2-dram glass vials and ozone bubbled through the solution via a 21-gauge
hypodermic needle. A small magnetic bar was placed in each vial to allow
continuous stirring during ozonization and all samples were treated 15 min.
The ozone (1% by wt in compressed air) was generated by a Marine Water Purifier
with a rated capacity of 2.0 g/hr (PCI Ozone Corp.). The gas flow rate was
determined by a Gilmont flow meter (size 1).
The results of ozonization of toxin, as tested by mouse and fish injection
are shown in Table 1.
The authors conclude that the study demonstrated the potential use of
ozone water treatment as a method of detoxifying red tide water prior to use
in aquarium systems, provided no ozone residual remains in the water. Residual
ozone may be removed by filtration through activated carbon.
The authors do not state the ratio of ozone dosage to toxin removed,
however this was calculated from the description of the experiment. An ozone
gas concentration of 1% by wt is equivalent to about 12 mg ozone/1 of gas.
Bubbling 15 min at the rate of 0.11 liter/min corresponds to an applied dose
of 19.8 mg of ozone. The 3 ml soln of toxin in saline for use on the mice
contained 45 mg of toxin; that for use on killifish contained 90 mg of toxin.
-------
From the table It can be seen that this amount of toxin was deactivated by
the preceding dosage of ozone. Data are not given for the amount of ozone in
the off-gases, so that the amount of ozone utilized cannot be determined.
TABLE 1. EFFECTS OF OZONATION OF GYMNODINIUM BREVE TOXIN ON MICE AND
KILLIFISH
MICE (Mus musculus)
nl 03/min
no
65
40
20
0
No. of Animals
10
10
5
5
10
Death time(min)
146-178
96-166
18-40
7-10
No. Alive (48 hr)
10
8
2
0
0
KILLIFISH (Fundulus heteroclitus)
nl 0,/min
110
0
No. of Animals
25
25
Death time(min)
240-360
15-30
No. Alive
23
0
AQ-10
Title: "Survey of Treatment and Recycle of Used Fish Hatchery Water"
Authors: J. Burkstaller and R.E. Speece
Source: New Mexico State University, Engineering Experiment Station,
Technical Report No. 64, June 1970.
Reuse of fish hatchery water is becoming more attractive for the following
reasons: (1) many water supplies are too cold and must be heated, and on a
once-through basis all heat remaining is wasted; (2) many areas do not have
sufficient water supplies to raise full capacities of fish during dry months,
and (3) spatial limitations are also becoming increasingly prevalent. Problems
encountered in recycling of hatchery water include:
(1) Smaller fish are much more susceptible to certain fish diseases and
recycle can take disease-producing organisms from older fish and start an
epidemic among the younger fish; (2) ammonia is extremely toxic to fish even
in very small amounts, and therefore, it must be removed from the water
before reuse; and (3) for growing cold water fish, recycle water may become
unsuitable since it eventually warms to the temperature of the surroundings.
Various treatment methods tested to alleviate these problems include the
use of UV light, chlorine, bromine, chlorine-bromine combinations, and the
suggested use of ozone for disinfection. Use of these methods, however,
8
-------
would require additional treatment for residual removal. A typical installa-
tion involving U-tube aeration, biological filters for nitrification, and
continuous monitoring of pH, DO and temperature is presented.
AQ-15
Title; "Residual Toxicity of Ozonized Seawater to Oyster Larvae"
Authors: J.M. DeManche, P.L. Donaghay, W.P. Breese & L.F. Small
Source: Oregon State Univ. Sea Grant Program, Pub!. No. ORESU-T-75-0003,
Oregon State Univ. School of Oceanography, Nov. 1975.
Ozonation Equipment: An Alron Industries Model WP-4 ozone generator was fed
with dry oxygen to produce 0.5 to 0.75 g ozone/hr, which was dispersed
through a medium porosity glass frit into seawater which had been filtered
through an 0.8 u pore size Millipore filter. No data are given from which
ozone utilization can be calculated.
Procedure: Ozonized water was treated as follows:
1) aged at room temperature for up to 4 weeks (to allow ozone to
decompose)
2) ambient air was bubbled 1 week through 1 liter of ozonized seawater
3) ozonized seawater was vacuum filtered through an 0.8 u Millipore
filter
4) 20 mg/1 sodium EDTA solution was added to ozonized seawater (to
remove any heavy metals that may have been decomplexed by ozonizing
5) vacuum filtered through a 0.5 to 4 cm thickness of activated carbon
above the Mi Hi pore filter
6) gravity filtered through a column (2.5 cm diameter x 20 cm length)
containing 100 cc of charcoal granules. Several types of charcoal
were tested
7) autoclaved 5 min at 15 Ibs/sq in (1.0 kg/sq cm)
Bioassays were conducted in replicate. 150 freshly fertilized oyster
eggs (Crassostrea gigas) were placed in approximately 100 ml of treated
seawater, and the degree of toxicity determined by counting the number which
showed normal growth after 24 hrs. Control values above 80% indicated valid
bioassays.
Results: Ozonized seawater causes a long term residual toxicity to oyster
larvae. Allowing ozonized seawater to stand up to 4 weeks (so as to allow
ozone decomposition back to oxygen) did not reduce this toxicity. Neither
did bubbling air through ozonized seawaters. Treatment with EDTA removed
heavy metals, but had no effect on the residual toxicity. The only effective
treatment was filtration through activated carbon, but the effectiveness of
various types of charcoal was highly variable. Darco granular coconut
charcoal was found to have a toxicity of its own. Darco D-60 (20 to 40 mesh)
satisfactorily removed toxicity caused by ozonation.
-------
Ozonization appeared to be effective in enhancing the quality of seawater,
when the toxicity was removed by activated carbon.
AQ-19
Title: "Use of Ozone as a Sterilizing Agent in Seawater for the Depuration
of Shellfish"
Author: Y. Fauvel
Source: Intl. Commission for Scientific Exploration of the Mediteranean
Ocean, Reports and Verbal Proceedings 17(3):701-706 (1963).
Ozone depuration of shellfish was proposed in 1929, but was not used
industrially until the early 1960s.
Two lots of 200 kg of bacterially contaminated mussels were treated 24
hrs in each of 2 tanks (48 hrs total treatment). The concentration of mussels
in seawater was 5 kg/sq m. Bacterial contamination of mussel flesh and
intervalve liquid was determined. Initial flesh contamination of 45,000 to
60,000 coliforms/1 was reduced in 24 hrs to 600 to 2,400 and to zero in 48
hrs of depuration.
Similarly, 10 kg of clams were depurated in 300 1 of seawater at a
concentration of 30 kg of clams/sq m. At the time the clams were placed in
the tank, tissue pollution was 60,000 coliforms/1. The count had fallen to
18,000 after 24 hrs, to 3,000 after 48 hrs, and to zero after 72 hrs. In
the intervalve liquid, the coliforms/1 were 400 after 72 hrs. Depuration of
clams is slower than that of mussels.
Another 20 kg of clams were fished from unhealthy zones near SSte
(France) and held 48 hrs near sewer outfalls. They were then divided into 2
lots, each placed in a 300 1 container and stored in chlorinated seawater and
in ozonized seawater. At the start, tissue coliform counts were 120,000/1 in
both samples. Data obtained with time are listed in Table 2.
Thus depuration with ozonized seawater is preferred over chlorinated
seawater, because depuration is attained faster. In addition, shellfish
depurated in ozonized seawater retain their original taste, whereas those
treated in chlorinated water appear soft and chewey. Finally, no detrimental
health effects were observed in shellfish treated in ozonized seawater.
10
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TABLE 2. DEPURATION OF CLAMS IN OZONIZED SEAWATER
days
exposure
start
48 hrs
72 hrs
4 days
5 days
5 days
5 days
tissue coliform counts
chlorinated
water
120,000 col i forms/1
90,000
60,000
24,000
1,200
400*
20 dead individuals
* interval ve liquid coliform counts
ozonized
water
120,000 coliforms/1
90,000
6,000
1 ,800
0
100*
8 dead individuals
AQ-30
Title: "Effects of Ozone-Treated Seawater On The Spawned, Fertilized
Meiotic and Cleaving Eggs Of The Commercial American Oyster"
Authors: S.A. MacLean, C. Longwell & W.J. Blogoslawski
Source: Mutation Research 21:283-285 (1973).
Discusses a number of adverse effects which appear to be caused by
residual ozone and/or its decomposition products upon eggs of the commercial
American oyster. Seawater was passed through 2 Dyne! filters to remove
parti oil ate matter larger than 15 y in diameter. A portion of the water was
then ozonized at 30 SCFH in a 15 liter bucket for 3 min (2% ozone-air mixture).
The ozone-treated water was allowed to stand in the open bucket for 2 hrs
during which time the ozone residual level decreased to approximately 0.18
mg/1.
Eggs were held in treated and control water up to 2 hrs at which time
the last cytological fixation was made. Results are summarized in Table 3.
Unfertilized eggs spawned by the same female in the control and in
treated water showed no cytological diffs. Fertilization occurred less
readily in the treated water, as evidenced by a decrease in polyspermy and an
increase in parthenogenesis. This is also indicated by the larger number of
eggs (more than double) retarded in their completion of meiosis, the increased
incidence of abnormal polar bodies in eggs held in the ozonized water (more
than triple the number of eggs), and the larger numbers of cleaving eggs with
abnormal nuclei (more than double). These nuclei showed signs of metabolic
difficulties or of degeneration, and were pycnotic, pale, diffuse, or even
fragmented. The background incidence of abnormalities in the control sample
is not atypical for this invertebrate.
11
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TABLE 3. EFFECTS OF OZONIZED SEAWATER ON SPAUNED, FERTILIZED MEIOTIC AND
CLEAVING OYSTER EGGS
Effect or
Condition Scored
Polyspermy
Parthenogenesis
Retarded meiosis
& cleavage
Irregularity of
polar bodies
Abnormal cleavage
Total
Number of
Eggs
Observed
400
200
200
400
200
% of Eggs
Spawned,
Fertilized &
Held in
Control
Seawater
9.0
9.0
12.5
5.0
19.5
% of Eggs
Spawned,
Fertilized
& Held in
Ozone
Treated
Seawater
1.75
18.0
28.0
16.0
41.5
Ratio
0,/Control
0.2
2.0
2.2
3.2
2.1
The authors concluded that for ozonized seawater:
1. Additional work is necessary to clarify whether the effects are due to
ozone or to the by-products of its oxidation of impurities in the seawater.
2. The cytological and cytogenetic effects of ozone appear to be radiomimetic.
This may be due to the positive radical (OH*and H02") decomposition
products of ozone which are considered to be the biologically active
products of irradiation of protoplasm.
3. The presence of fragment nuclei indicate that there likely was some
chromosome breakage. This is in agreement with other investigations of
ozone damage to cells.
4-. The increased parthenogenesis and decreased polyspermy may be attributable
to the effect of ozone on the membranes of the oyster egg.
5. Such consequences of ozonization might be accepted knowledgeably along
with the benefits. Practical post-ozonation steps, such as carbon
adsorption, possibly could be developed to remove the offending substances.
A reservation stated by the authors is that "just how much residual
ozone and the products of its decomposition were present in the seawater by
the time the oyster eggs were spawned in it is uncertain."
AQ-34
Title: "A Depuration Station for Shellfish Using Ozonized Seawater"
Authors: J. Salmon, A. Salmon, J. LeGall and D. Loir
12
-------
Source: Ann. Hyg. 15:581-584 (1937)
Pathogenic bacteria which can cause typhoid fever do not remain in the
bodies of shellfish bathed in seawater. A prolonged residence time of shell-
fish in seawater allows progressive elimination of these bacteria. If the
seawater in which the shellfish are bathed (depurated) is also ozonized,
these pathogenic bacteria will be killed by the action of the ozone.
Tests are described of shellfish depuration at the cities of Havre and
of Boulogne-sur-Mer using ozonized seawaters. Shellfish to be cleansed are
placed in baskets in 2 or more superimposed beds. They are submerged and
rinsed with ordinary seawater which cleanses them of impurities adhering to
the outside of the shellfish. The baskets then are transported by conveyer
belt to a first cleansing tank where they are kept 24 hrs in ozonized seawater.
In this tank the molluscs clean entrained bacteria from their intestines.
The bacteria are killed by the action of ozone.
After 24 hrs of cleansing, a rinse in ozonized seawater completes the
first treatment. The baskets then are sent to a second sterilization tank
where they are kept until ready for packaging and shipment to market. The
following are the pertinent treatment parameters:
Av wt of shellfish (mussel) 7-10 g
No of mussels/1 100
Amount of ozonized water/mussel/hr 20 ml
Oysters and other shellfish have different filtration coefficients, thus
these conditions should be modified.
The system at Havre cleanses 2,000 kg/day of shellfish; that at Boulogne-
sur-Mer cleanses 6,000 kg/day.
An Otto ozone generator is used at each station, but dosages and contact
times for the ozonation are not described.
AQ-35
Title: "Preliminary Note on Several Experiments of Purifying Edible Marine
Molluscs by Ozonized Seawater"
Authors: J. Salmon, J. Le Gall and A. Salmon
Source: Ann. Hyg. Publique, Industrielle et Sociale 15:44-50 (1937)
Preliminary tests made at the zoological station of Wirmereux are
described. An Otto plate type ozone generator, Model 102, generating 500
1/hr of ozonized air was employed, but the contacting and ozone contact times
and doses are not described. Ozonation was intermittent, not continuous.
13
-------
Oysters, mussels and other varied local shellfish were subjected to
bacterial analyses, then were stored in ozonized seawaters for varying
lengths of time, then analyzed again.
First pathogenic bacteria, then coliforms, then coli-bacillus disappear
on exposure (depuration) of shellfish in ozonized water. The minimum time
for depuration was not determined exactly, but is less than 4 days exposure.
Mussels were depurated in 24 hrs maximum. Oysters and other shellfish stored
48 hrs in freshly ozonized seawater showed complete destruction of all patho-
genic bacteria. Addition of ozonized seawater did not create any noxious
substance for treated molluscs; no change in health of the molluscs was
observed.
Article 16 of the Decree of 31 July 1923 (France) required that contami-
nated shellfish cannot be released to the public until after they have stayed
1 month in a depuration establishment. Since use of ozonized seawater can
reduce this holding time to 24 to 48 hrs, the practical benefits of using
ozone can be of great economic significance.
AQ-43
Title: "Sterilization of Seawater with Ozone: Application of This
Method to the Purification of Contaminated Shellfish"
Author: H. Violle
Source: Rev. Hyg. et de Med. Preventive 51:42-46 (1929)
Reports a laboratory study to determine the effects of ozonized seawater
to purify oysters. Samples of seawater, fresh water and distilled water (the
latter 2 containing chloride, bromide and iodide in the same quantities as in
seawater) were seeded with pathogenic bacteria (B. typhus, B^. coli, B_.
proteus, B_. pyocaneus, cholera vibrio, B_. dysenteria) and the samples ozonized
to determine the ozone dosages just necessary to attain disinfection. This
dosage was the same in all cases (not given, but stated to be the same as for
fresh water, which is 1 to 3 mg/1), and no oxidation of bromide was observed
even at double the amount of ozone necessary to produce disinfection.
Oysters were kept 18 to 20 days in ozonized seawater using twice the
ozone necessary for disinfection. The ozonized seawater was aerated to
remove excess ozone. A second batch was kept in seawater. After 5 to 6 hrs
the oysters in the ozonized water were free of bacteria. After 18 to 20 days
exposure to ozonized water, there was no change in the oyster protoplasm.
Quantities of ozonized water used were 1 l/oyster/24 hrs, or 83 ml/
oyster/hr, or 30 1/15 days/oyster, or 8,300 l/hr/10,000 oysters, or 14
1/min.
14
-------
The ozone generator used was an Otto plate type unit. Neither the
contacting apparatus, nor the ozone dosages, nor contact time were given.
The recommended depuration process consists of rapid sand filtration of
seawater, ozonation, aeration, and flow through at the rate of 100 ml/hr/oyster.
15
-------
LITERATURE CITED -- BIOFOULING CONTROL (BF)
BF-01 Blogoslawski, W.J. & M.E. Stewart, 1976, "Marine Applications of
Ozone Water Treatment", in Forum on Ozone Disinfection, E.G.
Fochtman, R.G. Rice & M.E. Browning, editors, Intl. Ozone Assoc.,
Cleveland, Ohio, p. 266-276.
BF-02 Chase, R.E., 1975, "The Federal Water Pollution Control Act Amend-
ments of 1972 -- PL 92-500 -- As It Relates to the Steam Electric
Power Generating Industry", in Aquatic Applications of Ozone, W.J.
Blogoslawski & R.G. Rice, editors, Intl. Ozone Assoc., Cleveland,
Ohio, p. 177-186.
BF-03 Garey, J., 1975, "Ozone For Anti-Fouling Control", presented at
Workshop on Assessment of Technology and Ecological Effects of
Biofouling Control Procedures at Thermal Power Plant Cooling Water
Systems, Baltimore, Md., June 16-17. Electric Power Research
Inst., Palo Alto, Calif.
BF-04 Garey, J., 1977, "A Comparison of the Effectiveness of Ozone and
Chlorine in Reducing Slime Growth Within the Condensers of an
Electric Generating Station Using Seawater as a Coolant", in Forum
on Ozone Disinfection, E.G. Fochtman, R.G. Rice & M.E. Browning,
ecTitors, Intl. Ozone Assoc., Cleveland, Ohio, p. 277-283.
BF-05 Helz, G.R., R.Y. Hsu & R.M. Block, 1978, "Bromoform Production by
Oxidative Biocides in Marine Waters", in Ozone/Chlorine Dioxide
Oxidation Products of Organic Materials, R.G. Rice & J.A. Cotruvo,
editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 68-76.
BF-06 Mangum, D.C. & W.F. Mcllhenny, 1975, "Control of Marine Fouling in
Intake Systems - A Comparison of Ozone and Chlorine", in Aquatic
Applications g_f Ozone, W.J. Blogoslawski and R.G. Rice, editors,
Intl. Ozone Assoc., Cleveland, Ohio, p. 138-153.
BF-07 Manning, G.B. & A.A. Bacher, 1975, "Ozone and the Steam Electric
Power Industry", in Aquatic Applications of Ozone, W.J. Blogo-
slawski and R.G. Rice, editors, Intl. Ozone Assoc., Cleveland,
Ohio, p. 161-176.
BF-08 Senguta, C., G. Levine, E.G. Wackenhuth & C.R. Guerra, 1975, "Power
Plant Cooling Water Treatment With Ozone", in Aquatic Applications
o£ Ozone, W.J. Blogoslawski & R.G Rice, editors, Intl. Ozone Assoc.,
Cleveland, Ohio, p. 119-137.
BF-09 Senguta, C. & R. Chakravorti, 1975, "Power Plants and Biofouling",
Discussion, Workshop No. 4, in Aquatic Applications of Ozone, W.J.
Blogoslawski & R.G. Rice, editors, Intl. Ozone Assoc., Cleveland,
Ohio, p. 215-226.
16
-------
BF-10 Siegrist, H.W., D.G. Tuttle & S.B. Majumdar, 1975, "Technical and
Economic Considerations of Biocide System Options for Cooling Water
Systems: A Review", in Proc. Sec. Intl. Symp. on_ Ozone Technol.,
R.G. Rice, P. Pichet & M.-A. Vincent, editors, Intl. Ozone Assoc.,
Cleveland, Ohio, p. 632-649.
BF-11 Toner, R.C. & B. Brooks, 1975, "The Effects of Ozone on Four Species
of Phytoplankton, Crab Zoea and Megalops and the Atlantic Silverside,
Menidia Menidia," in Aquatic Applications of Ozone. W.J. Blogoslawski
& R.G. Rice, editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 154-
160.
BF-12* Yu, H.H.S., G.A. Richardson & W.H. Medley, 1977, "Alternatives to
Chiorination for Control of Condenser Tube Bio-Fouling", EPA
Report No. EPA-600/7-77-030, March. U.S. Environmental Protection
Agency, Industrial Environmental Research Lab., Research Triangle
Park, North Carolina 27711. NTIS No. PB-266,269.
BF-12
Title: "Alternatives to Chlorination for Control of Condenser Tube Bio-
Fouling
Authors: H.H.S. Yu, G.A. Richardson & W.H. Hedley
Source: U.S. EPA Report i EPA/600/7-77-030 (March, 1977). Natl. Tech. Info
Service, Report # PB-266.269/OWP.
Reports a study of methods used to lower free chlorine residuals in
power plant effluents. Most U.S. power plants use chlorine (28,600 tons in
1972) to control biological fouling in their cooling systems, particularly in
their condenser tubes. Using chlorine raises many questions regarding the
toxicity of chlorinated compounds which may enter public drinking water
systems or harm aquatic organisms in the receiving waters. The report
considers viable alternatives to current chlorination practices used to
decrease passage of ecologically harmful effluents to receiving waters.
Alternative methods include: use of other chemicals (BrCl, C102, ozone,
controlled release pesticides); more efficient methods of chemical application
(serial dosing near the condenser inlet, adding dechlorination chemicals,
blowdown timing control, chlorination by residuals feedback control); on-line
mechanical cleaning (sponge ball system, brush system, hot water backflush
system); and physical/chemical treatment. Information on advantages, disadvan-
tages, costs and applicability for retrofit or new installations of these
methods is presented. Promising approaches to reducing free chlorine residuals
in power plant effluents are available.
17
-------
LITERATURE CITED — CYANIDES AND CYANATES (CY)
CY-01 Anonymous, 1974, Mitsui Shipbuilding Tech. Review 85:42-48 (Jan).
CY-02* Bahensky, V. & Z. Zika, 1966, "Treating Cyanide Wastes by Oxidation
with Ozone." Koroze Ochrana Materialu 10(1):19-21. Chem. Abstr.
65:6907c (1966).
CY-03* Balyanskii, G.V., M.E. Selin & V.B. Kolychev, 1972, "Ozonation of
Simple Cyanides in Water." Zhurnal Prikladnoi Khimii (J. Applied
Chem.) 45(10):2152-2156.
CY-04* Besselievre, E.H., 1957, "The Economical and Practical Use and
Handling of Chemicals Used in Industrial Waste Treatment", in
Proc. 12th Indl. Waste Conf., 342-363 (publ. 1958), Purdue Univ.,
Engrg. Bull. Ext. Serv. No. 94.
CY-05 Des Rosiers, P.E. & H.S. Skovronek, 1975, "The EPA Program and
Industrial Advanced Wastewater Treatment Needs—Ozone", in Proc.
1st Intl. Symp. 011 Ozone for Water &_ Wastewater Treatment, R.G.
Rice & M.E. Browning, editors, Intl. Ozone Assoc., Cleveland, Ohio,
p. 500-521.
CY-06 Diaper, E.W.J., 1972, "Ozone Moves to the Fore", Water & Wastes
Engrg., May, p. 65-69.
CY-07 Eiring, L.V., 1969, "Kinetics and Mechanism of Ozone Oxidation of
Cyanide-Containing Waste Water." Tstel Metal (USSR), 73-76.
CY-08* Fabjan, C. & R. Davies, 1976, "Decontamination with Ozone of Sewage
Containing Cyanide", Wasser, Luft & Betrieb 20(4):175-178. Chem.
Abstr. 85:148426u.
CY-09 Fabjan, C. & R. Davies, 1970-1977, "Die Reinigung Galvanischer und
Anderer Abwasser nach dem Ozonizieren Verfahren", U.S. Dept. of
Commerce, NTIS Report No. PS-77/0749.
CY-10* Fujisawa, T., Y. Matsuda, Y. Takasu, Y. Tanaka & H. Imagawa, 1973,
"On the Ozone-Oxidation Treatment of Sewage Containing Cyanide or
Cyanate." XXXI. Semi-Annual Autumn Mtg. of the Japanese Chemical
Soc., Lecture 131, Oct.
CY-11 Guillerd, J. & C. Valin, 1961, "Traitment par 1'Ozone", TEau,
May.
CY-12 Garrison, R.L., C.E. Mauk & H.W. Prengle, Jr., 1974, "Cyanide
Disposal by Ozone Oxidation". Final Report, U.S. Air Force Weapons
Lab., Kirtland Air Force Base, New Mexico, Feb. Report No. AFWL-
TR-73-212, U.S. Dept. of Commerce, NTIS Report No. AD-775,152/2WP.
18
-------
CY-13 Ikehata, A., 1975, "Treatment of Municipal Wastewater by the Use of
Ozone to Yield High Quality Water", in Proc. 1st Intl. Symp. oil
Ozone for Water & Wastewater Treatment., R.G.~RTce & M.E. Browning,
editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 227-231.
CY-14 Ishizaki, K., R.A. Dobbs & J.M. Cohen, 1978, "Ozonation of Hazar-
dous and Toxic Organic Compounds in Aqueous Solution", in Ozone/-
Chlorine Dioxide Oxidation Products of Organic Materials, R.G. Rice
& J.A. Cotruvo, editors. Intl. Ozone Assoc., Cleveland, Ohio, p.
210-226.
CY-15 Kandzas, P.P. & A.A. Mokina, 1968, "Use of Ozone for Purifying
Industrial Wastewaters." Trudy Vses. Nauchno-Issled. in-ta Vodosnabzh.,
Kanaliz., Gidrotekh. Soouzhenii Imzh. Gidrogeol, 20:40-45. Chem.
Abstr. 71:6388v (1969).
CY-16* Khandelwal, K.H., A.J. Barduhn & C.S. Grove, Jr., 1959, "Kinetics
of Ozonation of Cyanides", in Ozone Chem. & Techno!., Adv. in Chem.
Series No. 21, Am. Chem. Soc., Washington, O.C. p. 78-86.
CY-17 Kolthoff, I.M. & V. Stenger, 1947, Volumetric Analysis. Vol. II,
Interscience Publishers, New York, N.Y., p. 267.
CY-18 Kubo, A. & M. Nagata, 1974, "Highly Advanced Treatment of Water
Treated by Activated Sludge Process Effluent of Gas Liquor."
(Journal unknown)., Jan.
CY-19* Mathieu, G.I., 1973, "The Film Layer Purifying Process for Cyanide
Destruction", Canadian Mining J., June, p. 3-4.
CY-20 Mathieu, G.I., 1975, "Application of Film Layer Purifying Chamber
Process to Cyanide Destruction—A Progress Report," in Ozone for
Water & Wastewater Treatment, R.G. Rice & M.E. Browning, editors,
Intl. Ozone Assoc., Cleveland, Ohio, p. 533-550.
CY-21 Mathieu, G.I., 1977, "Ozonation for Destruction of Cyanide in
Canadian Effluents - A Preliminary Evaluation", Canada Centre for
Mineral and Energy Tech., Ottawa, Canada, CANMET Report 77-11.
Presented at Symp. on Advanced Ozone Technology, Toronto, Ontario,
Canada, Nov. 1977. Intl. Ozone Assoc., Cleveland, Ohio.
CY-22 Matsuoka, H., 1973, "On the Ozone Treatment of Industrial Sewage",
PPM 4(10):57-59.
CY-23 Neuwirth, F., 1933, Berg-u HUttenmann. Jahrb. Montan. Hochschule
Loeben, 81:126-131.
CY-24 Reznick, J.D., W.A. Moore & M.B. Ettinger, 1958, "Behavior of
Cyanates in Polluted Water", Indl. Engrg. Chem. 50(1):71-72.
CY-25 Sondak, N.E. & B.F. Dodge, 1961, "The Oxidation of Cyanide-Bearing
Plating Wastes by Ozone, Part 1", Plating, p. 173-180.
19
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CY-26 Sondak, N.E. & B.F. Dodge, 1961, "The Oxidation of Cyanide-Bearing
Plating Wastes by Ozone, Part 2", Plating, p. 280-284.
CY-27* Zumbrunn, J.P., 1971, "Produits et Proc§des--Epuration des Eaux
Residuaires Cyanurees." Chimie et Industrie. Genie Chimique
104(20):2573-2584.
CY-02
Title: "Treating Cyanide Wastes by Oxidation with Ozone."
Authors: V. Bahensky & Z. Zida
Source: Koroze Ochrana Materialu, 10(1):19-21 (1966). Chem. Abstr.
65:6907c (1966).
The effect of Cu (as a catalyst) and pH on the oxidation of cyanides
with ozone was investigated. CuCN and CuK(CN)p were oxidized rapidly, and
the oxidation of NaCN, KCN, Zn(.CN)2, and Cd(CN)2 was catalyzed with Cu 5 to
15 mg/1. The most suitable pH of the solutions for the oxidation was 10 to
11, because at lower pH HCN is liberated. A 500 mm column containing CN
absorbed ozone satisfactorily. The method is suitable for treating cyanide
wastes of higher concentration (minimum 100 mg/1).
CY-03
Title: "Ozonization of Simple Cyanides in Water."
Authors: G.V. Balyanskii, M.E. Selin & V.B. Kolychev
Source: Zhurnal Prikladnoi Khimii (Journal of Applied Chemistry)
45(10):2152-56 (1972).
Review: A study of the reaction of cyanide oxidation by ozone and of kinetic
parameters. Data are presented, from which a schematic representation of the
oxidation reaction is developed. CN ions are oxidized most rapidly, forming
CNO ions, which are, in turn, oxidized to nitrate ions, and to carbonate and
nitrogen. Overall consumption of ozone for the oxidation of CN ions to the
final products under the experimental conditions was 5.8 to 6.0 moles/mole.
The oxidation rate of CN and CNO ions conformed to a first-order equation
with respect to these ions. The process was controlled by diffusion. The
average value of the rate constant for the oxidation of CN ions (unit specific
interfacial area) was 0.803/min; for CNO ions it was 0.157/min.
Contactor: In a thermostatic reactor (glass cylinder, 32 mm diameter and 400
mm height), 250 to 300 ml of a KCN-water solution were combined with the
ozone-gas mixture at zero reaction time. At intervals its content was deter-
mined for CN, CNO, N03" ions and ozone content.
20
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Ozone Generator; Not described.
References: 16
CY-04
Title: "The Economical and Practical Use and Handling of Chemicals Used
in Industrial Waste Treatment."
Author: E. H. Besselievre
Source: Proc. 12th Industrial Waste Conf., 1957, 342-63, Publ. 1958).
Purdue Univ. Engr. Bull, Ext. Serv., No. 94, Lafayette, Indiana.
Review: Lime, chlorine and chlorine-containing compounds, sulfur dioxide and
ozone treatment for industrial wastes were analyzed from an economic point of
view. Ozone costs were determined for the treatment of CN-containing wastes.
Economics: For daily wastes with a CN content of 160 Ibs/day, the theoretical
chlorine demand (1092.80 Ibs/day) plus operating costs were estimated to
total $130.25/day (1957 prices). Equipment for ozone generation (360 Ibs/day)
and use were estimated at an initial cost of $165,000. Using 2 Ibs ozone/lb
of cyanide, and with 13 kwhr of current needed to produce 1 Ib of ozone,
total daily costs are $111.46.
An alternative method, the use of "metered ozone", was studied. With
the same ozone demands as above, charges paid to the owner of the ozone
process equipment were determined to be $151.36/day. If 2000 Ibs of cyanide/-
day were to be treated, 4000 Ibs of ozone at 17.5<£/lb would total $560.00.
Comparable costs for chlorine use (7<£/day) would be $1120/day.
CY-08
Title: "Decontamination with Ozone of Sewage Containing Cyanide".
Authors: C. Fabjan & R. Davies
Source: Wasser, Luft & Betrieb 20(4):175-178 (1976). Chem. Abstr.
85:148426u.
The oxidation of CN~ and complex metallic cyanides with ozone in an
alkaline medium is catalyzed by transition metal ions and is the basis of a
treatment for wastewater containing CN" and its complexes. By using a packed
column and a countercurrent flow for the wastewater and ozone,_the oxidation
reaction was studied as a function of the concentrations of CN" in the waste-
water, of the ozone in the inlet gas and of the characteristics of the packed
column. The concentration of ozone in the outlet gas also was determined and
related to the parameters influencing the oxidation reaction. During waste-
water treatment it was necessary to remove the heavy metal hydroxide sludge
21
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formed, because the sludge catalytically decomposed the ozone with a concomi-
tant loss of the oxidizing agent. Based on the results obtained, plant
design criteria are presented, and procedures are suggested for a continuous
operation and for automation of the plant.
CY-10
Title:
"On the Ozone-Oxidation Treatment of Sewage Containing
Cyanide or Cyanate."
Authors: T. Fugisawa, Y. Matsuda, Y. Takasu & Y. Imagawa, II.,
Source: IXXX Seminannual Autumn Meeting of the Japanese Chemical
Society, Lectures, p. 131, October 1973.
Solutions initially containing 350 mg/1 of CN and 3 mole/1 of CNO,
respectively, obtained by dissolving pure KCN and KCNO, were reacted with a
mixture of ozone and oxygen at 8.4 to 17.3 mg ozone/1 in various states of pH
controlled by adding NaOH. The reaction of CNO and ozone in alkaline solution
followed the equation, v = K[OH~][03L and that CNO ion was oxidized to
nitrogen.
CY-16
Title: "Kinetics of Ozonation of Cyanides."
Authors: Khandelwal, K.K., A.J. Barduhn & C.S. Grove, Jr.
Source: Ozone Chemistry & Technology, Advances In Chemistry Series, Vol. 21,
American Chemical Society, Washington, O.C., 78-86.
Review: The rate of ozonation of an aqueous KCN solution was determined
under controlled conditions using a packed tower and a bottle sparger as
contactors. The effects of the following variables on the reaction rate were
considered:
1) Cu(II) concentration from Cu sulfate. Addition of Cu(II) ions more than
doubled the rate of decomposition of cyanides. Increasing the Cu(II)
concentration did not markedly increase this further.
2) Cu(II) from other salts—cupric chloride, nitrate, acetate and sulfate.
The presence of various anions had no effect on the reaction rate constant.
3) The manner in which ozone and cyanide interact—reactor bottle or
packed column. There was no marked difference in the reaction rate
constants, although that of the packed tower was slightly lower than
that of the bottle. The controlling factor was the rate of reaction
with CN. The rate of dissolution of ozone was very fast compared to the
rate of its reaction with cyanide.
22
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4) Cii(II). Ni(II), Mn(II), and Cd(II) sulfate. Cu(II) gave the highest
rate constant (K = 2.20), followed by Ni(II) (K = 11.50), Mn(II) (K =
1.33) and Cd. The rate constant for Cd was nearly the same as for the
uncatalyzed reaction (K = 0.95).
5) Solution temperature over 13°C to 30°C did not substantially affect the
rate constant.
Ozone Generator: A Welsbach T23 Model laboratory ozone generator produced
ozone from cylinder oxygen.
Contactor: Batch reactions were done in 2 types of reactors—a 1,500 ml
packed tower and a 1,500 ml borosilicate glass bottle. Nearly all runs were
conducted at 20° C with the pH maintained at 11.3 ± 0.5.
Economics: No cost assessments were made.
References: 9
CY-19
Title: "The Film Layer Purifying Process for Cyanide Destruction."
Author: G.I. Mathieu
Source: Canadian Mining J., June, 1973, 3-4.
Review: An explanation of the FLPC (Film Layer Purifying Chamber)
contacting system.
Process: FLPC basically is the conventional ozone contact system in reverse.
The aqueous solution is atomized and sprayed into a concentrated atmosphere
of ozone and oxygen. This produces rapid oxidation (about 12 sec/reactor).
The oxidized liquid is passed through an electric coagulator which removes SS
and precipitates metal hydroxides. This is followed by sedimentation.
Discussion: Best results occurred with high concentrations of cyanides at a
cost of 5 to 7 (t/1,000 gal of 50 mg/1 CN. Also discusses methods of reducing
cost and improving efficiency. 91% to 97% of the CN was decomposed in less
than 2 min using synthetic CN wastes.
References: None.
CY-27
Title: "Purification of Wastewaters Containing Cyanides"
Author: J.P. Zumbrunn
23
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Source: Chemie et Industrie - Genie Chemique 104(20):2573-2584 (1971).
Reviews methods of treating cyanides. Ozonation is mentioned only and no
experiments with ozone are described.
For conversion of CN to nitrogen and COg, excess ozone is required and
the pH must be very alkaline.
CN"+ 03 -»• (CNO)~ + 02
or:
2(CN)~ + 503 + 2NaOH -»• 2(NaHC03)~ + N2 + 502 + H20
References: 14
24
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LITERATURE CITED -- ELECTROPLATING (EP)
EP-01* Anonymous, 1958, "Ozone Counters Waste Cyanides Lethal Punch",
Chem. Engr., March 24, p. 63-64.
EP-02 Anonymous, 1974, "Ozonation: Another Way to Treat Plating Wastes",
Prod. Finish 38:10, 98; Engrg. Index Monthly 12:049085 (1975).
EP-03 Anonymous, 1975, French Patent, FR 2,265,691 (Nov. 28). Derwent
French Patent Abstracts x(3):D5, Feb. 1976.
EP-04 Bollyky, L.J., 1975, "Ozone Treatment of Cyanide and Plating Waste",
in Proc. 1st Intl. Symp. on_ Ozone for Water ^ Wastewater Treatment,
R.G. Rice & M.E. Browning, editors, Intl. Ozone Assoc., Cleveland,
Ohio, p. 587-590.
EP-05 Bollyky, L.J., C. Balint & B. Siegel, 1976, "Ozone Treatment of
Cyanide and Plating Waste on a Plant Scale", in Proc. Sec. Intl.
Symp. on Ozone Techno]., R.G. Rice, P. Pichet & M.-A. Vincent,
editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 393-420.
EP-06* Bollyky, L.J., 1977, "Ozone Treatment of Cyanide-Bearing Plating
Waste", EPA Report No. EPA-600/2-77-104, June. U.S. Environmental
Protection Agency, Industrial Environmental Research Lab., Cincinnati,
Ohio 45268.
EP-07* Browning, M.E., 1976, "Wastewater Treatment in the U.S.A", Galvano-
technik 67(6):465-470.
EP-08 Cheremisinoff, P.N., A.J. Perna & J. Ciancia, 1977, "Treating Metal
Finishing Wastes, Part 2", Indl. Wastes Jan/Feb, p. 32-34.
EP-09* Ciancia, J., 1973, "New Waste Treatment Technology in the Metal
Finishing Industry." Plating 60:1037.
EP-10 Ellerbusch, F. & H.S. Skovronek, 1977, "Oxidation Treatment of
Industrial Wastewater", Indl. Water Engrg., Sept., p. 20-29.
EP-11* Fabjan, C., 1975, "Purification of Electroplating and Other Effluent
Waters by the Ozone Process." Galvanotechnik 66(2):100-107.
EP-12 Fabjan, C., R. Davies & K. Marschall, 1970-1977, "Destruction of
Complexing Agents in Electroplating and Other Effluents by Ozone",
U.S. Dept. of Commerce, NTIS Report No. PS-77/0749, p. 643-645.
EP-13* Garrison, R.L., C.E. Mauk & H.W. Prengle, Jr. 1974, "Cyanide Disposal
by Ozone Oxidation." Final Report, U.S. Air Force Weapons Lab.,
Kirtland Air Force Base, New Mex., Feb., #AFWL-TR-73-212, U.S.
Dept. of Commerce, NTIS Report No. AD-775.152/2WP.
25
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EP-14 Garrison, R.L., C.E. Mauk & H.W. Prengle, Jr., 1975, "Advanced
Ozone Oxidation System for Complexed Cyanides." In Proc. 1st Intl.
Symp. on Ozone for Water & Wastewater Treatment, R.G. Rice & M.E.
Browning, editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 551-577.
EP-15* Garrison, R.L., H.W. Prengle, Jr. & C.E. Mauk, 1975, "Ozone-based
System Treats Plating Effluent." Metal Progress 108(6):61-62.
EP-16* Goldstein, M., 1976, "Economics of Treating Cyanide Wastes",
Pollution Engineering, March, p. 36-38.
EP-17* Ikehata, A., K. Ishizaki, N. Tabata & R. Hashimoto, 1972, "Oxida-
tion of Cyanides in Plating Wastes by Use of Ozone." J. Japan Soc.
for Safety Engr. II (2):74-84.
EP-18 Klingsick, G., 1975, "Application of Ozone at the Boeing Co.,
Wichita, Kansas", in Proc. 1st Intl. Symp. on Ozone for Water &
Wastewater Treatment, R.G. Rice & M.E. Browning, editors, Intl.
Ozone Assoc., Cleveland, Ohio, p. 587-590.
EP-19 Kubala, F., 1964, "Regeneration of Chromium Bath with Ozone",
Korose A Ochrana Materialu.
EP-20 Morquardt, K., 1973, "Treatment of Wastewater in the Metal Working
Industry", Belg. Ned. Tijdschr. Oppervlakte Tech. Metal 16:306.
Chem. Abstr. 81:63529 (1974).
EP-21 Pinner, W.L., 1952, "Progress Report of Am. Electroplaters Soc.
Research Projects on Plating Room Waste", in Proc. 7th Indl. Waste
Cpjvf., Purdue Univ. Engr. Ser. 79:518-540.
EP-22 Prengle, H.W., Jr., 1977, "Evolution of the Ozone/UV Process for
Wastewater Treatment", Presented at Seminar on Wastewater Treatment
& Disinfection with Ozone, Cincinnati, Ohio, Sept. 15. Intl. Ozone
Assoc., Cleveland, Ohio.
EP-23* Selm, R.P., 1959, "Ozone Oxidation of Aqueous Cyanide Waste Solu-
tions in Stirred Batch Reactors and Packed Towers." In Ozone Chem.
& Techno!., Am. Chem. Soc., Adv. in Chem. Series, Vol. 21:66-67.
EP-24* Serota, L., 1958, "Science for Electroplaters 33. Cyanide Waste
Treatment—Ozonation and Electrolysis", Metal Finishing, Feb., p.
71-74.
EP-25* Sondak, N.E. & B.F. Dodge, 1961, "The Oxidation of Cyanide-Bearing
Plating Wastes by Ozone, Part 1", Plating, p. 173-180.
EP-26 Sondak, N.E. & B.F. Dodge, "The Oxidation of Cyanide-Bearing
Plating Wastes by Ozone. Part 2", Plating, p. 280-284.
26
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EP-27* Trejtnar, J., 1974, "Ozonization as a Means of Wastewater Purifi-
cation", Czechoslovak Heavy Industry 10:34-35.
EP-28 Tyler, R.G., W. Maske, M.J. Westing & W. Mathews, 1951, Sewage &
Indl. Wastes 23:1150-1153.
EP-29* Walker, C.A. & W. Zabban, 1953, "Disposal of Plating Room Wastes
VI. Treatment of Plating Room Waste Solutions with Ozone", Plating,
p. 777-780.
EP-01
Title: "Ozone Counters Waste Cyanide's Lethal Punch"
Author: Anonymous
Source: Chemical Engineering, March 24, 1958, p. 63-64
Describes the Boeing Aircraft (Wichita, Kansas) wastewater treatment
facility serving the metal working plant.
Cyanide content in the 500 gpm influent ranges from 0.0 to 25 mg/1.
Plant wastes first undergo oil separation, S02 reduction of chromates,
alkaline precipitation of heavy metals and clarification. Treated wastes (at
pH 9) pass through a contact tower packed with Intalox saddles, running
countercurrent to air containing 1% ozone.
Liquid flow rate is 20,000 Ibs/sq ft/hr; total air flow rate is 120 cu
ft/min. Liquid effluent from this tower is acidified to pH 7 (carbonation),
clarified, then passed through a second packed column countercurrent to the
gaseous flow from the first tower, which still contains some ozone.
This double pass technique ensures complete oxidation of cyanide to
cyanate and beyond, and also removes any excess SO? present from the chromate
step. After ozonation, cyanide content of the effluent is below the limit of
detection (0.1 mg/1).
Ozone Generators: Two 60 Ib/day (from air feed) Welsbach generators.
Costs: For 120 Ibs/day: $70,000 installed (about $600/lb of ozone generation
capacity) including auxiliaries; operating costs: 14 to 15$/lb of ozone
(1958 prices).
Ozone is considered to be cost-effective over chlorine when the accesso-
ries needed to support chlorination (large detention basins, facilities for
chemicals handling and storage, a gas-tight room for chlorinators), railway
spurs for moving chlorine cylinders, dechlorinating equipment, etc.) are
considered. Also, chlorination of cyanide produces 8 to 15 parts of chloride/-
part of CN eliminated, and this fact must be considered in discharge of
treated effluents.
27
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EP-06
Title: "Ozone Treatment of Cyanide-Bearing Plating Waste"
Author: L. J. Bollyky
Source: EPA Report No. EPA-600/2-77-104, June, 1977. U.S. Environmental
Protection Agency, Industrial Environmental Research Laboratory,
Cincinnati, Ohio.
A plating waste treatment plant was installed at the Sealectro Corp,
Mamaroneck, New York, to demonstrate the effectiveness of ozone treatment for
the oxidative destruction of cyanides and cyanates and for the removal of Cu
and Ag oxides on a full plant scale. The treatment process was designed to
treat wastewaters from Cu, Au and Ag plating operations. A 9-month study was
carried out to evaluate the effect of process parameters, to identify and
optimize key parameters, to establish capital and operating costs, and to
produce an effluent meeting current discharge standards.
Wastewaters: The Sealectro plant plates about 2.6 sq m/hr (1200 amps capacity)
and produces 2 wastewaters: an acid wastewater (16 gpm, with surges to 24.6
gpm), containing Ni up to 14 mg/1, Sn up to 10 mg/1 and Pb up to 0.08 mg/1;
and an alkaline CN wastewater (6.75 gpm, with surges to 10.4 gpm), containing
up to 60 mg/1 CN, up to 32 mg/1 Cu and up to 3.4 mg/1 Ag. The combined flow
averages 34 gpm, with surges up to 50 gpm.
Process: Alkaline CN wastewater is ozonized and the ozonate sent to a flash
mixing tank where it is mixed with the acid wastewater stream. The pH is
adjusted by addition of caustic or sulfuric acid (controlled by pH monitor),
then discharged to a settling tank (50 min retention time). The clear effluent
is discharged to the sewer system.
Ozone Generator: A 20 Ib/day (from air) PCI Ozone Corp. generator which can
be fitted with an auxiliary air blower to increase production to 26 Ibs/day.
Contactor: A cylindrical, 2-compartment fiberglass tower 5.6 m (18.5 ft)
tall and 0.8 m (30 inches) in diameter. Total volume 2,250 liters (600 gal).
In the lower compartment are porous tube spargers for treating the alkaline
CN-containing wastewater. In the smaller, upper compartment, off-gases from
the lower compartment are reintroduced into the incoming alkaline wastewater,
and either are passed through a packed column (sprayed with incoming alkaline
CN-containing wastewater, or diffused into incoming wastewater. In this
manner nearly all ozone introduced is utilized. Vent off-gases from the
ozone contactor consistently contain <0.05 ppm (by volume) of ozone.
Results: The plant was designed in 1968 to meet the following local wastewater
discharge standards: pH 5.5-9.5, 65°C (max), Cu 3.0 mg/1, CNO 10.0, CN 1.0,
Ni 10.0, Ag 0.05, Cl 100.0 mg/1. To meet the current EPA BPTCA monthly
average heavy metal discharge standards (based on 80 1/sq m flow and 30 day
average maximum discharge rates): CN oxidizable by chlorine 0.1 mg/1, total
28
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CN 1.0, Cu 1.0, Fe 2.0, Pb 1.0, Ni 1.0, Ag 0.1, Sn 2.0, Zn 1.0, TSS 40.0
mg/1, pH 6.0-9.5 (average daily discharge). The plating plant uses 1,200
amps only for plating and falls under local discharge standards.
To meet the current discharge standards requires ozone dosages of 1.85
to 2.8 mg/1 of ozone per mg/1 of CN (1.0 to 1.5 mole ozone/mole CN) at an
initial alkaline CN wastewater pH of 7.0 to 9.5. Final effluent from the
settling tank has a pH of 9.0 to 9.5 and temperature of 14° to 20°C. The
effluent wastewater consistently contains 0.08 mg/1 CN, 6 mg/1 CNO, 1.7 mg/1
Cu, 0.4 mg/1 Ni and <0.1 mg/1 Ag. [CNO~] can be reduced even further by
additional ozone, but this is not required by the current discharge standard.
The amount of ozone required depends upon the initial [CN"]. Below 20
mg/1 of CN", the mole ratio of ozone/CN is 1:1 to reduce [CN~] to <0.1 mg/1.
Concentrations of 20 to 40 mg/1 CN" require 2:1 to obtain <1 mg/1 CN" and 3.6
to attain < 0.1 mg/1 CN". Above 50 mg/1 CN", a mole ratio of 1.33 ozone/CN
is required to obtain 0.52 mg/1 CN" in the effluent, but CNO" discharge
requirements are not met. The pH is not critical; the standards are met
consistently over the range of 7 to 13.
Plant scale studies of ozonation of NaCN solns showed that at mole
ratios of 2.65 ozone/CN, 97.6% of the CN was destroyed. Mole ratios of 4.3
removed 44.8% of the CNO and mole ratios of 14.0 removed 97% CNO.
For Cu cyanide solutions, 1 to 1.5 moles ozone/mole of CN reduces [CN"]
to <0.1 mg/1 at [CN~] up to 20 mg/1. As [CN~] increases to 75 mg/1, the mole
ratio of ozone/CN rises to 3.0 to meet the discharge standard.
Costs: The optimum treatment process (described above) operated 24 hrs/day
is estimated (capital + operating, 1975 prices, 15 yr amortization) to cost
$1.31/1,000 gal of combined plant wastewater. Capital investment for this
optimized system is estimated at $51,200. With increased ozone dosages (up
to 2 moles ozone/mole CN), plus the addition of flocculant or settling tubes
in the settling tank, the effluent water could be used to cool the ozone
generator or air conditioning equipment.
In 2 weeks of operation, only 1 to 2 kg of sludge is produced in the
settling tank.
EP-07
Title: "Wastewater Treatment in the USA"
Author: M.E. Browning
Source; Galvanotechnik 67(6):465-470 (1976)
Reviews wastewater treatment techniques for electroplating wastes in the
USA. Use of ozonation for destruction of cyanides and removal of heavy
29
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metals Is mentioned. Boeing Aircraft Co. has been using 55 to 160 kg/day of
ozone for cyanide destruction since 1957.
References: 29
EP-09
Title: "New Waste Treatment Technology in the Metal Finishing Industry."
Author: J. Ciancia
Source: Plating, October, 1973, 1037-42.
Review: Reviews current technologies in the treatment of plating wastes, one
of which is ozone. No experimental data are reported.
Oxidation of CN" to CNO" by ozone is rapid and practically instantaneous
in the presence of a trace of Cu, but oxidation of CNO" is slow. However,
hydrolysis can convert CNO" to ammonium ion.
Ozonation adds no salts or toxic constituents to the wastewater. The
U.S. EPA is sponsoring a full scale demonstration study (see EPA-600/2-77-104)
of the use of ozonation to destroy CN" in plating wastewaters to determine
the effectiveness of treatment and establish capital and operating costs of
the process.
References: 1.
EP-11
Title: "Purification of Electroplating and other Effluent Water by
the Ozone Process."
Author: C. Fabjan
Source: Galvanotechnik 66(2):100-107 (1975)
Review; Reviews various uses of ozone for purification of galvanic and other
wastewaters. Ozone was efficient in the detoxification of CN-containing
galvanic wastewater, reaching with CN" to form CNO". The CNO" was further
hydrolyzed to C02 and Nfy at low pH values. Ozone is used on a full scale
for the treatment of wastewaters containing cyanides, phenols, oil residues,
detergents, sulfides, sulfites and for the oxidation of Fe and Mn compounds,
as well as nitrates.
Nitrogen, C02, ammonium carbonate and urea are formed during ozonation
of CN-containing wastewaters. It was recommended that ozone_be generated
from oxygen rather than air for treatment of concentrated CN" solutions.
30
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CN~ concentrations of 20 to 100 mg/1 were studied. At pH 10, 3 vol %
ozone in air (2 1/hr) reduced 50 mg/1 KCN to below 10 mg/1 in 12 min. At pH
12, the CN" level was reduced to below 0.1 mg/1 in 12 min. Under the same
conditions, Cu complex cyanides were destroyed faster (less than 10 min). 1
mole of CN" requires 1 mole of ozone for destruction in 20 to 30 min.
Contacting: is not discussed.
Economics: In the U.S. the cost of ozone production is figured at around 16
and 7it/kg, depending on whether ozone is produced with air or oxygen. These
numbers show that, in some cases, the use of ozone instead of C12 or OC1" is
more economical.
The capital expense should amount to $1,000 to $2,000/kg generated per
day (oxygen or air, respectively). With rising capital cost of the plant,
operating expenses decrease. Production of ozone represents 75% of the total
cost of operation.
Efficiency: 1 kg of ozone is produced with an energy expense of 8 to 20 kwh
at a concentration of 20 to 30 g/cu m of air. The use of oxygen instead of
air reduces the specific energy consumption by half while ozone capacity is
increased 2 to 3 times.
References: 20
EP-13
Title: "Cyanide Disposal by Ozone Oxidation"
Authors: R.L. Garrison, C.E. Mauk and H.W. Prengle, Jr.
Source: AFWL Report TR-73-212. Final Report for Period April 1972-Nov.
1973 (Feb. 1974). U.S. Air Force Weapons Laboratory, Kirtland Air
Force Base, N. Mexico 87117
Review: A process was developed for complete destruction of total CN" in
influents as high as 100,000 mg/1, or below 1 mg/1, to produce effluents with
total CN" below the limits of detection. Influents were aqueous CN" and
complexed metal CN~ wastes from Air Force electroplating operations and color
photographic film processing.
Laboratory studies showed that destruction of concentrated CN" is limited
by mass transfer of ozone, and destruction of dilute CN" is limited by chemical
reaction rate. Ozone at slightly elevated temperatures in the liquid (150°F)
was more effective than ozone alone, but ozone with UV light was effective
enough to permit design of a successful system. A 4 watt, 253.7 nm UV bulb,
submerged in the liquid in the reactor, was the UV source.
31
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A pilot scale prototype was designed, constructed and operated to
destroy CN wastes to below the detectable limit. The conceptual design of a
full scale system is included.
Wastewaters Studied: included Ni stripping, Cu plating, Cd plating, photo-
graphic bleach and photographic fixer, each treated by UV/ozone in low and
high concentrations. In all cases, total [CN"] in the effluents was below
the detectable limit.
Experimental Details: Acrylic plastic was used for the reactor (it is
transparent) and stainless steel and Al were used for portions of the system
in contact with the dry gas phase. Synthetic wastes were studied first.
Ozonation at pH 11.0 converted all CN to CNO", after which acidification to
pH 4 immediately hydrolyzed CNO". Three Ibs of ozone were found to react
with 1 Ib of free CN, except for Cu-containing solutions, in which the ratio
was 2.5/1. Similar results were obtained using actual plating and photopro-
cessing wastes.
Prototype Reactor: 3 vertical countercurrent contact stages were used, each
containing UV light sources and 420 RPM agitation. UV light was used only
when the [CN~] was expected to be <50 mg/1 or when Fe cyanide complexes were
present. The prototype was designed to treat 0.5 gal/8 hrs of waste containing
40,000 mg/1 CN , or 15 gal/24 hrs of waste containing 4,000 mg/1 CN", or
lower.
Each contacting stage was 12 inches in diameter and 16.5 inches tall.
Six 15-watt tubular UV lamps (253.7 nm) were mounted vertically in each
stage, 1 inch from the reactor sidewalls. A W.R. Grace LG-2-L2 ozone generator
(oxygen feed) was used, producing 3.2% (by weight) ozone.
Prototype Results: With dilute CN" wastes (photo bleach, photo fixer, Cu
plating and Ni strip) containing 10 mg/1 CN , at waste_feed rates of 20
gal/day and UV lamps on in all 3 reactor stages, no CN" was detectable in the
2nd or 3rd stages for any runs.
Four additional runs were made on concentrated wastes. For Cu plating
waste, UV and heat (150°F) were used in the 3rd stage only (ozone only in the
1st and 2nd stages). The liquid feed contained 4,000 mg/1 CN" (pH 11.5); pH
in stage 3 was controlled at 7 to 8 using sulfuric acid; the effluent contained
below 0.1 mg/1 CN". 2.4 wt % ozone was fed to the 3rd and 2nd stages (0.14
Ib/day and 1.96 Ibs/day, respectively) and off-gases from these stages were
fed to the 1st stage (2.1 Ibs ozone/day total). Approximately 1,600 mg/1 of
SS were formed. Over 99.5% of the CN" was destroyed in the 1st stage,
leaving only Fe-complexed-CN~.
Ni strip (4,000 mg/1 CN~) was treated similarly with similar results.
(0.16, 0.26 and 1.68 Ibs/day of ozone were fed to the 3rd, 2nd and 1st
stages, respectively. 97% to 99% of the CN" was removed in the 1st stage.
The treated effluent contained 130 mg/1 SS.
32
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With photo fixer (700 mg/1 CN~), 0.43, 0.43 and 1.23 Ibs/day of ozone
were fed to the 3rd, 2nd and 1st stages, respectively. UV was used in stage
3 only, but 150°F was maintained in all 3 stages. pH in stage 1 was controlled
at 7 with NaOH. [CN~] was reduced to 550 mg/1 in stage 1, to 70 mg/1 in
stage 2 and to <0.2 mg/1 in stage 3. Treated water contained 625 mg/1 SS.
Photo bleach (4,000 mg/1 CN~ complexed with Fe) was treated in 6 stages
and 5.9% ozone was employed. 0.50, 0.38, 0.38, 0.50, 0.38 and 0.38 Ibs/day
of ozone were fed to the 6 successive stages. UV was used in stages 5 and 6,
and 150°F was maintained in all stages. [CN~] leaving the 6 successive
stages, respectively, were 2,680, 1,630, 710, 105, 13 and <0.3 mg/1. About
1,900 mg/1 SS were produced.
In all 4 concentrated wastewater runs, 93% to 99% of the CNO" also was
destroyed.
Cost Estimates: A 3-staged system to treat 5 gpm of cyanide (50,000 mg/1
total CN~), allowing 10.7 hrs/contact stage and using UV and pH control in
the 3rd stage only, and 7,560 Ibs/day of ozone (from oxygen) is estimated to
cost $2.5 MM (plus liquid oxygen storage) and will use 1.35 megawatts of
electricity. This unit would operate 24 hrs/day - 7 days/week.
For treating 1,000 gal/week in 5 24-hr days, ozone (210 Ibs/day) would
be generated from air and the installed cost is estimated at $217,000.
Operating costs would be 8 man hrs/week, 60 Kw of electrical power and $5,000/yr
replacement UV lights.
EP-15
Title: "Ozone-based System Treats Plating Effluent."
Authors; R.L. Garrison, H.W. Prengle, Jr. and C.E. Mauk
Source: Metal Progress 108(6):61-62 (1975).
Describes the advantages of treatment of CN compounds with a combination
of ozone with a small amount of UV light over alkaline chlorination. Cyanides
are destroyed to below the limit of detection in multi-staged ozone/UV reactors.
After oxidation, the pH is adjusted to 10 with alkali, followed by precipita-
tion of all heavy metals in a settling tank. >80% of the treated water is
recycleable, saving rinse water cost.
First cost of ozone/UV equipment is comparable to that of chlorination,
but operating costs are substantially less. These are not cited.
EP-16
Title: "Economics of Treating Cyanide wastes."
33
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Author: M. Goldstein
Source: Pollution Engineering, March 1976, 36-38.
Review; The cost factors of various methods of CN~ waste treatment were
discussed. Included were the processes of chlorination by Cl2 gas and NaOCl,
oxidation by KMn04, HgC^, wet air oxidation, activated carbon treatment and
ozonation.
Economics: Ozone treatment was practical for partial destruction of 20 Ibs
of CN'/day, or for total destruction of 10 Ibs/day. The generator would cost
about $30,000 with annual operating costs being $1,200, vs $6,000 to $10,000/yr
operating costs for C12 gas treatment (Table 4).
Efficiency: Only 40% as much ozone is needed as Cl? gas to oxidize each Ib
of CN-. *
TABLE 4. COST COMPARISONS OF TREATING CYANIDE WASTEWATERS BY A VARIETY OF
TECHNIQUES
Treatment
Process
C12 gas
NaOCl
KMn04
H2°2
Wet Oxi-
dation
Activated
Carbon
Ozone
Cyanide
Treatment
Rate
5 Ibs/hr
4-5 Ibs/hr
5 Ibs/hr
100-1000
ppm as NaCN
2000-4000
mg/1
20 gpm
(1 Ib CN/hr
20 Ibs/day
to CN or 10
Ibs/day to-
tally destr
Capital
Costs
$15,000-
30,000
$75,000-
90,000
$15,000-
30,000
not
estd.
not
estd.
$45,000
)
$30,000
jyed
Operating
Costs
$0.75-1.00/lb CN to CNO
$1.50-2.00/lb($6000-10,000/year)
CN completely destroyed
2.5 kwhr
($2.00/lb CN to CNO)
$6.00/lb CN to CNO/@40£/lb
of KMn04
$1.50/lb CN to CNO followed
by acid hydrolysis
nearly complete CN removed in
5 acrylonitrile plants
$6.00/lb of CN destroyed,
assuming no regeneration.
Carbon must be replaced every 4 days
$l,200/yr
34
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EP-17
Title: "Oxidation of Cyanide in Plating Wastes by Use of Ozone"
Authors: A. Ikehata, K. Ishizaki, N. Tobata & R. Hashimoto
Source: 0. Japan Soc. Safety Engrg. II(2):74-84 (1972)
Batch and continuous run tests were conducted on Ag and Cu plating
wastes.
Ozone Generator: Mitsubishi Electric Corp. tube-type, producing 70 g/hr
ozone from dry air. Oxygen was used to produce ozone for the batch tests;
air for the continuous tests. «
Contactor: Sparger for batch tests in a vessel containing 300 ml of sample.
For continuous run tests, a circulating type ejector. Flow rate of wastewater:
3.6 cu m/hr. Ozonized air flow: 4.8 cu m/hr. 3rd and 4th stage contacting
in series was preferable so as to complete decomposition of CNO'.
Results: CN~ is decomposed and CNO~ is generated soon after ozonation begins.
CNO~ decomposes upon further ozonation. Decomposition of CNO" starts when
total [CN~] becomes about 60 mg/1 (Cu plating wastes) and about 5 mg/1 (Ag
plating wastes). Ferrous CN complex is the most difficult to be decomposed,
whereas Ni and Cu complexes are decomposed rapidly.
Ozone consumption increases considerably as [CN~] decreases. Rate of
ozone decomposition was zero order between pH 6 and 8, 1st order with respect
to CN", and 0.5th order with respect to (OH)".
Unreacted ozone should be recycled (increasing its absorption efficiency
to 95%) and any excess destroyed by feeding into a boiler combustion chamber
or absorption onto activated carbon.
For complete decomposition of CN~ by alkaline chlorination, 6.82 moles
of C12 theoretically are necessary/mole of CN", but practically, large excesses
are required and the pH must be kept at 9 or above. However, cyanic acid
decomposition occurs rapidly only at pH 6.5 to 7. Thus alkaline chlorination
requires 2-stage pH control.
On the other hand, ozonation of either CN" or CNO" can be done under
nearly neutral conditions. The CN/ozone mass ratio for 1st stage oxidation
is 0.542; for 2nd stage decomposition (of CNO") 0.217. In acidic solution,
the CN/ozone mass ratio for 2nd stage decomposition of CNO" is 0.361.
The biggest drawback of ozonation is equipment costs. Present generating
costs are 200 yen/kg, including depreciation of equipment. Ozonation of CN"
wastes thus is somewhat less costly than alkaline chlorination.
35
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EP-23
Title: "Ozone Oxidation of Aqueous Cyanide Waste Solutions in Stirred
Batch Reactors and Packed Towers."
Author: R.P. Selm
Source: Ozone Chemistry & Technology, Advances in Chemistry Series, No.
21, American Chemical Society, Washington, D.C., 66-77 (1959).
Review: Methods of treatment of CN~ wastes are reviewed, comparing the
efficiency and costs of ozone oxidation with those of Cl2 use, with emphasis
on pH factors and on the use of redox potential in the control of ozone
addition. In the ozonation of cyanides there is an extremely rapid absorption
of ozone, with no ozone being in solution during this phase (CN + 03 * CNO"
+ Og). The redox potential is at a low value, rising slowly as the CN~ is
consumed, but rises suddenly when the CN" has been practically completely
oxidized. _The pH is lowered as CN" is oxidized. As the pH falls, the amount
of free CN" decreases rapidly; at the end of ozonation the CN" is almost
exclusively present as hydrocyanic acid, with a neutral pH.
Ozone is more soluble in acid than in alkaline solutions, dissolving in
dilute acid with a rapid rise in pH as long as the pH is <10.5. The pH
returns to the original level as ozone decomposes. The reaction is controlled
by mass transfer. The presence of some metals, particularly Cu, appears to
speed up the reaction. CN requirements are between 1 and 0.33 moles of
ozone/mole of CN".
In the laboratory, ozone oxidized ferrocyam'des first to ferricyanates
and then to ferric hydroxide sols. Traces of ferricyanide remained even
after prolonged ozonation, as did some ferrocyanide ions. 39% of the total
flow of ozone was absorbed. A ratio of 7.25/1 moles of ozone absorbed:mole
of K4Fe(CN)g.3H20 was found, including the ozone decomposed by catalysis due
to hydroxyl ion and other causes.
The redox potential of ozonized distilled water decayed at an approxi-
mately linear rate on a plot of millivolts vs log time. The decay was much
faster for solutions containing ozone demand, and was roughly proportional to
the amount of the ozone demand.
Packed tower studies indicated that ozone may react on the basis of 0.33
mole of ozone/mole of CN~.
Ozone Generator: Ozone was generated by a Welsbach T23 lab ozonator fed with
oxygen. 0.12 cu ft/min of ozonized oxygen at 70° F and 8 psig were fed to
the reaction system.
Contacting: For batch solutions, a 3.5 1 ceramic vessel with a variable
speed, all-glass tubing agitator, and fritted glass diffusion bulb at the
bottom was used for the ozonation at atmospheric pressure. Packed tower
studies were made with a borosilicate glass column 4 inch I.D. and 4 ft long,
36
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packed with 0.25 Inch ceramic Intalox saddles. The feed was distributed
through the tower with a perforated aluminum plate. Feed solution flow rates
were increased to as high as 30,000 Ibs/sq ft/hr, with ozone at 1.78% by wt.
Each soln was held .at least 15 min.
Economics: Chlorine costs depend on plant location and size, and vary from
1510 was
recommended as a safeguard against HCN volatilizing. Oxidation of CN~ to
CNO" is Instantaneous, and the pH range for effective oxidation is 7 to 12.5.
Hydrolysis of CNO" to NH4+ can be effected by lowering the pH to about 3.
Ozonation is satisfactory for large volumes of solutions with concentra-
tions <5 mg/1 of CN", since the [CNO"] formed would be <10 mg/1, which is
below the toxic concentration.
EP-25
Title: "The Oxidation of Cyanide-Bearing Plating Wastes by Ozone. Part I"
Authors: N.E. Sondak & B.F. Dodge.
Source: Plating (1961) 173-80.
37
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Review: This was a study of the system variables required to design an
adequate ozone-CN waste disposal unit. The variables tested were:
(1) Flow rate of ozonized air through the solution: 0.024 to 0.084 cu
ft/min.
(2) Inlet ozone concentration: 4.29 W45.2 mg/1.
(3) Solution constituents: pure aqueous CM' solution, synthetic and actual
plating solutions, and pure aqueous solution.
(4) Operating temperature: 25.9° to 30.6°C.
(5) Solution pH: (initial) 10.3 to 12.4.
(6) Possible catalysts: Cu, Mn, V and Fe salts at concentrations of 1 to 10
mg/1.
(7) Effect of reactor geometry: the ratio of liquid depth to reactor diameter.
Results indicated that the reaction between ozone and CN~ follows the
equation:
CN" + 03 * CNO" + 02
with the rate-controlling step being the mass transfer of ozone. Raw data
are presented with no interpretation.
Ozone Generator: Dry air ozonized in a Welsbach T-23 lab ozonator.
Contactor: Nitrogen oxides were removed from the ozonized air mixt by passing
through dilute NaOH solution. The ozone concentration was measured, the
solution then being sent to a Pyrex column reactor, 4 ft by 2-3/8 inches
I.D., which was usually operated two-thirds full. From here exiting gases
were run through an ozone-absorption system, metered by a wet-test meter.
Assays were done for CN", CN plating solutions, CNO" and Cu plating solutions.
Economics: Specific cost data are not presented.
References: 6
EP-27
Title: "Ozonization as a Means of Wastewater Purification."
Author: J. Trejtnar
Source: Czechoslovak Heavy Industry 10:34-35 (1974)
Review: The technology of ozone removal of cyanides from metal surface
finishing wastewaters was tested at the Water Conservancy Research Institute
and at the Chemical Equipment Research Institute, both of Brno, Czechoslovakia.
Ozone was used to oxidize substances to be neutralized, as well as
materials such as Fe(II), manganous salts, ^S or nitrates. There was a 2-
step reaction between ozone and cyanides:
38
-------
2KCN + 203 * KCNO + 202
2KCNO + H20 + 303 * KHC03 + N2 + 303
About 1.1 to 1.6 volumes of ozone were required for 1 volume of CN~ to
be oxidized to CNO". Purified water could be recirculated as service water.
EP-29
Title: "Disposal of Plating Room Wastes VI. Treatment of Plating Room
Waste Solutions with Ozone."
Authors: C.A. Walker & W. Zabban
Source: Plating 777-780 (1953).
Review: A second paper on removal of CN~ from plating waste solutions, the
first being on Clg and OC1" use. Attention was given to the ability of ozone
to oxidize_CN~ ions in plating wastes to cyanates. Oxidation of the free and
complex CN~ ions by ozone was instantaneous, resulting in the formation of
free cyanates, soluble metallic cyanates and hydroxides. The reaction required
a catalyst (Cu in the sulfate form and Mn(II) were used) if the solution did
not contain metals known to be oxidation catalysts. If no catalyst was
present when treating NaCN and Zn, large amounts of unreacted ozone would
leave the solution; a catalyst was not required for the Cu plating solutions.
Ozone requirements varied from 1.1 to 1.6 Ibs/lb of reacted CN~.
Ozone Generator: Ozone was produced by an apparatus constructed in the
project lab, using dried air. It consisted of a glass tube with tin foil and
the usual electrical accessories. It was not water-cooled. A 1.2 volume %
concentration of ozone was generated.
Contactor: The reaction vessel was a 500 ml, wide-mouthed bottle. The
ozone-air mixture was bubbled through a sintered glass tubing and then
through the reactor. A 5% aqueous KI solution was used to measure the amount
of unreacted ozone.
Economics: Information on cost was not included.
References: 12
39
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LITERATURE CITED ~ FOOD & KINDRED PRODUCTS (FO) & BREWING (8R)
FOOD & KINDRED PRODUCTS (FO)
FO-01 Barrett, F., 1970, "Minimizing the Waste Disposal Problem in Vege-
table Processing." Proc. Symp. Farm Wastes. The Institute of
Water Pollution Control & the Univ. of Newcastle-upon-Tyne (8):57-
65.
FO-02* Coffre, R., 1931, "Process for Ozonization of Fermented Liquids",
English Patent 340,647, January 8. Abstracted in J. Inst. Brewing,
London (1931), p. 449.
FO-03 Leavitt, P. & J.V. Ziemba, 1969, "At Gerber Water Does Triple
Duty", Food Engrg. 41:90-91.
FO-04* Leavitt, P., 1972, "Water Reuse Through Ozone Sterilization", ISA
FID-726,408, p. 19-24.
FO-05 Netzer, A., M.J. Riddle, I.J. Marvan & S.G. Nutt, 1977, "Use of
Ozone for Disinfection of Salmonella in Poultry Plant Effluent",
presented at Symp. on Advanced Ozone Technology, Toronto, Ontario,
Canada, Nov. Intl. Ozone Assoc., Cleveland, Ohio.
FO-06 Rivkowich, H., W.C. Rehman, W. Knapp & B. Borders, 1974, "Method of
Extracting Tea", U.S. Patent 3,809,769, 3 May. Chem. Abstr. 81:90130
(1979).
FO-07* Walter, R.H. & R.M. Sherman, 1974, "Ozonation of Lactic Acid Fermen-
tation Effluent." J. Water Poll. Control Fed. 46(7):1800-1803.
FO-08* Walter, R.H. & R.M. Sherman, 1976, "Efficiency of Oxygen Demand
Reduction of Sauerkraut Brine by Ozone." In Proc. Second Intl.
Symp. on Ozone Technology, R.G. Rice, P. Pichet & M.-A. Vincent,
Editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 694-698.
FO-09 Yim, B., R.H.F. Young, N.C. Burbank, Jr. & G.L. Dugan, 1975, "Bakery
Waste: Its Characteristics & Treatability. Part I", Indl. Wastes,
March/April, p. 24-25. Part II, Ibid. Sept/Oct., p. 41-44.
BREWING (BR)
BR-01 Coffre, R., 1931, "Process for Ozonisation of Fermented Liquids",
British Patent 340,647, Jan. 8. Abstracted in J. Inst. Brewing
(London), p. 449 (1931).
BR-02* Du Jardin, E., 1924, "The Application of Ozone in the Brewery",
Ann. Brass, et Dist. 23:122. Abstracted in J. Inst. Brewing,
London (1925), p. 88.
40
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BR-03* Fergason, R.R., H.L. Harding & M.A. Smith, 1973, "Ozone Treatment
of Waste Effluent", Research Technical Completion Report, OWRR
Project No. A-037-1 DA, Water Resources Research Inst., Univ. of
Idaho, April. U.S. Dept. of Commerce, NTIS Report No. PB 220,008.
BR-04* Geminn, C.C., 1974, "Concentrated Wort Processing Method", Master
Brewers Assoc. of America, Tech. Quarterly 11(1):21-25.
BR-05* Mayrhofer, K.G. & H. Steinhardt, 1955, "Use of Ozonized Water in
Yeast Manufacture", Brauwelt, 857-859. Abstracted in J. Inst.
Brewing, London 61:530 (1955).
BR-06* Schauble, R. & M. Gillardin, 1958, "Ozonized Water in the Brewing
and Mineral Water Industries", Brauerei, Wissenschaft Beil. 11:75-
86. Abstracted in 0. Inst. Brewing, London 64:515 (1958).
BR-07* Tenney, R.I., 1973, "Ozone Generation and Use in the Brewery",
Brewer's Digest 48(6):64-66.
BR-08* Tenney, R.I., 1973, "Ozone, the Add-Nothing Sterilant", MBAA Tech-
nical Quarterly 10(1)': 35-41.
BR-09* Van Laer, M., 1928, "The Use of Ozone in Brewing", Petit J. Brass.
36:854-856. Abstracted in J. Inst. Brewing, London, p. 497 (1928).
FO-02
Title: "Process for Ozonization of Fermented Liquids."
Author: R. Coffre
Source: English Patent 340,647, January 8, 1931. Abstracted in J.
Inst. Brewing, London, (1931), p. 449.
Describes a process to accelerate the natural aging of wines and spirits
without formation of bad flavors. A metal vat is packed with wicker baskets
of oak chips which are ozonated and alternately soaked with the fermented
liquid. This avoids any taste problems associated with direct application of
ozone to the fermented liquid.
This process is claimed to create the same aged qualities observed in
liquids aged 10 to 15 yrs by means of 15 to 20 soakings at intervals of 24
hrs.
FO-04
Title: "Water Reuse Through Ozone Sterilization"
Author: P. Leavitt
41
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Source: Instrumentation in the Food & Beverage Industry, 1972, p.19-24.
Potable quality hot water at the rate of about 350 gpm is required at
the Rochester, N. Y., Gerber Products Plant (baby foods production). The 2
major uses are the empty jar rinsers (where glassware is cleaned and preheated
just prior to filling), and the pressure retorts (where about 509-gal/batch
of 180° F water is added as a medium in which capped jars are heat processed).
Ozonation is used as a method of sterilization in a system that conserves
water and steam by recycling.
The water returns to a 20,000 gal holding tank to which make-up city
water is added. With an adequate supply of warm water in the storage tank, a
550 gpm pump will transfer on demand to the ozone charge tank. The pump is
controlled by a level controller in the charge tank to maintain a water level
that will provide a min residence time of 10 min. The ozone charging tank
holds 7,500 gal of water and is made of stainless steel to resist corrosion.
The tank has a height of 16 ft. Ozone is introduced through ceramic diffusers
on the tank bottom. Ozone is produced in a Welsbach Model C-34-D generator.
water is withdrawn as required from the ozone charging tank by 2 pumps
which feed the 2 closed loops.
Major emphasis is placed on the instrumentation which controls the
recycled water.
The entire system, including instrumentation, was purchased for about
$80,000 in 1968, to which another 30% must be added to include installation
($135,000 total). The savings in water and steam amounts to $125,000/yr, a
return on investment of 82%. This results in a payoff period of 1.9 years.
FO-07
Title: "Ozonation of Lactic Acid Fermentation Effluent."
Authors: R.H. Walter & R.M. Sherman
Source: J. Water Poll. Control Fed. 46(7):1800-1803 (1974).
Review: An approach to treating refractory sauerkraut brine not readily
treatable in a biological process because of its very high BOD (up to 40,000
mg/1) and high acidity.
Contactor: A gas dispersion cylinder 120 x 24 mm, 00 with a medium porosity
fritted disc. A small ozonator (Sander Co., W. Germany, Type II) was employed,
producing 25 mg/hr from oxygen.
Dosages: Very high COD levels (upwards of 15,000 mg/1) were subjected to up
to 3 days of ozonation with an influent 02 flow rate to the ozonator of 9
ml/min. This rate maintained a constant ozone concentration of 400 to 500
mg/1 at 25°C.
42
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Results: Lactic acid (I) and sugar (II) were present in filtered or oxygenated
brines in concentrations of 1.30 and 0.04 g/ml, resp. After 24 hrs of ozona-
tion, [I] was 0.70 g/ml, and [II] was zero. Pyruvic acid (III) appeared
(0.28 g/ml) (but was absent before ozonation), and positive tests for acetalde-
hyde (IV) and C02 were obtained. After 48 hrs of ozonation, [I] was 0.20
g/ml and [III] was 0.03 g/ml. After 72 hrs of ozonation [I] was 0.05
g/ml and [III] was 0.01 g/ml. Thus III is formed upon ozonation, but is
destroyed upon further ozonation. IV appears to be an ozonation product of
I, II. Ill, or all 3.
Comment: Efficiency of ozone application was not a concern in this experiment.
The ratio of ozone consumed to COD removed in 72 hrs was approximately 2.0.
Costs were not projected, but the authors conclude that where ozone generators
already have been installed in the food processing industry, and where small
batches of refractory effluents are not amenable to biological stabilization,
ozonation may be applied as a chemical alternative.
References: 10
FO-08
Title: "Efficiency of Oxygen Demand Reduction of Sauerkraut Brine by Ozone".
Authors: R.H. Walter & R.M. Sherman
Source: Proc. Second Intl. Symposium on Ozone Technology, R.G. Rice, P.
Pichet & M.-A. Vincent, Editors, Intl. Ozone Assoc., Cleveland,
Ohio, 1976, p. 694-704.
Review: Ozone reduced the [COD] of sauerkraut brine in which lactic acid was
the major oxidizable constituent. The stoichiometry of the lactate-ozone
reaction required a weight ratio of 1.87, or 1.01 in terms of COD. The ratio
decreased proportionally with COD during ozonation.
Process: An open loop ozonation system was constructed from a 100 x 8 cm
pyrex cylinder to which was fused a fritted glass filter funnel of medium
porosity and a stopcock 4 cm above the fritted disc. The stem of the funnel
was tapered and connected to an elevated W.R. Grace & Co. Model LG-2-L1
ozonator with 0.25-inch stainless steel tubing. Cylinder oxygen was supplied
through a 2-stage diaphragm regulator preset at 10 psi. Flow rate (75 ml/min)
was controlled by a stainless steel micrometer needle valve, in-line between
the ozonator and the contacting cylinder, and monitored with a soap-film
meter at the discharge end of the KI trap.
Results: Lactic acid in water solution was analyzed (0.50 g/1 and 90 g/1)
and it was found that COD = 0.54 (C) [where C = wt/vol concentration of
lactic acid]. Therefore, the theoretical (COD) efficiency index was 0.54 x
(1.87) or 1.01. There is a tabular illustration of the ratio of COD removal
to ozone generated at 24 hr intervals in 3 liters of brine, which shows the
43
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process achieved the greatest efficiency throughout ozonation at the higher
concentration. In dilute brine ozone was progressively lost in inverse
proportion to the decreased rate of loss of COD.
Conclusion: Existing water quality criteria should be met by dilution
after, rather than before, ozonation of sauerkraut brine when effecting COD
removal.
Economics: Not discussed.
BR-02
Title: "The Application of Ozone in the Brewery."
Author: E. Du Jardin
Source: Ann. Brass, et Dist., 23:122 (1924). Abstracted in J. Inst. Brewing,
London (1925), p. 88.
Review: The germicidal properties of ozone are reinforced and its property
of not leaving unwanted by-products upon degradation is mentioned.
The use of ozone for sterilizing aqueous solutions is cited, but its
capability to sterilize an environment's atmosphere when added in the air
circulation system is questioned. Ozone's ability to deodorize the air is
recognized and since it is such a powerful deodorizer, a lesser circulation
of air is necessary for removing bad odors. Consequently, the temperature in
cellars, etc., is more readily and economically controlled.
BR-03
Title: "Ozone Treatment of Waste Effluent"
Authors: R.R. Furgason, H.L. Harding & M.A. Smith
Source: Research Technical Completion Report, OWRR Project No. A-037-1 DA,
Water Resources Research Inst., Univ. of Idaho, April 1973. NTIS
Rept. No. PB 220,008.
Review; Describes a portable ozone test unit assembled by the Water Resources
Research Inst. at the Univ. of Idaho, and several field tests made with the
unit. Details of the portable test unit are as follows:
Reactor Volume 2 gal
Reactor Residence time 1 to 20 min
Feed Rate 0 to 1.5 gpm
Ozone Production 12 g/hr
Contactor Venturi type
44
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Experimental: The unit was light and easily moved in a van or pickup truck
and required only 110 v of electricity, cooling water and the material to be
treated for its operation.
This portable ozone test unit was shipped to a major brewery to examine
the use of ozone for elimination of tastes and odors. As a result of these
tests, the brewer- is installing a full-sized plant to treat a portion of the
brewery water.
Conclusions: The portable ozone unit has demonstrated its ability to obtain
information, but a larger ozonator should be incorporated into the unit;
other methods of contacting, however, also should be considered.
Economics: Preliminary estimates indicated costs to be 304/1,000 gal for
decolorization and deodorization with a full sized plant (size not specified),
but the authors recommend further tests on larger scale to refine these
estimates.
BR-04
Title: "Concentrated Wort Processing Method".
Author: C.C. Geminn
Source: Master Brewers Assoc. of America, Tech. Quarterly 11(1):21-25 (1974).
Review: Discusses processing of concentrated wort or "high gravity" brews
and describes processing at the Genesee Brewing Co., Rochester, N.Y. Dilution
water is tap water treated by filtration (through sand and gravel, then
activated carbon), ozonation, deaeration, carbonation, cooling and storage.
Dilution Water Treatment: Dilution water should be of the same high quality
as the beer, biologically stable, free of odor, taste and oxygen, carbonated
and be at the proper pH and temperature. After filtration through sand/gravel,
then activated carbon, municipal water (63 gal/min) is ozonized (2 mg/1
dosage; 3 to 5 min contact time through diffusers) to polish the water beyond
activated carbon filtration to sterilize, remove tastes and odors and possible
entrained bacteria. The 0.2 mg/1 residual ozone decays in about 6 min.
Deaeration occurs in a separate vessel by spraying heated (to 105°F)
ozonized water against the chamber walls under vacuum (28 in of Hg) in the
1st stage. In the 2nd stage, the water is passed through a packed column
(ceramic or stainless steel packing). This reduces the oxygen content to
0.15 to 0.20 mg/1. Water then is carbonated to 1.5 to 2.0 vol% C02, then
cooled to 34° to 36°F and stored at 28 in of Hg in tanks equipped with ceramic
diffusers through which a constant low flow of COg is maintained. Blending
of this dilution water with concentrated wort is accomplished with an Analog
Ratio Blending System, and the beer production process is continued.
45
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Ozone Generator: is not identified, but the subsystem includes an inlet air
filter, motor compressor set, dual desiccant tower, 3 dielectric assemblies
and variable voltage transformers which range up to 20,000 v. The unit
produces 1.5 Ibs of ozone/24 hrs or 28.5 g/hr. Clean dry air at 3 to 5 psig
and 1.5 cfm is fed through the dielectrics, producing 1% ozone in air.
This unit treats 63 gpm of dilution water with 2 mg/1 (by vol) ozone
dosages. A dissolved ozone residual of 0.2 mg/1 is attained which decays in
about 6 min. Power requirements are "the same as burning a 200 watt light
bulb, plus an additional cost of about 15 gal/hr of tap water to cool the
electrodes".
Contacting: is effected through porous diffusers. Off-gases containing
excess ozone are vented to the atmosphere. Ozone concentrations in water are
measured by the o-tolidine color comparator test. Residual Cl« interferes
with this test, but with proper pretreatment (activated carbon; Clg is removed.
Biological counts on dilution water consistently plate out zero growth.
BR-05
Title: "Use of Ozonized Water in Yeast Manufacture."
Author: K.G. Mayrhofer & H. Steinhart
Source: Brauwelt 857-859 (1955). Abstracted in J. Inst. Brewing,
London 61:530x (1955).
Review: Discusses the water treatment process using ozone, and its incorpora-
tion into the yeast manufacturing process. In addition, coverage is given to
the biological examination of water, yeast reaction to ozone and behavior of
yeast after ozonation.
Bacteria and coliform counts were substantially reduced (to zero) over
untreated and filtered water and no apparent effect of the yeast's fermentation
abilities were observed, even though its color was affected.
Overall, ozone had no injurious effect on yeast and stabilization was
better than in the previous yr when the water had not been treated with
ozone. Baking properties and appearance of the yeast also were favorably
affected by ozone treatment, and the process imposed no additional technical
burden.
BR-06
Title: "Ozonized Water in the Brewing and Mineral Water Industries."
Authors: R. SchSuble & M. Gillardin
46
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Source: Brauerei, Wissenschaft Beil. 11:75-86 (1958). Abstracted in
J. Inst. Brewing (London) 64:515 (1958).
Ozonation: Describes progress made in developing plant and equipment for
efficient ozonation of water.
Determination oj Ozone: Although this material is now historical in nature,
the author comments on potentiometric titration, colorimetric methods and
acid o-tolidine with Nal.
Germicidal Effects: Experiments were conducted with various forms of yeasts,
rhodotorulae, cocci, short rods, mold hyphae and spores to destroy their
presence. 0.5 g of ozone/cu m was sufficient to sterilize the water and
reduce foreign taste and odor problems. One disadvantage was the waste of
ozone caused by the inefficiencies of the mechanical contacting system.
Applications: The author believes ozonation to be excellently suited to the
fruit juice industry, and feels its many advantages outweigh the slightly
greater cost compared with a chlorination system.
BR-07
Title: "Ozone Generation and Use in the Brewery."
Author: R. I. Tenney
Source; Brewer's Digest 48(6):64-66 (1973).
Review: Discusses ozone production and handling methods. Mention is made of
power costs and materials of construction resistant to ozone. Emphasis is
placed on small quantity production, in the neighborhood of 10 g/hr. Ozone
absorption and toxicity are briefly considered.
Ozone Generator: The basic design for a commercial type corona discharge
ozone generator is presented. Oxidation of phenolic wastes from algae
growth on tannins to CO,, and water was accomplished.
Economics; Under ordinary brewery conditions, ozone half-life is approximately
3 min. Power requirements vary from 13 watt hrs/g of ozone to 20 wh/g.
Assuming electrical costs to be 1.5$/kwh, ozone generation costs <30
-------
impaired by 1 hr exposure to 2.4 ppm of ozone. Adequate control of ozone
levels may, under certain circumstances, be accomplished by a simple vent to
the outside atmosphere, especially if a number of small production units are
employed.
References: 7
BR-08
Title: "Ozone, The Add-Nothing Sterilant"
Author: R.I. Tenney
Source: MBAA Technical Quarterly 10(1):35-41 (1973).
Discusses the physical and chemical properties, production methods,
natural occurrence, and sterilizing efficiency of ozone. Applications are
presented for water and air purification in breweries. The author is a
consultant whose principal interest is applying ozone to the brewing industry.
The following is a recommended list of uses of ozone for this industry:
1. Yeast washing with freshly ozonated water containing 1 to 3 ppm of
ozone. This will quickly destroy the most easily oxidizable substances
in the yeast mass, including melanoidins which create color in the beer
residue. Bacteria will be destroyed with minimum damage to the yeast.
Use of ozonated water is preferable to bubbling ozonated air directly.
2. Final rinsing of bottles or cans with ozone-containing water will
remove trace materials and eliminate beer spoiling microorganisms. The
maximum amount of oxygen which will be introduced to the beer is 9
millionths of a gram/bottle, which will have negligible influence on the
normal variation in air content.
3. Beer fillers and process equipment such as filters are frequently
sterilized before use by circulating hot solutions through them. The
cooling water which follows should be sterile. Water containing 1 mg/1
ozone would be effective for this use while minimizing the corrosive
effect upon brass fittings. If the equipment exposes only impervious
surfaces, then a 2 or 3 mg/1 ozone solution could be used cold for a
sterilant.
4. Rinsing of tanks and pipelines with water containing 1 or 2 mg/1 of
ozone would be advantageous. This practice is not recommended for
rubber hose lines.
5. A final rinse of filter mass with ozonated water just before packing the
new pads will insure sterility at this point for those plants still
using this equipment. It would be practical to coat the interior of the
cake press with polyvinyl chloride or other ozone resistant material.
The original bronze would corrode.
48
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6. Brewers have applied ozone for air purification in rooms used by taste
panels for controlling mold growth and odors in cellars. Ozone can be
used for purifying air in yeast handling areas, in wort cooling and
aeration, and might replace chemical scrubbing of COp, such as by
permanganate.
7. Pretreatment of wastewaters before discharge.
To add 1 mg/1 of ozone to a water stream flowing at 1 bbl/min requires
117 mg/min or about 7 g/hr. Unless ozone is needed in the air to reach walls
and surfaces, it is generally more efficient to wash the air with ozonated
water. Free ozone in the air will discolor brass and bronze fittings, unless
they have been Cr plated.
References: 10
BR-09
Title: "The Use of Ozone in Brewing."
Author: M. Van Laer
Source: Petit J. Brass. 36:854-56, (1928). Abstracted in J. Inst. Brewing
(London) p. 497 (1928).
Ozone's use in sterilizing brewing water is economical since it requires
no after-treatment in the absence of degradation produsts. 2.25 g of ozone
is required to sterilize 1 cu m of water. Due to ozone's affinity for degra-
ding organic matter, as much organic matter as possible should be removed in
a preliminary wash to ensure its disinfectant properties.
Sterilization of vats, piping, etc. has been more successful with
aqueous solutions of ozone as opposed to ozonized air. However, ozonized air
has been used to sterilize bottles that have been prewashed.
The author also notes the deodorizing property of ozone and its applica-
tions in fermentation rooms.
49
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LITERATURE CITED (HOSPITAL WASTEWATERS) (HE)
HE-01 Bryce, C.A., J.A. Heist, R. Leon, R.J. Daley & R.D. Holyer Black,
1973, "MUST Waste Water Treatment System", Final Report to U.S.
Army Medical Research & Development Command, Contract DADA 17-71-C-
1090.
HE-02 Chian, E.S.K. & P.P.K. Kuo, 1975, "Fundamental Study on the Post
Treatment of RO Permeates From Army Wastewaters", First Annual
Summary Rept., U.S. Army Medical R & D Command, Washington, D.C.,
Contract No. DAMD 17-75-C-5006. UILU-ENG-75-2026. NTIS Rept. No.
AD-AD-A021 476/7WP.
HE-03* Chian, E.S.K. & P.P.K. Kuo, 1976, "Fundamental Study on the Post
Treatment of RO Permeates from Army Wastewater", Sec. Annual
Summary Rept. U.S. Army Med. R & D Command, Washington, D.C.
Contract DAMD 17-75-C-5006. Rept. No. UILU-ENG 76-2019. NTIS No.
AD-A035, 912/5WP.
HE-04 Chian, E.S.K., P.P.K Kuo & B.J. Chang, 1978, "Fundamental Study on
the Post Treatment of RO Permeates from Army Wastewaters," U.S.
Army Medical Research & Development Command, Ft. Detrick, Md.,
Contract DAMD 17-75-C-5006, Final Report, 1974-1977.
HE-05 Cowen, W.F., W.J. Cooper & J.W. Highfill, 1975, "Evacuated Gas
Sampling Value for Quantitative Head Space Analysis of Volatile
Organic Compounds in Water by Gas Chromatography," Analytical
Chemistry 47(14):2483.
HE-06 Cowen, W.F. & W.J. Cooper, 1975, "Analysis of Volatile Organic
Compounds in Walden Research MUST Integrated Test Samples and in a
Laboratory Waste Reverse Osmosis Permeate," Memorandum For Record,
Environmental Protection Research Division, U.S. Army Bioengineering
Research & Development Laboratory, Ft. Detrick, Md.
HE-07 Gollan, A.Z., K.J. McNulty, R.L. Goldsmith, M.H. Kleper & D.C.
Grant, 1976, "Evaluation of Membrane Separation Processes, Carbon
Adsorption and Ozonation for Treatment of MUST Hospital Wastes",
Final Report to U.S. Army Medical Research and Development Command,
Contract DAMD 17-74-C-4066.
HE-08 Hewes, C.G., H.W. Prengle, C.E. Mauk & O.D. Sparkman, 1974, "Oxida-
tion of Refractory Organic Materials by Ozone and UV Light", Final
Report to U.S. Army Mobility Equipment Research & Development
Center, Ft. Belvoir, Va. Contract DAAK 02-74-C-0239.
HE-09 Hill, A.G. & J.B. Howell, 1977, "Compression of 03/02 and 03/Air
Mixtures", presented at Symp. on Advanced Ozone Techno!., Toronto,
Ontario, Canada, Nov. Intl. Ozone Assoc., Cleveland, Ohio.
50
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HE-10 Hill, A.G. & J.B. Howell, 1978, "Feasibility of Treating MUST
Reverse Osmosis Permeates by High Pressure Ozonation", Final Report
to U.S. Army Medical Bioengineering R&D Command, Ft. Detrick, Md.,
Contract DAMD 17-77-C-7030.
HE-11 Lambert, W.P. & L.H. Reuter, 1976, "Wastewater Reuse Within An Army
Field Hospital", Proc. Third Natl. Conf. oji Complete Mater Reuse,
Cincinnati, Ohio. Am. Inst. Chem. Engrs., New York, N.Y.
HE-12 Lambert, W.P. & J.J. McCarthy, 1977, "Ozone Oxidation for Reuse of
Army Field Hospital Wastewaters", in Forum on Ozone Disinfection,
E.G. Fochtman, R.G. Rice & M.E. Browning, editors, Intl. Ozone
Assoc., Cleveland, Ohio, p. 108-124.
HE-13 Lee, M. & G. See, 1977, "Ozone Technology Presentation", Life
Systems, Inc., Engineering Report 314-35, Cleveland, Ohio.
HE-14 Lee, M.K., G.G. See & R.A. Wynveen, 1977, "Reaction Kinetics of UV-
Ozone with Organic Compounds in Hospital Wastewater", presented at
Symp. on Advanced Ozone Technol., Toronto, Ontario, Canada, Nov.
Intl. Ozone Assoc., Cleveland, Ohio.
HE-15 McCarthy, J.J., W.F. Cowen, E.S.K. Chian & B.W. Peterman, 1977,
"Evaluation of an Air Stripping-Ozone Contactor System", Technical
Report 7707, U.S. Army Medical Bioengineering R&D Laboratory, Ft.
Detrick, Md.
HE-16 McCarthy, J.J., W.P. Lambert & L.H. Reuter, 1977, "Research and
Development Efforts Concerning Ozonation of Army Field Hospital
Wastewaters", presented at Seminar on the Current Status of Ozonation
for Wastewater Treatment and Disinfection, Cincinnati, Ohio, Sept.
15. Intl. Ozone Assoc., Cleveland, Ohio.
HE-17 Mix, T.W. & H. Scharen, 1974, "Organic Solute Detection", NTIS
Rept. No. PS-770,749, U.S. Dept. of Commerce, 8 p.
HE-18 Mix, T.W. & H. Scharen, 1975, "Development of Techniques for
Detection of Low Molecular Weight Contaminants in Product Water
from Water Purification of Water Reuse Systems", Final Report to
U.S. Army Medical R&D Command, Washington, D.C., Contract DADA 17-
72-C-2169.
HE-19 Reuter, L.H., 1975, "Ozone Research Supported by the U.S. Army
Medical Research and Development Command," in Proc. First Intl.
Symposium on_ Ozone for Water and Wastewater Treatment, R.G. Rice &
M.E. Browning, editors, Intl."DTone Assoc., Cleveland, Ohio, p.
476-482.
51
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HE-20 See, G.G., K.K. Kacholia & R.A. Wynveen, 1975, "Control and Monitor
Instrumentation for MUST Water Processing Element", Final Report to
U.S. Army Medical R&D Command, Washington, O.C., Contract No. DADA
17-73-C-3163.
HE-21 See, G.G., P.Y. Yang & K.K. Kacholia, 1976, "Research.and Develop-
ment of an Ozone Contactor System", Final Report to UiS. Army
Medical Bioengineering R&D Command, Ft. Detrick, Md., Contract DAMD
17-76-C-6041.
HE-22* Sierka, R.A., 1975, "Activated Carbon Treatment and Ozonation of
MUST Hospital Composite and Individual Component Waste-waters",
Technical Report 7502, U.S. Army Medical Bioengineering R&D Labora-
tory, Ft. Detrick, Md.
HE-23 Sierka, R.A., 1976, "Mass Transfer and Reaction Rate Studies of
Ozonated MUST Wastewaters in the Presence of Sound Waves", Final
Report to U.S. Army Medical Research and Development Command,
Contract DAMD 17-76-C-6057.
HE-24 Sierka, R.A., 1977, "The Effects of Sonic and Ultrasonic Waves on
the Mass Transfer of Ozone and the Oxidation of Organic Substances
in Aqueous Solution", Presented at Third Intl. Symp. on Ozone
Technol., Paris, France, May, 1977. Intl. Ozone Assoc., Cleveland,
Ohio.
HE-25 Sierka, R.A. & R.L. Skaggs, 1978, "Effects of Ultrasound on MUST
Hospital Composite Wastewater", Final Report to U.S. Army Medical
Bioengineering R&D Command, Ft. Detrick, Md. Contract DAMD 17-77-C-
7031.
HE-26* Tencza, S.J. & R.A. Sierka, 1975, "Ozonation of Low Molecular
Weight Compounds", Presented at Sec. Natl. Conf. on Water Reuse,
May 4-8. Am. Inst. Chem. Engrs., New York, N.Y.
HE-27 Vlahakis, J.G., 1975, "Renovation of a Hospital-Type Wastewater for
Recycle", Presented at the Second National Conference on Complete
WateReuse, Waters Interface With Energy, Air, and Solids, May. Am.
Inst. Chem. Engrs., New York, N.Y.
HE-28* Zeff, J.R., R.R. Barton, B. Smiley & E. Alhadeff, 1974, "UV-Ozone
Water Oxidation/Sterilization Process". Final Report #1401 to U.S.
Army Medical R&D Command, Contract DADA 17-73C-3138.
HE-29 Zeff, J.D., R. Shuman & E.S. Alhadeff, 1975, "UV-Ozone Water
Oxidation/Sterilization Process", Annual Report, U.S. Army Medical
R&D Command, Washington, D.C., Contract DAMD 17-75-C-5013.
HE-30 Zeff, J.D., R. Shuman, E.S. Alhadeff, J. Wark, F.C. Parrel!, D.T.
Boylan & A. Forsythe, 1976, "UV-Ozone Water Oxidation/Sterilization
Process", Final Report (;973-1976) to U.S. Army Medical Bioengi-
neering R&D Command, Ft. Detrick, Md., Contract DAMD 17-75-C-5013.
52
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HE-03
Title: "Fundamental Study on the Post-Treatment of RO Permeates from
Army Wastewater"
Author: E.S.K. Chian & P.P.K. Kuo
Reference: Sec. Annual Summary Rept., U.S. Army Medical R&D Command, Washing-
ton, D.C., Rept. No. UILU-ENG-76-2019, Oct. 1976. Contract
No. DAMD 17-75-C-5006.
Nine model organic compounds in aqueous solution were treated with ozone
and ozone/UV combinations. The organic compounds studied were: 1-propanol
(I), propionic acid (II), 2-propanol (III), methyl ethyl ketone (MEK), acetic
acid (HOAC), diethyl ether (IV), o-toluidine (V), methanol (MeOH) and N,N-
diethyl-m-toluamide (VI). These compounds were selected because they have
been identified in the RO permeates of hospital waste composites.
Ozone was produced from oxygen at 33 mg/1 at a gas flow rate of 1
1/min. The contactor was a 4 1. fermentor with a stirrer speed of 695 RPM and
a 15 watt, low pressure Hg germicidal lamp emitting major UV energy at 253.7
nm. The pH was controlled by means of a solonoid valve which activated HC1
or NaOH solns if the pH rose or dropped, respectively, during reaction.
An aqueous solution of I (408 mg/1) was ozonized 1 hr at pH 9. Dissolved
ozone concentration was zero, indicating that the ozone demand had not been
fully satisfied. Propionaldehyde (VII)(85 mg/1) was formed and a C-balance
showed that this and I (145 mg/1 remaining) were the only 2 organics present.
Starting TOC (225 mg/1) was reduced to 210 mg/1.
UV/ozone treatment of 410 mg/1 I under the same conditions produced 95
mg/1 of VII; 120 mg/1 of I remained after 1 hr, and TOC was reduced to 205
mg/1. In both cases, TOC levels did not start to fall significantly until
after the VII formation had peaked (45 min with ozone, 40 min with ozone/UV).
This suggests that reduction of TOC concentration occurs by air stripping of
VII.
II (490 mg/1) was ozonized at pH 9, at 25°C, over 2 hrs. Dissolved
ozone was absent from all solutions, again indicating that the ozone demand
had not been satisfied. After 2 hrs the concentration of II was 235 mg/1.
TOC concentration dropped from 235 to 200 mg/1. Since not all C was accounted
for by the amount of II present, there must have been oxidation products
formed which were not detected by gas chromatography. UV/ozonation of II
(490 mg/1) under the same conditions lowered its concentration to 60 mg/1 in
2 hrs. TOC values fell from 235 to 140 mg/1.
For the balance of this work, lower concentrations of organics were
treated, such that concentrations of dissolved ozone of 4 mg/1 or higher were
determined. Ozonation of II at pH 7 and 25°C removed 17% TOC and gave complete
oxidation to acetone. No monocarboxylic acids were detected and acetone
accounted for over 85% of the TOC of the reaction mixture.
53
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UV/ozonation of III substantially improved the rate of TOC removal. An
initial TOC of 110 mg/1 was reduced to 20 mg/1 (85%) after 135 min of UV/ozona-
tion. II disappeared after 30 min, at which time the concentration of
acetone reached its maximum value; this in turn decreased to zero after 75
min. C2-Cs monocarboxylic acids were not detected in the ozonate, but NaOH
was required to maintain constant pH. This indicates that formic and/or
oxalic acids were produced from oxidation of acetone.
Ozonation of MEK 2 hrs at pH 7 and 25°C produced a small amount of
acetate anion. MEK accounted for over 85% of the TOC in the ozonate, and
much of the "loss" of MEK was attributed to air stripping (40% of TOC removed
after 2 hrs of ozonation). By contrast, after 105 min of UV/ozonation, the
concentration of MEK was depleted completely. Acetate ion concentration
reached its maximum value after 35 min, then also decreased to zero at 105
min. Trace amounts of acetone and EtOH also were detected.
Ozonation of HOAc 2 hrs at pH 7 (adjusted at beginning, but allowed to
rise gradually during treatment) and 25° resulted in 14% removal of TOC. The
concentration of glyoxylate anion increased with time, but its concentration
was always very low.
UV/ozonation of acetate anion was much more rapid. After 75 min, no
acetate was detected. Glyoxylate (at lower concentrations than with ozone
alone) remained fairly constant during the first hr, but then disappeared.
No alcohols or monocarboxylic acids (other than acetate) were detected. Thus
the discrepancy between observed and calculated TOC could only be attributed
to the presence of formate and/or oxalate anions. It was proven later that
oxalate is present and formate is absent.
Ozonation of IV 2 hrs at pH 9 and 25°C produced ethyl acetate (EtOAc)
and acetate anion as the major degradation products, but small amounts of
AcH, Me formate, EtOH, acetone and Et formate also were isolated. An overall
TOC removal rate of 61% was obtained in 2 stages. Slower removal of TOC
occurred during the later stages of ozonation, when EtOAc and acetate anion
were the major portions of the TOC. The faster removal rate observed in the
earlier stages may have been due to air stripping of IV and its smaller
oxidation products (AcH, EtOH, acetone, etc.). Good agreement between the
calculated and experimentally determined TOC values indicates that all the
oxidation products were accounted for (therefore C02 was not an oxidation
product).
UV/ozonation gave 94% removal of TOC under the same conditions, because
of further oxidation of EtOAc and acetate ion to C02- Formation of acetate
occurs by 2 routes: 1 from IV, 1 from EtOAc. Small-amounts of the same other
organics as obtained during ozonation also were isolated after UV/ozonation.
Quantitative determination of oxalate and glyoxylate showed that acetate
concentration reached zero when oxalate concentration reached its maximum.
This indicates that the degradation route of acetate by UV/ozonation is
through glyoxylate and oxalate to C02- Since the amount of oxalate formed
was not equal to the amount of acetate present, it is likely that glyoxylate
(precursor of oxalate) can be oxidized directly to C02-
54
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donation of V 2 hrs at pH 9 and 25°C produced 42% TOC removal, but no
V was observed after 15 min. Acetate (about 10 ppm as C) was identified and
its concentration decreased only gradually with time. Oxalate concentration
was slightly higher than that of acetate and appeared to be resistant to
ozonation. Glyoxylate also was identified.
UV/ozonation of V showed 2 different zero order TOC removal rates.
During the first 15 min, all V disappeared completely. Acetate and oxalate
formed during the initial stages, but neither substance was present after 75
min of reaction. Cleavage of the benzene ring appears to be the major mecha-
nism by which V disappears, and no aromatic compounds were detected either by
gas chromatography or by UV absorption at 210 to 270 nm. Volatile aldehydes,
ketones, esters and acids also were not detected, thus the unaccounted for
organics likely are aliphatic amino compds. Final nitrate-N accounted for 34
and 40% of the initial N present (in ozonation and UV/ozonation, respectively),
and the remainder probably was present as organic-N and/or stripped-off NH.,.
Ozonation of MeOH 2 hrs at pH 9 and 25°C produced HCHO and HCOOH as the
only 2 oxidation products. Organic removal was only 72% after 2 hrs, and its
rate slowed after 75 min. UV/ozonation of MeOH gave the same results.
Ozonation of VI 2 hrs at pH 9 and 25° showed no VI or other aromatic
compounds after 15 min. Formic, acetic and oxalic acids were isolated, and
their concentrations were at maximum values after 2 hrs. TOC level was
reduced from 85 to 45 mg/1. Oxalate concentration was 20 mg/1 after 2 hrs of
ozonation.
UV/ozonation gave similar results but acetic and oxalic acids were
further oxidized toward the end of the period, and their concentrations
decreased. HCOOH concentration passed through a minimum, thus it is produced
from more than 1 source. TOC levels decreased from 82 to 28 mg/1. All
organic carbon was accounted for after 105 min. 45% of VI-N had been oxidized
to nitrate after 2 hrs, the unaccounted for N probably having been stripped
off as ammonia. The same result (46% of VI-N found as nitrate) was obtained
by ozonation alone, but 12.5% of the TOC could not be accounted for after 2
hrs. Thus the balance of the N could have been stripped NH.,, but also organic-
N (aliphatic amines).
Summary: Oxidation of formic, glyoxylic and oxalic acids (major end products
of all 9 compounds, along with acetic acid) to COg is believed to be the
major mechanism of organic removal by ozonation. HOAc oxidizes to glyoxylic
acid which further oxidizes to oxalic acid or to C02 (or both). Ozonation of
glyoxylic acid is rapid, since large amounts of it never were found. AcH,
EtOH, EtOAc, IV, and MEK all produced HOAc. HCOOH forms by oxidation of
large molecules as well as from HCHO and MeOH. Cleavage of the aromatic ring
is very rapid, even without UV. UV enhanced the rates of initial oxidation
of all compounds studied except MeOH and IV, but did enhance the oxidation
rates of their initial oxidation products.
55
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HE-22
Title: "Activated Carbon Treatment and Ozonation of MUST Hospital and Indi-
vidual Component Wastewaters"
Author: R.A. Sierk'a
Source: Tech. Report 7502, U.S. Army Medical Bioengineering R&D Laboratory,
Ft. Detrick, Md. (1975)
Review; The objective of this work was to identify the capabilities of
activated carbon and ozone to reduce the TOC and COD levels of the MUST
laundry composite waste, the MUST hospital composite waste, as well as of
their individual component streams, to 10 and 5 mg/1 levels, resp. The
component streams consisted of shower, operating room, kitchen, lab and X-ray
lab wastes and have the following characteristics:
hospital laundry
composite composite
Parameter wastewater wastewater
TDS (mg/1) 1,240 1,630
SS (mg/1) 70 194
pH 6.6 10.5
COD (mg/1) 870 1,740
TOC (mg/1) 229 457
The activated carbon and ozone treatments were studied as post-treatments
after ultrafiltration (UF) and reverse osmosis (RO). Adsorption isotherms
were determined on the UF and RO treated wastes at ambient conditions of pH
and temperature and at pH 7.0. The solutions then were filtered and analyzed
for TOC, inorganic carbon, total carbon and foaming potential.
Treated wastes were ozonized at ambient conditions, then post-treated
with activated carbon filtration, then analyzed for TOC, total carbon and
inorganic carbon. Tests also were made skipping the activated carbon step.
Ozonation was effective in reducing the shower wastes levels to the 5 mg/1
TOC objective, but only after 120 min of treatment. For RO permeates, ozona-
tion for 60 min is required. Lab wastewaters were the least responsive to
treatment.
Carbon Adsorption Isotherm Tests — These were performed by contacting 250
ml of water with known weights of powdered activated carbon (PAC) (Filtrasorb-
400) for 2 hrs at room temperature (24°), then filtering through a 0.45 u
Mlllipore membrane. 60 ml of filtrate was used for TOC analysis and the
foaming potential test.
Foaming Potential Test (FPT) -- was conducted by placing 50 ml of sample in
a 250 ml graduated cylinder and sparging with ozone for 15 sec. The height
and properties of the foam at cessation of ozonation were recorded.
56
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Ozonation Tests -- An ozone reactor was constructed from a 4 liter Nalgene
plastic graduated cylinder cut off at the 3,500 ml mark, a 1/18 hp motor at
350 RPM and containing 2 lucite baffles extending 0.5 inch into the cylinder
at 180° to each other running from the top to bottom of the cylinder.
Ozone was generated in a W.R. Grace Model LG-2-L1 corona generator at a
rate of 167 mg/min. The reactor was filled with wastewater to the 2 liter
mark, a small aliquot was removed for an initial TOC analysis. The UV spectro-
photometric method of Shechter was used to monitor ambient aqueous concentra-
tions of ozone.
UF permeates were treated with 1,000 mg/1 of PAC prior to ozonation and
mixed at 150 RPM for 1/2 hr using a 1/18 hp motor with a 2-bladed propeller.
Economics: No figures were given, although the U.S. Army is evaluating this
system to identify possible processing trade-offs to meet Army requirements
with respect to power, weight, cost, ease of maintenance, reliability,
safety, and simplicity of operation.
References: 7
HE-26
Title: "Ozonation of Low Molecular Weight Compounds"
Authors: S.J. Tencza and R.A. Sierka
Source: Presented at Sec. Natl. Conf. on Water Reuse, May 4-8 (1975). Am.
Inst. Chem. Engrs., New York, N.Y.
Review: Ozonation of aqueous solutions of formic, acetic, propionic and
butyric acids, butyl and isobutyl alcohols, butyraldehyde and methyl ethyl
ketone was studied. These materials are not rejected well by reverse osmosis
membranes. In addition, oxidant concentrations, mixing temperature and pH
were investigated for their effects on the oxidation rates.
Contactor: Ozone was generated in oxygen and passed through a 12 in high,
3.5 in diameter sparger reactor containing 2 opposite baffles which eliminated
a mixing vortex. Sample size was 1.2 1 for all experiments, and changes in
COD were measured.
At a mixing speed of 1500 RPM the interfacial area for transfer of ozone
gas approached its maximum value, and this was the speed used for all experi-
ments. Ozone production rate was 8,210 mg/hr.
Butyric acid was the easiest butyl compound to oxidize by ozone, followed
by the alcohols, methyl ethyl ketone and butyraldehyde. Formic acid was the
easiest to oxidize to C02 and water—-99% was converted in 15 min. Ease of
oxidation decreased in tne order: formic, butyric, acetic, then propionic
57
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acids. The most influential parameters were pH, temperature, mixing and
ozone concentration, in that order.
References: 28
HE-30
Title: "UV-Ozone Water Oxidation/Sterilization Process"
Authors: J. Zeff, R. Barton, B. Smiley & E. Alhadeff
Source: Westgate Research Corporation, Final Report #1401, to U.S. Army
Medical R&D Command, Washington, D.C. Contract DADA 17-73C-3138,
Sept., 1974.
Review: A detailed report of tests performed to determine the feasibility of
combining ozonation and UV radiation simultaneously to remove predetermined
levels of microbial contaminants and organic substances from water. Stirred
reactors and column reactors were compared, with column reactors apparently
being more effective; a definition was made of the general constraints for
operating variables.
The combination of UV and ozone was more effective in destroying the
microbial and organic contaminants. 99.7% of the organisms present were
destroyed by about 2.25 mg/1 of ozone plus UV; 3 mg/1 of ozone plus UV
resulted in their complete destruction. 0.07 mg of ozone and 0.1 watt of
253.7 nm UV could reduce the TOC level of tap water from 10 to 2 mg/1 in 1
minute. 90% of 10 mg/1 hydroquinone and pyrogallol in 3 1 batches were
removed by 65 mg of ozone in 1 hr. UV plus air without ozone oxidized 80%
of 10 mg/1 hydroquinone, 75% of 10 mg/1 pyrogallol and 40% of 10 mg/1 of
xylenol in 1 hr. Increasing the temperature to 50° had little effect on
reaction rate of the above compounds. The energy demand of the non-optimized
process is 8 to 10 watt hours/lb of water processed. Reaction products were
not identified.
No chemical changes were detected upon treating acetate ion or urea with
UV/ozone. All 3 aromatics were significantly degraded by UV alone in a 60
min period: hydroquinone-39%; pyrogallol-33%; xylenol-28%.
Ozone Generator: The UV light and ozone gas were generated with 1 to 3 4-
watt mercury UV ozone lamps installed above the surface of the water in the
reactor.
Contact: A 1 gal stirred batch battery jar reactor was used, and column
reactors were investigated in comparison. All 3 aromatic compounds were
oxidized to a greater extent in 60 min in the column reactor, compared with
the batch reactor. The UV lamp extended throughout the length of the column
reactor. Power demand of the UV lamp is 50 watts and ozone generation requires
10 watts. Three 1, or 6.6 Ibs of water can be treated in 1 hr; thus 9.1 watt-
hours are required to treat 1 Ib of water. This does not include energy re-
quired for pumping or compressing. References: 19.
58
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LITERATURE CITED (INORGANICS) (1C)
IC-01* Geisel, R., H. Krause & W. Kluger, 1972, "Decontamination of Radio-
active Waters", Ger. Patent 2,120,754, 9 Nov., Addn. to Ger. Patent
1,517,664 (Chem. Abstr. 75:40130x for 1,517,664).
IC-02* Lizunov, V.V., E.V. Leontovich, & V.A. Skripnik, 1972, "Ozone
Oxidation of Mercury in Waste Waters from Chlorine and Alkali
Production", Vodopodgotovka Ochistka Prom. Stokov 9:19-22 (Russ).
From Ref. Zh., Khim, 1972, Abstr. No. 171412.
IC-03 Marcy, J. & F. Matthes, 1967, "The Reaction of Manganese (II) Salt
Solution with Ozone", Chem. Tech. 19:430.
IC-04* Netzer, A., A. Bowers & J.D. Norman, 1972, "Removal of Trace Metals
from Waste Water by Lime and Ozonation", Pollut. Eng. Sci. Solutions,
Proc. Intl. Meet. Soc. Eng. Sci., 1st, (Pub. 1973), p. 380-386.
IC-05 Netzer, A. & A. Bowers, 1975, "Removal of Trace Metals from Waste-
water by Lime and Ozonation", in Proc. First Intl. Symp. on Ozone
for Water & Wastewater Treatment, R.G. Rice & M.E. Browning, editors.
Intl. Ozone Assoc., Cleveland, Ohio, p. 731-747.
IC-06 Rohner, E., 1969, "Removal of Manganese in Water with Ozone", Swiss
Patent 481,020, December 31.
IC-07 Senzaki, T. & A. Ikehata, 1968, "Oxidation of Manganese (II) in
Aqueous Solutions by Ozone", Kogyo Yosui, 116:46; Chem. Abstr.
69:100209t (1968).
IC-08 Sergeev, 1964, Y.S., "Iron Removal and Quality Improvement of
Alluvial Water", Kommun Khoz. sb., 2:72, Chem. Abstr. 65:5218g
(1966).
IC-09* Shambaugh, R.L. & P.B. Melnyk, 1978, "Removal of Heavy Metals via
Ozonation", J. Water Poll. Control Fed. 50:113.
IC-10 Singer, P.C. & W.B. Zilli, 1975, "Ozonation of Ammonia in Municipal
Wastewater", in Proc. First Intl. Symp. on Ozone for Water &
Wastewater Treatment, R.G. Rice & M.E. Browning, ecfitors. Intl.
Ozone Assoc., Cleveland, Ohio, p. 269-287.
IC-11 Somiya, I., H. Yamada & T. Goda, 1977, "The Ozonation of Nitro-
genous Compounds in Water", presented at Symp. on Advanced Ozone
Technol., Toronto, Ontario, Canada, Nov. Intl. Ozone Assoc.,
Cleveland, Ohio.
IC-12* Weber, P. & W.L. Waters, 1973, "Ozonation of Aqueous Dimethyl-
mercury", Proc. Montana Acad. Sci., 32:66-69.
59
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IC-13 Whitson, J.T.B., 1947, "The Effect of Ozone on Waters Containing
Manganese", J. Inst. Mater Engrs. 1:464.
IC-14 Yakobi, V.A., G.A. Galstyan & T.M. Galstyan, 1975, "Oxidation
of Compounds of Trivalent Chromium by Ozone", Zhurnal Prikladnoi
Khimii 48(1):16-19.
IC-01
Title: "Decontamination of Radioactive Waters
Authors: R. Giesel, H. Krause & W. Kluger
Source: German Patent 2,120,754, 9 Nov. 1972; Addn to German Patent
1,517,664 (Chem. Abstr. 75:40130x for 1,517,664)
Foaming during evaporation of radioactive wastewater is prevented by
ozonation before evaporation.
IC-02
Title: "Ozone Oxidation of Mercury in Waste Waters From Chlorine and
Alkali Production"
Authors; V.V. Lizunov, E.V. Leontovich & V.A. Skripnik
Source: Vodopodgotovka Ochistka Prom. Stokov 9:19-22 (1972) (Russ.). From
Ref. Zh. Khim., 1972, Abstr. No. 171412
An air mixture with 22 to 24 ppm of ozone was passed through a 50 mm x 2
m column containing 0.124 mg/1 of Hg in wastewater for 6 to 32 minutes. The
oxidation rate increased with decreasing pH and was complete at pH 4. No
metallic Hg vapor was produced.
IC-04
Title: "Removal of Trace Metals From Waste Water by Lime and Ozonation"
Authors: A. Netzer, A. Bowers & J.D. Norman
Source: Pollut. Engr. Sci. Solns., Proc. Intl. Meet. Soc. Engr. Sci., 1st,
1972 (Publ. 1973), p. 380-386
A bench scale plant for removal of trace metals by lime and ozonation is
described. Stock solutions of metals were prepared to a concentration of
about 100 mg/1; the exact concentrations were determined spectrophotometrically.
Lime was added to adjust the pH to 7 to 9. Ozonation was carried out to
60
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saturation In a 120 x 6.5 cm perspex column. Metal removal was >99.5% for
Al, Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn. Hg removal was lower.
IC-09
Title: "Removal of Heavy Metals by donation"
Authors; R.L. Shambaugh & P.B. Melnyk
Source: J. Water Poll. Control Fed. 50:113 (1978)
Toxic heavy metals are present in many industrial and municipal wastes
and potable streams, in both complexed and uncomplexed forms. Ozonation was
investigated as a method of removing heavy metals. Reaction rate constants
for the 2nd-order reaction of aqueous ozone with EOTA-complexed Mn, Cd, Ni
and Pb are 1.39 x 1Q5, 1.52 x 105, 2.88 x IflS and 2.96 x 10$ cu cm/mole,
resp. The ozonation of uncomplexed Pb, Mn, Ni, Co, Ba and Zn was investigated.
When higher oxidation states of the metal ion are possible, the ozone oxidation
of uncomplexed metals appears to be very rapid, with reaction rate constants
exceeding 10' cu cm/mole.
"Ozonation of Aqueous Dimethyl mercury"
Authors: P. Weber & W.L. Waters
Source; Proc. Montana Acad. Sci. 32:66-69 (1973)
Generator: Welsbach, Model T-408 operating with oxygen at 0.01 mmole/min
produced 4% ozone in oxygen.
Contactor: A reaction flask maintained at 25°C.
Experimental: Dimethylmercury (I) solutions in water (0.0005 M) were ozonized
about 10 minutes. The reaction was too fast to allow calculation of a rate
constant or reaction order. This agrees with earlier work on the same reaction
in chloroform. No detectable I remained after 10 minutes of ozonation (limit
of detection, 0.00005 M), and at least 90% had reacted.
Expected reaction products (HCOOH, C02, HgO) were not identified. It
was concluded that ozonation can be used to remove aIkylmercurials from water
and wastewater.
References: 7.
61
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LITERATURE CITED — IRON & STEEL (IS)
IS-01 Anonymous, 1951a, "Ozone Kills Phenols in Waste", Chem. Engineering
225-228, Sept. 1951.
IS-02 Anonymous, 1951b, "Phenol Wastes, Treatment by-Chemical Oxidation",
Cooperative Study, Ohio River Valley Water Sanitation Commission,
Cincinnati, Ohio, 15 June 1951.
IS-03 Cleary, E.J. & J.E. Kinney, 1951, "Findings from a Cooperative
Study of Phenol Waste Treatment", Engineering Bull., Purdue Univ.
Engr. Ext. Serv. 76:158-170.
IS-04* Hall, D.A., 1958, "The Treatment of Coke Works Effluent with Ozone",
Gas World 147(3829): Coking Sect. 52(539):7-13.
IS-05* Hall, D.A. & G.R. Nellist, 1959, "Treatment of Phenolic Effluents",
J. Appl. Chem. 9:565-576.
IS-06* Hall, D.A. & G.R. Nellist, 1965, "Phenolic Effluents Treatment",
Chem. Trade. J. & Chem. Engineer 156(4072):786.
IS-07* Kucharski, J.K., E. Ladouceur & B.P. Le Clair, 1976, "Treatment of
Blast Furnace Scrubber Water", Presented at llth Canadian Symp. on
Water Pollution Research, Burlington, Ontario, 5 Feb.
IS-08 Leggett, 1920, U.S. Patent 1,341,913.
IS-09 Marechal, 1905, French Patent 350,679.
IS-10* Murdock, H.R., 1951, "Ozone Provides an Economical Means for
Oxidizing Phenolic Compounds in Coke Oven Wastes", Indl. Engr.
Chem. 43(11):125A, 126A, 128A.
IS-11 Niegowski, S.J., 1953, "Destruction of Phenols by Oxidation with
Ozone", Indl. Engrg. Chem. 45:632.
IS-12* Nebolsine, R., 1957, "The Treatment of Waterborne Wastes from Steel
Plants", Iron & Steel Engr., Dec., p. 125-150.
IS-13* Prober, R., P.B. Melnyk & L.A. Mansfield, 1977, "Ozone-Ultraviolet
Treatment of Coke Oven and Blast Furnace Effluents for Destruction
of Ferricyanides", Presented at 32nd Annual Indl. Waste Conf.,
Purdue Univ., Lafayette, Indiana, May.
IS-14 Rozhnyatovskii, 1.1., D.P. Dubrovaskaya & F.A. Melamed, 1959, "The
Purification of Waste Waters from Coke Plants by Ozonation". Koks
i Khim, 7:63-66.
62
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IS-04
Title: "The Treatment of Coke Works Effluent with Ozone"
Author: D.A. Hall
Source: Gas World 147(3829):Coking Sect. 52(539):7-13 (1958)
Review: Laboratory ozonation studies were conducted on iron and steel wastes.
Durham coke works ammoniacal waste liquors were ozonized, destroying most
normal chemicals present (cyanides, thiocyanates, sulfides, thiosulfates) but
leaving a high oxygen absorption value (OAV) and producing other obnoxious
substances (cyanides from thiocyanates, oxalic acid and sulfuric acid).
About 150 mg/1 of final OAV was due to oxalic acid, which, though not detect-
able before ozonation, was present afterward in amounts up to 800 mg/1.
Other OAV apparently was due to some condensation products of a resin or gum
type. The liquor became almost colorless after ozonation, after passing
through a dark brown or nearly black intermediate stage. The following
compounds present in ammoniacal waste liquor were tested:
(1) Phenols. The ozone/phenol ratio averaged 1.7, varying between 0.7 and
2.8 (17 Ib of ozone would be required/1,000 gal of ammoniacal waste
liquor). The efficiency of ozonation could be increased by about 25% by
increasing the pH of the original liquor to about 10.
(2) Polyhydric phenols. These were destroyed by ozonation, though somewhat
more slowly than were monohydric compounds. In the ozonation of pure
dihydric phenols there was an apparent production of phenol-aldehyde
resins, which themselves were ozonized at a later stage in the process.
(3) Thiosulfates. At concentrations up to about 4,000 mg/1 complete destruc-
tion of the thiosulfate took place in the early stages of ozonation;
about 98% of the sulfur was converted to sulfuric acid.
(4) Thiocyanates and Cyanides. Thiocyanates were converted to CN~, which
was oxidized to CNO" only after phenols had been completely oxidized.
CNO~ underwent complete oxidation to C02 and N£. Ammonium sulfate and
sulfuric acid also were formed. Increased pH had the reverse effect on
CNO" oxidation as on phenol oxidation, the reaction slowing down consider-
ably at pH >8.0. At an initial pH of 11.5 the time required for destruc-
tion of SCN" was near]y 10 times that at pH <8.0. There was practically
no accumulation of CN~ when the pH was >9.0; otherwise the maximum CN~
. concentration reached usually varied between 25 and 50 mg/1.
(5) Sulfides. At concentrations up to at least 108 mg/1, sulfides were
easily oxidized to sulfuric acid.
(6) Ferrocyanides. Conversion to ferricyanide may have occurred to a small
extent, as the liquor sometimes turned a pale blue color.
63
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Ozonation was a more efficient process when used after pretreatment by
froth flotation or by biological means. In the first case, <1 Ib of ozone
destroyed all the phenols in 1,000 gal of pretreated liquor; when phenol
concentrations were reduced to <1 mg/1, the ozone/phenol ratio was about 3:1,
there was only a small change in pH, and OAV was reduced to about 20. In
the second case, ozonation destroyed phenols and thiocyanates, and reduced
the OAV, but an increase in [CN~] occurred which could be eliminated completely
only by doubling the ozone dosage. The efficiency of ozone absorption decrea-
sed rapidly after completion of phenol oxidation. The use of ferrous sulfate
or chlorine would be more economical for the removal of CN" created upon
ozonation of SCN".
Ozone Generation: A Tack Air Conditioning Co., Ltd. "Ozonair" apparatus,
produced 2.5 g ozone/hr (12,000 volts) at a concentration of about 5 mg/1 and
dry air throughput rate of 6 I/ min. Contactor details are not given.
Contact: Ozonized air was distributed by a sintered glass filter upwards
through the waste liquor in a vertical wide-bore glass tube. The amount of
air required to give an ozone dosage of 200 (or 300) mg/1 was passed through
at about 25 1/hr. Ozone was measured in the influent and effluent gases, so
that the amount of ozone actually consumed was determined.
Economics: Costs were estimated at about 42£/lb of ozone for a plant producing
10 Ib ozone/hr. This was further broken down as follows: 1410), however, the increase in [CN"] upon
ozonation does not occur.
64
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The amount of ozone required to oxidize 1 unit of phenol Increases as
the total [phenol] is reduced, especially at very low concentrations. At
higher [phenol], the ratio is sometimes <1. To reduce [phenol] to <1 mg/1
for treated liquors containing 50 mg/1, the ozone/phenol ratio is 3; but when
the initial liquor contains only 5 mg/1, the ratio becomes 10:1.
References: 8
IS-05
Title: "Treatment of Phenolic Effluents"
Authors: D.A. Hall & G.R. Nellist
Source: J. Appl. Chem. 9:565-576 (1959)
A review article describing treatment of phenolic effluents iron and
steel plants.
Marechal patented the use of ozone for oxidation of phenols in 1905
(French Patent 350,679). In ammoniacal wastewaters, ozone is more effective
in removing phenols than chlorine, which must destroy chloramines produced
before phenols are attacked. Chlorine dioxide does not react with ammonia,
reacts with phenols, but is more costly than ozone.
Laboratory experiments were conducted using an ozone contactor 3 ft high
and 3 in diameter. Each batch was 1,500 ml in volume. Ozonized air (5 mg/1)
was diffused through a sintered tube. The generator was not specified.
Effluent from a coke oven froth flotation plant required <1 lb/1,000 gal
to destroy all phenols (initial concentration about 100 mg/1). The ozone/-
phenol ratio for removal of phenol to <1 mg/1 was about 3/1, and the cost of
ozonizing froth flotation plant effluent would add 2tf to 5
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For high phenol-containing effluents, dephenolization (rotary contactor)
should be the first step, followed by biological treatment or froth flotation
to reduce phenol concentrations to 10 to 50 mg/1. If further reductions are
necessary, ozonation now can produce an effluent containing <1 mg/1.
References: 16
IS-06
Title: "Phenolic Effluents Treatment"
Authors: D.A. Hall & 6.R. Nellist
Source: Chem. Trade J. & Chem. Engineer, 156(4072):786 (1965)
Reviews ORSANCO (Ohio River Valley Water Sanitation Commission) 1951
study of treatment of phenol-containing (100 mg/1) effluents with ozone,
chlorine and chlorine dioxide. All were successful technically, but ozone
was the most cost-effective, was free of obnoxiuos residuals and had no
interferences from ammonia (Abstractors' Note: Pure chlorine dioxide does
not react with ammonia. However, when synthesized using excess chlorine,
then the excess chlorine will react with ammonia.) For complete oxidation of
phenol, however, 6 parts of ozone were required/part of phenol.
In the present work, 15 different British coke works liquors were tested
batchwise with ozone (in 1958). Ozone/phenol ratios ranged from 0.7 to 2.8,
with an average of 1.7. Assuming 42
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Conclusions: In a 2-staged process using this type of reactor, it should be
possible to produce an effluent containing a residual permanganate value
(P.V.) of about 30 mg/1 from a coke works spent liquor which has been biologi-
cally treated. Ozone consumption should not exceed 1.5 Ibs/lb of P.V.
destroyed. Assuming that ozone costs 42
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Source: Indl. Engr. Chem. 43(11):125A, 126A, 128A (1951)
This research project was sponsored by the Ohio River Valley Water
Sanitation Commission and several iron and steel companies. Effluent from an
ammonia still following a Koppers vapor recirculation dephenolizer was used
to obtain laboratory, then pilot plant data. Engineering data necessary for
design of a full scale facility also were obtained. Phenol contents from the
still effluent varied from 28 to 332 mg/1, and the objective was to reduce
this to 5 parts/billion, the taste-producing limit for water supply.
Laboratory studies indicated that ozone, chlorine and chlorine dioxide
would destroy phenols. Ozone (400 mg/1) reduced the phenols content of 2
ammonia still wastes containing 170 and 80 mg/1 to about 5 mg/1; 500 mg/1 of
ozone reduced them both to nearly zero. Much less ozone (160 mg/1) was
required to reduce 80 mg/1 of pure phenol to zero.
6,000 mg/1 of chlorine was required to reduce 170 and 80 mg/1 of phenols
in still wastes to 3 mg/1, probably because chlorine oxidizes ammonia and
ozone does not. Thus the cost of treating phenols in an ammonia still waste
with ozone is less than the cost of treating with chlorine.
In a 100-oven coke plant, the fixed and operating costs for ozone treat-
ment of phenols are estimated to be 3£/ton of coal carbonized. Costs for a
300-oven plant are estimated at 24/ton of coal carbonized. Using oxygen, the
cost would approach 1.25£/ton of coal, but the oxygen would have to be
recycled. These estimates assume 12 yr depreciation of ozonation equipment.
With 5 yr amortization, a large plant could expect costs of U/ton of coal
carbonized. Corresponding chlorination costs would be 2 to 3 times as high
as ozonation costs.
No discussion is given of ClOg experiments nor of the ozone contactor.
A Welsbach ozone generator, using air feed gas, was used.
IS-12
Title: "The Treatment of Waterborne Wastes from Steel Plants"
Author: R. Nebolsine
Source: Iron & Steel Engineer, 125-151 Dec. 1957
A comprehensive review of wastewater treatment in steel plants written
by a consulting engineer, but reports no experimental data nor cites references.
Use of ozone is mentioned, along with chlorine and chlorine dioxide, as a
chemical oxidant for phenolic wastes only.
Use of chlorine is sensitive to dosage, pH and temperature. If the
chlorine dosage falls too low, phenols are not destroyed, but are converted
to chlorophenols, which present a worse disposal problem than the original
68
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phenols. An excessively large quantity of chlorine is required to reduce
phenol concentrations to the low limits desired.
Neither ozone nor chlorine dioxide are as sensitive as chlorine to
operating conditions and they do not produce complications if underfed.
Ozone requires a large initial investment, but has relatively low operating
costs. Chlorine dioxide requires lower investment than ozone, but has
higher operating costs.
"Ozone-Ultraviolet Treatment of Coke Oven and Blast Furnace
Effluents for Destruction of Ferricyanides"
Authors: R. Prober, P.B. Melnyk & L.A. Mansfield
Source: Presented at 32nd Annual Industrial Waste Conference, Purdue
University, West Lafayette, Indiana, May 10-14, 1977.
Preliminary results are presented for destruction of ferricyanlde in
simulated blast furnace effluent and coking liquor compositions.
Decomposition rates of iron-cyanide complexes in the presence of ozone
and UV irradiation were determined for pH 4.5 to 9.5, 8° to 50°C, ozone
feed rates of 0 to 65 mg/l-min, and UV intensities of 0 to 10 watts/1.
Ozone/UV treatment resulted in effective destruction of ferricyanide.
This was attributed to a synergistic effect of the UV irradiation on ozone,
which generates highly reactive species.
Ozone consumption was 5 to 80 fold greater than stoichiometric require-
ments, due to parasitic reactions of ozone.
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LITERATURE CITED — LEATHER TANNERIES (LT)
LT-01 Dye, J.D., 1956, "The Treatment and Disposal of Tannery Wastes",
in The Chemistry and Technology of Leather, F. 0'Flaherty et a1.,
editors, Reinhold Publ. Corp., New York, N.Y.
LT-02* Eye, J.D. & D.P. Clement, 1972, "Oxidation of Sulfides in Tannery
Wastewaters," J. Am. Leather Chem. Assoc., 67:256-267.
LT-03* Shevchenko, M.A. & R.N. Kas'yanchuk, 1964, "Adsorption of Tanning
Substances from Water and Their Stability to Destructive Oxida-
tion", Ukr. Khim. Zh., 30(10):1103-1107.
LT-02
Title: "Oxidation of Sulfides in Tannery Waste Waters"
Authors: J.D. Eye & D.P. Clement
Source: J. Am. Leather Chemists Assoc. 67:256-267 (1972).
Several methods of eliminating sulfide from lime-Na sulfide solutions
were studied in laboratory experiments, including Nfy persulfate (I),
ozone, precipitation with FeS04 (II) and the use of MnS04 (III), Cr+3 (IV)
and KMnO. (V) as catalysts during air oxidation.
Ozone rapidly oxidized the sulfide, as did air when Mn was the catalyst.
V was more effective than III. Attempts at removing sulfide with I, II and
IV were not successful. The V catalyzed air oxidation reaction then was
applied successfully to a wastewater from a hair burning operation which
had [sulfide] of 5,000 mg/1. [V] of 500 mg/1 provided complete oxidation
in 90 min.
In the laboratory study phase, samples containing 100 mg/1 sulfide
were treated with 100 mg/1 V and air, 100 mg/1 III with air and with 3.0
and 6.4 standard 1/min of ozone (method of generating, contacting and
concentrations of ozone in feed gas are not given). In all cases, the
final [sulfide] was zero mg/1. Times of contact required to attain complete
oxidation of sulfide were: 290 min for V; 1,800 min for III; 180 min for
ozone at 6.4 std 1/min and 220 min for ozone at 3.0 std 1/min.
The authors rejected ozone because it "is only slightly soluble in
water and technical problems in efficiently applying this oxidant prevented
further study. An efficient contact device might make ozone a feasible
means for sulfide elimination, especially in applications where treatment
space was limited. Ozone generation equipment currently is expensive and
its use must be evaluated carefully".
70
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Costs for sulfide oxidation using V at $0.35/lb were estimated to be
$4.25/gal at a wastewater flow of 1,000 gal/day. Two stage aeration would
be necessary, and require 1.25 hrs of aeration in stage 1 plus 0.25 hr
aeration in stage 2.
Abstractors' Note: Since efficient contacting devices are available for
laboratory and full scale ozonation studies, it appears that these investi-
gators were not provided with sufficient technical details regarding contac-
ting by the supplier of the ozonation system employed.
"Adsorption of Tanning Substances From Water and Their Stability
to Destructive Oxidation"
Authors: M.A. Shevchenko & R.S. Kas'yanchuk
Source: Ukr. Khim. Zh. 30(10);1103-1107 (1964)
It is recommended that ozone and either a coagulant containing 16 to
18% Al2(S04h or a 1:1 Al2(SO.),-FeCl, mixture be used in treating colored
waters containing plant extract:
71
-------
LITERATURE CITED -- MINING (MI)
MI-01* Seller, M. C..Waide & M. Steinberg, 1970, "Treatment of Acid Mine
Drainage by Ozone Oxidation", U.S. EPA Report No. EPA-WQO-14010-
FMH-12/70, 99 pages. U.S. EPA, Washington, D.C., NTIS No. PB-
198,225.
MI-02 Bespamyatov, O.K., A.N. Kvyatkovskii, E.K. Rochin & L.F. Atyaks-
heva, 1975, "Decomposition of Cyanide-Containing Wastewaters of
Concentration Plants by Ozonation with Separate Use of Non-Ferrous
Metals", Ref. Zh. Metall.
MI-03 Chernobrov, S.M. & S.M. Rozinoer, 1975, "Ozone Purification of
Waste Water from Dressing Plants", Obogashchenie Rud, 20(1).
MI-04 Eiring, L.V., 1967, "Detoxification of Industrial Wastewaters of
Gold Mines by Ozonation. I. Behavior of Simple and Complex
Anions During Ozonation", Uch. Zap., Erevan, Gos. Univ., 2:49-
64.
MI-05 Eiring, L.V., 1969, "Kinetics and Mechanism of Ozone Oxidation of
Cyanide-Containing Waste Water", Tsvet. Metal, Nov., p. 42.
MI-06 Fridman, I.D., L.E. Ponchkina, N.N. Khavskii, I.A. Yakubovich &
B.A. Agranat, 1969, "Removal of Toxic Cyanides from Wastewaters
of Gold Extracting Mills." Sh. Mosk. Inst. Stall Splavov Sbornik,
3:106.
MI-07 Kvyatkovskii, A.N., L.G. Konchina & E.K. Roshchin, 1975, "Possi-
bility of the Use of Catalysts for Purification of Cyanide-
Containing Wastewaters with Ozone", Ref. Zh. Metall.
MI-08 Mathieu, G.I., 1975, "Application of the Film Layer Purifying
Chamber Ozonation Process to Cyanide Destruction," in Proc. First
Int'l. Symp. cm Ozone for Water &_ Wastewater Treatment, R.G. Rice
& M.E. Browning (eds.), Intl. Ozone Assoc., Cleveland, Ohio, p.
533-550.
MI-09 Mathieu, G.I., 1977, "Ozonation for Destruction of Cyanide in
Canadian Gold Mill Effluents — A Preliminary Evaluation", Presen-
ted at Symposium on Advanced Ozone Technology, Toronto, Canada,
Nov. Intl. Ozone Assoc., Cleveland, Ohio.
MI-10 Rozelle, R.B., etal_., 1968, "Studies on the Removal of Iron from
Acid Mine Drainage Water", Wilkes College Research & Graduate
Center, Wilkes-Barre Penn., Submitted to Coal Research Board,
Commonwealth of Pennsylvania.
MI-11 Rozelle, R.B. & H.A. Swain, 1975, "Removal of Manganese from Mine
Drainage by Ozone and Chlorine", EPA Report EPA/670/2-75/006.
U.S. EPA, Washington, D.C. NTIS Report No. PB-241.143/7WP.
72
-------
MI-12 Sumitomo Metal and Mining Co., Central Research Dressing Group,
1973, Wastewater Treatment With Ozone at the Konomai Mine", Feb.
12.
MI-13 Swain, H.A., Jr. & R.B. Rozelle, 1974, "Removal of Manganese from
Mine Waters", Proc. Fifth Symp. Coal Mine Drainage Research
Preprints, 357.
MI-14* Swain, H.A. & R.B. Rozelle, 1975, "Use of Ozone for Treatment of
Mine Drainage Discharges", in Proc. First Int'1. Symp. on Ozone
for Water & Uastewater Treatment, R.G. Rice & M.E. Browning
(eds.), Intl. Ozone Assoc., Cleveland, Ohio, p. 748-753.
MI-01
Title: "Treatment of Acid Mine Drainage by Ozone Oxidation"
Authors: M. Seller, C. Waide & M. Steinberg
Source: EPA Document No. 14010 FMH, 12/70, Water Pollution Control
Research Series, 1970. U.S. EPA, Washington, D.C.
Review: An in-depth evaluation of the use of ozone to treat acid mine
drainage. Ozone is stable at low pH, thus Fe and Mn can be oxidized at low
pH. Other methods depend on raising pH before treatment. In addition,
sludge production would be less using ozone.
Ozone Production: Ozone production by means of electrical discharge,
isotopic radiation and chemonuclear methods are reviewed. In addition,
the
economics of ozone production at the point of usage as well as of distribu-
tion from a central production facility are presented. Designs for these
systems are outlined.
Waste Characteristics: Acid mine drainage flow varied from 25,000 to
6,000,000 gpd with Fe(II) concentrations varying from 50 to 1,000 rng/1.
Cost: The article concludes that the lowest cost process would involve a
central plant with ozone generation, distribution systems, high volume acid
mine drainage flows and chemonuclear production of ozone. The highest cost
process would involve on-site production of ozone via corona discharge,
treating low flows. Costs depend upon the amount of Fe and Mn present.
Ozone oxidation combined with limestone neutralization was found to be
an effective treatment with relatively simple process control, good removal,
reduced sludge handling and costs equal to or less than those of current
technology.
References: 40
73
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MI-14
Title: "Use of Ozone for Treatment of Mine Drainage Discharges"
Authors: H.A. Swain & R.B. Rozelle
Source: Proc. 1st Intl. Symp. on Ozone for Water & Wastewater Treatment,
R.G. Rice & M.E. Browning, Eds., Intl. Ozone Assoc., Cleveland,
Ohio (1975), 748-753.
Review: Mine drainages from both anthracite and bituminous coal mines are
characterized by high levels of soluble Fe(II), Mn(II) and acidity. The
conventional treatment of lime neutralization and aeration is effective
only for the acid and Fe(II) removal, not the Mn(II). This EPA-sponsored
research was undertaken to investigate the oxidation of Mn(H) to Mn(IV)
and precipitation of Mn(IV) as MnOg. The variables investigated were
initial [Mn], initial [63] in the gas stream leading to the reactor, pH and
temperature. The rates of Mn removal are as follows:
Variable Order of dependence
Mn(II) 1st
Mn(II) 0.5
Ozone 0.5
pH 0.1
Temp. 0
Concentration Range
<10 mg/1 of Mn(II)
>10 mg/1 of Mn(II)
>2 mg/1 of 0 in gas stream
At higher pH, lower levels of Mn can be attained (<0.1 mg/1).
Two reactions seem to be occuring with Mn:
oxidation of Mn(II) to Mn(IV),
Mn(IV) reacting with ozone to form a higher oxidation state
(permanganate) which becomes soluble.
Ozone reacts with Fe(II) before it reacts with Mn(II). For efficient
ozone utilization, removal of the Fe(II) should be accomplished first.
Transition metals are more acidic in higher oxidation states and acidity is
expected to increase after ozonation.
Chlorine was not found to oxidize Mn(II) at pH values of 1, 3, 5, and
7. Ozone use efficiency was <10%. Further research on ozone contacting is
required.
Generator: Model T-23 Welsbach fed by low dew point oxygen.
References: none cited
74
-------
LITERATURE CITED (ORGANIC CHEMICALS) (OC)
OC-01 Anonymous, 1973, "New Process for Colored Wastewater Treatment",
Source Unknown, March 22.
OC-02 Akimova, N.A. & R.A. Karvatskaya, 1968, "Purification of Waste From
Organosilicon Production by Ozonation", (Inst. Titan. Zaporozhe,
USSR) Khim. PromUgr. 5:48-50.
OC-03 Bauch, H. & H. Burchard, 1970, "Investigations Concerning the
Influence of Ozone on Water with Few Impurities", Wasser Luft
u. Betrieb 14(7):270-273.
OC-04 Besselievre, E.H., 1957, "The Economical and Practical Use and
Handling of Chemicals Used in Industrial Waste Treatment", Proc.
12th Indl. Waste Conf. p. 342-363. Purdue Univ. Engr. Bull., Ext.
Serv., No. 94, Lafayette, Indiana.
OC-05 Brower, G.R. 1967, "Ozonation Reactions of Selected Pesticides for
Water Pollution Abatement", Wash. Univ., St. Louis, Mo., Ph.D.
Diss. #67-9384, 211 pp.
OC-06* Buescher, C.A., J.H. Dougherty & R.T. Skrinde, 1964, "Chemical
Oxidation of Selected Organic Pesticides", J. Water Poll. Control
Fed. 36(8):1005-1014.
OC-07* Cheremisinoff, P.N., A.J. Pema & E.R. Swaszek, 1975, "Controlling
Organic Pollutants in Industrial Wastewaters", Indl. Wastes,
Sept./Oct., p. 26-35.
OC-08 Collier, H.E., Jr., 1967, "Recovery of Alkyl Lead Compounds From
the Aqueous Effluent From Alkyl Lead Manufacture", U.S. Patent
#3,308,061, March 7.
OC-09 Davis, G.M., C.D. Magee, R.M. Stein & C.E. Adams, Jr., 1976, "Ozo-
nation of Wastewaters from Organic Chemicals Manufacture", in Proc.
Sec. Intl. Symp. on Ozone Technol., R.G. Rice, P. Pichet & M.-A.
Vincent, editors, Intl. Ozone Assoc., Cleveland, Ohio, p. 421-435.
OC-10 Farrell, F.C., J.D. Zeff, T.C. Crase & D.T. Boyland, 1977, "Develop-
ment Effort to Design and Describe Pink Water Abatement Processes",
Final Technol. Report No. 1701 to U.S. Army Armament R&D Command,
Dover, N.J., August.
OC-11 Fochtman, E.G. & J.E. Huff, 1976, "Ozone-Ultraviolet Light Treat-
ment of TNT Wastewaters", in Proc. Sec. Intl. Symp. on Ozone Technol.
R.G. Rice, P. Pichet & M.-A. Vincent, editors. Intl. Ozone Assoc.,
Cleveland, Ohio, p. 211-223.
75
-------
OC-12 Foshko, L.S. & D.M. Maryanchuk, 1974, "Possibility of Utilization
of Sewage Waters at Water Treatment Plants of Power Stations",
Terploinergetica (USSR), Jan., p. 72. .
OC-13* Gabovich, R.D., J.L. Kurinnyi & Z.P. Fedorenko, 1969, "The Effect
of Ozone and Chlorine on 3,4-Benzopyrene During Water Treatment".
Gig. Naselennkh Mest., p. 88.
OC-14 Gabovich, R.D. & I.L. Kurinnyi, 1966, in Voprosy Kommunal'noy
Gigreny (Questions of Community Hygiene), Kiev, p. 11.
OC-15 Gabovich, R.D. & I.L. Kurinnyi, year unknown, "Ozonation of Water
Containing Petroleum Products, Aromatic Hydrocarbons, Nitro Compounds
and Organochlorine Pesticides", U.S. Army Medical Intelligence &
Information Agency, Rept. No. USAMIIA-K-4567.
OC-16 Gavrilov, M.S., M.Ya. Rozkin, L.V. Storozhenko, G.F. Slezko,
V.Ya. Storozhenko & A.A. Chumachenk, 1970, "Use of Ozone to Purify
Industrial Discharge", Isv. Vyssh. Uckeb. Zared., Khim. Tekhanol.
OC-17 Goda, T., I. Munemiya & 0. Kawahara, 1973, "Ozone Treatment of
Secondary Treatment Liquid", J. Japan Sewage Works Assoc. 10(112):14-
24.
OC-18* Gorbenko-Germanov, D.S., N.M. Vodop'yanova, N.M Kharina, M.M.
Gorodnov, V.A. Zaitsev, A.K. Koldashov & Ya. M. Murav'ev, 1974,
"Oxidation of Acetone by Ozone in Aqueous media, as Applicable to
the Treatment of Wastewater Containing Ozone", The Soviet Chemical
Industry 6(12):756-757.
OC-19* Gregersen, J.K., 1971, "Evaluation of an Ozonation-Activated
Carbon Treatment for a Colored Industrial Waste", Thesis, Iowa
State Univ., Ames, Iowa.
OC-20 Hoffman, J. & D. Eichelsdflrfer, 1971, "Zur Ozone Einwirkung auf
Pestizide der Chlorkohlenwasserstoffegruppe im Wasser", Vom Wasser
38:197-206.
OC-21 HoignS, J., 1975, "Comparison of the Chemical Effects of Ozone and
of Irradiation on Organic Impurities in Water", Radiation for a
Clean Environment, Intl. Atomic Energy Agency, Vienna, p. 297-305.
OC-22 Il'nitskii, A.P., 1969, "Experimental Investigation of the Elimi-
nation of Carcinogenic Hydrocarbons From Water During Clarification
and Disinfection", Gig. y Sanit. 9:26-29.
OC-23 Il'nitskii, A.P. & A.Ya. Khesina, 1969, Gig. y Sanit. 6:116.
OC-24 Il'nitskii, A.P., A. Ya. Khesina, S.N. Cherkinskii & L.M. Shabad,
1968, "Vliyanie Ozonirovaniya na Aromatisheskie, v Chastnosti
76
-------
Kantserogennye, Uglevodorody" ("Effect of Ozonization on Aromatic,
in Particular Carcinogenic, Carbohydrates"), Gig. y Sanit. 33(3):8-
11. Chem. Abstr. 69:5026X (1968).
OC-25 Ishizaki, K., R.A. Dobbs & J.M. Cohen, 1978, "Oxidation of Hazar-
dous and Toxic Organic Compounds in Aqueous Solution", in Ozone/-
Chlorine Dioxide Oxidation Products p_f Organic Materials, R.G. Rice
& J.A. Cotruvo, editors. Intl. Ozone Assoc., Cleveland, Ohio, p.
210-226.
OC-26 Kalnins, A., et al_., year unknown, "Removal of Organic Substances
From Industrial Wastewater" Izobret., Prom. Obraztsy, Tovarnye Znaki,
45(24):153.
OC-27 Kandzas, P.P., A.A. Mokina, R.F. Marchenko & L.A. Savina, 1970,
"Oxidation of Cyclohexane in an Aqueous Solution Under the Action
of Ozone", Tr. Vses. Nauch-Issled. Inst. Vodosnabzh., Kanaliz.,
Gidrotekh. Scoruzhenii Inzh. Gidrogeol. 28:18-23.
OC-28* Korolov, A.A., 1972,•"Ozonation as a Method of Decontaminating
Water Contaminated by Chemical Compounds", Gig. y Sanit. 37:78-82.
OC-29* Krasnov, B.P., D.L. Pakul & T.V. Kirillova, 1974, "Use of Ozone for
the Treatment of Industrial Wastewaters." Intl. Chem. Engr., 14(4):-
747-750 (1974). Transl. from Khim. Promy. 1:28-30.
OC-30 Lapidot, H. 1975, "Estimated Cost of Ozone Treatment of an Indus-
trial Wastewater," in Proc. 1st Intl. Symp. on Ozone for Water &
Wastewater Treatment, R.G. Rice & M.E. Browning, Eds., Intl. Ozone
Assoc., Cleveland, Ohio, p. 712-730.
OC-31 LaPlanche, A., G. Martin & Y. Richard, 1974, "Etude de la Dggra-
dation des Pesticides par 1'Ozone: Cas du Parathion", Ctre. Beige
d1Etude et de Documentation des Eaux 362:22-26.
OC-32 LaPlanche, A., G. Martin & Y. Richard, 1974, "L'Etude de la Dggra-
dation par 1'Ozone de Quelques Insecticides du Groupe des Organo-
PhosphorSs", T.S.M.-TEau 7:407-413.
OC-33 Livke, V.A. & S.I. Velushchak, 1971, "Supplementary Ozone Treatment
of Wastewaters from Acetylene Production", Khim. Tekhanol. 1:58-60.
OC-34* Livke, V.A., S.I. Velushchak & A.A. Plysynk, 1972, "Ozonation as a
Method of Final Purification and Disinfection of Wastewaters That
Have Undergone Biological Treatment", The Soviet Chemical Industry
3:156-158.
77
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OC-35 Mallevialle, J., Y. Laval, M. Lefebvre & C. Rousseau, 1978, "The
Degradation of Hunric Substances in Water by Various Oxidation
Agents (Ozone, Chlorine, Chlorine Dioxide) in Ozone/Chlorine
Dioxide Oxidation Products of Organic Materials. R.G. Rice & J.A.
Cotruvo, editors. Intl. Ozone Assoc., Cleveland, Ohio, p. 189-199.
OC-36* Mauk, C.E. & H.W. Prengle, Jr., 1976, "Ozone with Ultraviolet Light
Provides Improved Chemical Oxidation of Refractory Organics",
Pollution Engineering, Jan. p. 42-43.
OC-37 Moldavskii, B.L. & V.K. Tsyskovskii, 1971, "Oxidation of Hydro-
carbons—An Economical Way to Produce Petrochemical Products",
Khim. I Tech. Top. I Masel 7(5-6):409-413.
OC-38 Oehlschlaeger, H.F., 1978, "Reactions of Ozone with Organic Com-
pounds", in Ozone/Chlorine Dioxide Oxidation Products of Organic
Materials, R.G. Rice & J.A. Cotruvo, editors.Intl. Ozone Assoc.,
Cleveland, Ohio, p. 302-320.
OC-39* Pakul, D.L., A.M. Sazhina & B.P. Krasnov, 1974, "Oxidation of
Alcohols in Dilute Aqueous Solutions By Ozone", J. Appl. Chem. USSR
47(l):34-37.
OC-40* Prengle, H.W., Jr., C.E. Mauk, R.W. Legan & C.G. Hewes, III, 1975,
"Ozone/UV Process Effective for Wastewater Treatment", Hydrocarbon
Processing 54(10):82-87.
OC-41* Prengle, H.W., Jr., C.G. Hewes & C.E. Mauk, 1976, "Oxidation of
Refractory Materials by Ozone With Ultraviolet Radiation", in Proc.
Sec. Intl. Symp. oji Ozone Technol., R.G. Rice, P. Pichet & M.-A.
Vincent, editors. Intl. Ozone Assoc., Cleveland, Ohio, p. 224-252.
OC-42 Prengle, H.W., Jr. & C.E. Mauk, 1978, "Ozone/UV Oxidation of
Pesticides in Aqueous Solution", in Ozone/Chlorine Dioxide Oxidation
Products of Organic Materials, R.G. Rice & J.A. Cotruvo, editors.
Intl. Ozone Assoc., Cleveland, Ohio, p. 302-320.
OC-43 Reichert, J., 1969, "Examination for the Elimination of Carcino-
genic, Aromatic Polycyclics in the Treatment of Drinking Water,
with Special Consideration of Ozone." Wasser u. Abwasser 110(18):477-
482.
OC-44 Rice, R.G. & G.W. Miller, 1977, "Reaction Products of Organic
Materials with Ozone & with Chlorine Dioxide in Water", Presented
at Symp. on Advanced Ozone Technology, Toronto, Ontario, Canada,
Nov., Intl. Ozone Assoc., Cleveland, Ohio.
OC-45 Richard, Y. & L. Brener, 1978, "Organic Materials Produced Upon
Ozonization of Water", in Ozone/Chlorine Dioxide Oxidation Products
of Organic Materials, R.G. Rice & J.A. Cotruvo, editors. Intl.
Ozone Assoc., Cleveland, Ohio, p. 169-188.
78
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OC-46 Robeck, G., K. Dostal, J.M. Cohen & J.F. Kreissl, 1965, "Effective-
ness of Water Treatment Processes in Pesticide Removal", J. Am.
Water Works Assoc. 57(2):181-199.
OC-47 Rogozhkin, G.I., 1970, Trudy Vsesoyuzn Nauchno - Issled. Inta
Vodo'snabzheniya, Kanalizatsii, Gidrotekhnicheskikh Sooruzheniy i
Gidrogeologii (Works of the All-Union Sci. Rsch. Inst. of Water
Supply, Sewerage, Hydraulic Structures & Hydrogeology) 27:45.
OC-48 Sforzolini, G.S., A. Savino & S. Monarca, 1974a, "Decontamination
of Water Contaminated with Polycyclic Aromatic Hydrocarbons (PAH)
I. Action of Chlorine and Ozone on PAH Dissolved in Doubly Distilled
and in Deionized Water", Igiene Moderna 66(3):309-335.
OC-49 Sforzolini, G.S., A. Savino & S. Monarca, 1974b, "Decontamination
of Water Contaminated With Polycyclic Aromatic Hydrocarbons (PAH).
II. Action of Chlorine and Ozone on PAH Dissolved in Drinking and
River Water", Igiene Moderna 66(6):595-619.
OC-50 Sharifov, R.R., L.A..Mamediarova & E.V. Shul'ts, 1973, "Treatment
of Wastewaters Containing Petroleum Product", Azer. Neft. Khoz.
53(4):36-38. Chem. Abstr. 70:107925P (1973).
OC-51 Sharonova, N.F., N.A. Kuzmina & Yu.A. Kuhbabin, 1968, "Ozonization
of Wastewaters of the Isoprene Industry", Prom. Sin. Kauch.
OC-52 Shevchenko, M.A. & P.N. Taran, 1966, "Products of Ozonization of
Humus Materials", Ukr. Khim. Zh. 32(5):532-536. Chem. Abstr.
65:5393h (1966).
OC-53 Shevchenko, M.A., 1965, "Kinetics of Ozonization of Organic Impu-
rities in Natural Waters", Ozonirov. Vody i Vybor Rats. Tipa.
Ozonatorn. St., Sb. 37-42.
OC-54 Shkolich, P.W., M.P. Gracheva & E.O. Pen'Kov, 1972, "Carcinogen-
Removing Effectiveness of Biological Methods of Purification of
Wastewaters from Organic Synthesis Plants", Ref. Zh. Khim., Abstr.
No. 231387.
OC-55* Sigworth, E.A., 1965, "Identification & Removal of Herbicides and
Pesticides." J. Am. Water Works Assoc., 57(8):1016-1022.
OC-56 Somiya, I., H. Yamoda & T. Goda, 1977, "The Ozonation of Nitro-
genous Compounds in Water", Presented at Symp. on'Advanced Ozone
Technology, Toronto, Ontario, Canada, Nov. 1977. Intl. Ozone
Assoc., Cleveland, Ohio.
OC-57 Stepanyan, I.S., I.A. Vinokur & C.M. Padaryan. 1973, "Liquid Phase
Oxidation of Phenol, Methanol and Formaldehyde as Applied to Waste-
water Purification." Intl. Chem. Engr. 12(14):649-650.
79
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OC-58 Stoveken, J. & T. Sproston, 1974, "Ozone & Chlorine Degradation of
Wastewater Pollutants." U.S.' Dept. Interior, OWRR Rpt. A-017-VT(1),
NTIS Rpt. #PB 238,365/lWP, June. U.S. Dept. of Commerce, Natl. .
Tech. Info. Service, Springfield, Va.
OC-59 Strackenbrock, K.H., 1958, "Chromatographic Separation of Uro-
chromes and Removal from Water by Ozone", Gesundneits Ingenieur
79:54-55.
OC-60 Tencza, S.J. & R.A. Sierka, 1975, "Ozonation of Low Molecular
Weight Compounds". Proc. Second Natl. Conf. on Water Reuse, May 4-
8. Am. Inst. Chem. Engrs., New York, N.Y.
OC-61 Tyutyunnikov, B.N., A.A. Drozdov, Z.V. Didenko & S.S. Potatueva,
1968, "Initiation of the Oxidation of a Paraffin by Ozonized Air",
Khim. Tekhanol, Topi. Masel 13(2):22-25.
OC-62 Vagobi, V.A., M.S. Gavrilov, V.L. Plakidin, G.F. Siezko & B.A.
Ponomarev, 1968, "Ozone Oxidation of Industrial Waste Streams",
Vodosnabek. Sanit. Tekh. 4:23-26.
OC-63 Versar, Inc., 1976, "Assessment of Wastewater Management, Treatment
Technology and Associated Costs for Abatement of PCB Concentrations
in Industrial Effluents", Feb.; "Refinement of Alternative Technolo-
gies and Estimated Costs for Reduction of PCBs in Industrial Waste-
waters from the Capacitor and Transformer Manufacturing Categories",
Jan. 1977; "PCBs in the United States: Industrial Use and Distribu-
tion", Feb. 1976. Natl. Tech. Info. Service, Springfield, Va.,
Rept. No. PB-252.402/3WP.
OC-64 Weil, L., B. Struif & K.E. Quentin, 1977, "Reaktionsmechanismen
beim Abbau Organischer Suktanzen im Wasser mit Ozon", Wasser
Berlin. Proc. Intl. Symp. — Ozon und Wasser, AMK Berlin, Germany
(1978), p. 294-307. Intl. Ozone Assoc., Cleveland, Ohio.
OC-65 Wingard, L.B., Jr. & R.K. Finn, 1969, "Oxidation of Catechol to
cis, cis-Muconic Acid with Ozone", Indl. Engrg. Chem., Prod. R&D
8(l):65-69.
OC-66 Yocum, F.H., 1978, "Oxidation of Styrene with Ozone in Aqueous
Solution", in Ozone/Chlorine Dioxide Oxidation Products of Organic
Materials, R.G. Rice & J.A. Cotruvo, editors. Intl. Ozone Assoc.,
Cleveland, Ohio, p. 243-263.
80
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OC-06
Title: "Chemical Oxidation of Selected Organic Pesticides"
Author: C.A. Buescher, J.H. Dougherty & R.T. Skrinde
Source: J. Water Poll. Control Fed. 36(8):1005-1014 (1964)
A laboratory study of the oxidation of the chlorinated hydrocarbon group
of pesticides: lindane, aldrin, and dieldrin. Oxidants used were chlorine,
peroxide, sodium peroxide, potassium permanganate and ozone.
Equipment: Barber-Coleman Model 10 gas chromatograph, modified to increase
sensitivity of electron capture detection system. No ozonator was mentioned.
Experimental Conditions: All experiments were done with distilled, deionized
and carbon-filtered water, with pesticide samples allowed to stand 24 hrs.
Solutions then were membrane filtered to remove excess pesticide. No attempt
was made to quantify the amount of ozone reacting with any of the samples.
Ozone reaction towers were pyrex columns 4 ft (1.2 m) tall and 3 inches
(7.6 cm) in diameter with teflon gaskets and teflon-covered end plates.
Products of ozonation were extracted twice with pre-purified benzene.
Results: In preliminary studies with 4 hrs contact time, lindane was not
removed with chlorine, H«02 or Na^O-. KMn04 and ozone markedly affected
lindane concentration but aid not completely remove it. Aldrin was completely
removed by chlorine [as Ca(OCl)2L was not affected by the peroxides, and was
completely removed by permanganate and ozone (3.9% by wt ozonized air at 0.3
1/min—4 hrs contact time).
In more quantitative experiments, lindane required 40 mg/1 of permanganate
and 24 hrs contact time for about 40% reduction in concentration. Aldrin was
completely removed by permanganate at 1 mg/1 in 15 minutes of contact.
No attempt was made to obtain the highest utilization of all ozone
produced. In fact, in all runs the maximum amount of ozone absorbed into
solution was about 10% of the ozone produced. Thus air stripping effects
were determined in all ozonation studies.
Aeration had no effect on removal of lindane, but 40 1 of ozonized air
removed 75% (20 1 removed 70%). Aldrin was removed by air stripping and by
ozonation (100% by the combustion with 2 to 3 1 of ozonized air). Dieldrin
was also removed both by air stripping and ozonation (90% with 40 1 of ozonized
air).
It was postulated that the more volatile the pesticide in water, the
easier it can be removed by chemical oxidation.
81
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Lindane was added to Missouri River water in concentrations of 2.2 mg/1
and 0.550 mg/1. Ozonation removed 90% of the lindane at dosages of 20 1 of
ozonized air. Aeration had very little effect.
References: 13
OC-07
Title: "Controlling Organic Pollutants in Industrial Wastewaters"
Authors: P.N. Cheremisinoff, A.J. Pema & E.R. Swaszek
Source: Industrial Wastes, Sept./Oct., 1975, 26-35.
Describes various methods used in the treatment and removal of organic
pollutants from industrial wastewater. Variations of each method are included.
Biological, physical and chemical treatments were reviewed, including a brief
coverage of ozone use. Descriptions were general, giving a broad range of
methods rather than an in-depth coverage of any particular one.
Efficiency: About 11 kwhrs of electrical power are needed to produce 1 Ib of
ozone from air; power requirements are about one-half this amount if pure
oxygen is used. Amounts of ozone used to treat each Ib of contaminant range
from 1.5 to 2.5 Ibs.
Contact: Although contact equipment types were not discussed, it is reported
that a contact time of 15 min will reduce wastewater organic content from 40
mg/1 to around 10 mg/1.
OC-13
Title: "The Effect of Ozone and Chlorine on 3,4-Benzopyrene During Water
Treatment"
Authors: R.D. Gabovich, I.L. Kurinnyi & Z.P. Fedorenko
Source: Gig. Naselennkh Mest. (1969), p. 88
Solutions of 3,4-benzopyrene (I) in benzene were added to distilled or
tap water (without residual chlorine). Chlorination was conducted with
Ca(OCl)2. After treatment with ozone or chlorine, residual I was measured by
luminescence spectroscopy at 402.1 nm.
Both chlorine and ozone treatment decreased the amount of I present, but
neither completely destroyed it, under drinking water conditions (0.5 to 2
hrs chlorination or 3 to 5 min ozonation). Chlorination reduced [I] 5 to 10
times; ozonation 10 to 50 times.
82
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If water was free of ammonia, chlorination was significantly more
effective. At a chlorine dosage of 0.4 to 0.6 mg/1, 4 mkg/1 concentrations
of I were reduced to 1.0 to 1.3 mkg/1 in 30 min, to 0.7 to 0.8 in 2 hrs and
to 0.4 to 0.5 in 24 hrs. Overchlorination with 5 mg/1 chlorine lowered 4
mkg/1 of I to 0.5 mkg/1 in 30 min, to 0.4 in 2 hrs, and to 0.2 in 24 hrs. If
the water contained <0.5 mkg/1 of I, then small dosages of chlorine completely
eliminated I in 12 hrs.
It has been proposed [Gref e_t al_., (1953)] that oxidation products of I
with chlorine are 5-chloro-I and I-5,8-quinone.
Treatment of water containing 4 mkg/1 of I with 2.5 mg/1 of ozone for 3
min reduced the level of I to 0.06 mkg/1; 4.5 mkg/1 of ozone over 5 min
reduced the level of I to 0.04 mkg/1. However, even using large ozone
dosages over 10 to 15 min did not decrease I to less than 0.02 mkg/1.
Treatment of water containing 0.5 mkg/1 of I with 2 mg/1 ozone for 3 min
reduced the level of I to 0.03 to 0.04 mkg/1. Further increase in ozone
dosage was not further effective.
"Oxidation of Acetone by Ozone in Aqueous Media, as Applicable
to the Treatment of Wastewater Containing Ozone."
Author: D.S. Gorbenko-Germanov, N.M. Vodop'yanova, N.M. Kharina, M.M.
Gorodnov, V.A. Zaitsev, A.K. Koldashov & Ya. M. Murav'ev.
Source; The Soviet Chemical Industry 6(12):756-57 (1974).
Primary emphasis is on the methods and equipment employed in oxidation
of acetone to C0« and H~0.
Equipment: An undescribed contact device that provided 98% utilization of
ozone, whereas only 50 to 70% utilization had been realized previously with
methods such as sparging, airlift ejector devices, etc.
Ozonator: OP-66, 11.4 kg/hr. Ozone generated with 960 cu m/hr of air feed
at 12 g ozone/cu m concentration.
jjH_: Close monitoring and control of pH conditions were used in this experiment
to realize the complete oxidation of acetone and all of its degradation
products to C02 + H20. pH varied from 12.1 to 11.0.
Cost Data: 0.54 ruble/kg (capacity was 10 kg/hr) or 256 rubles (100 cu m/day
of acetone).
References: 5
83
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OC-19
Title: "Evaluation of an Ozonation - Activated Carbon Treatment for a
Colored Industrial Waste"
Author: Jack K. Gregersen
Source: M. Sci. Thesis, Iowa State Univ., Ames, Iowa, 1971, 114 pages.
Review: Chemical and physical treatment methods that might be effective in
removing color from an industrial waste (unidentified) containing aromatic
compounds were surveyed. Ozonation eliminated much of the color and some
organic carbon. The nature of the ozonized end products was not determined.
Activated carbon is recommended over other techniques because the techno-
logy needed to design treatment systems already exists. Ozonation followed
by biological treatment is listed second because it is not yet known to what
extent the residues from ozonation are truly biodegradable. This process is
potentially less expensive to operate than a GAC column.
Ozone Generator: A Welsbach Model T-23 generator operated on oxygen at 0.015
cfm at 8 psi produced 2.9 g/hr of ozone at 5% (by wt) concentration.
Contactor: A fritted glass stick in a 125 ml erlenmeyer flask; 100 ml
samples were ozonized.
Experimental: 4 chemical plant (unidentified) wastewater streams were
ozonized. These included a combined waste (I), a process waste (II), an As
waste (III) and a low pH nitrification process waste containing primarily a
salicylic acid derivative. This low pH waste did not appear to be affected
by ozone.
In addition, solutions of pure compounds known to be present or related
to compounds present in the wastes were ozonized. These compounds included
o-nitrobenzoic acid (IV), o-nitroaniline (V), m-nitroam'line (VI), p-nitroani-
line (VII), o-nitrophenol (VIII), p-nitrophenol (IX), 3-m'tro-4-hydroxyphenyl-
arsonic acid (X) and 4-nitrophenylarsonic acid (XI), all at 200 mg/1 in
distilled water.
Results: Ozonation of V, VIII, VII and IX produced 9 to 16% organic carbon
removal after 90 sec and 18 to 26% removal after 300 sec at pH 8. The rate
of ozone application was 7 moles/min/mole of compound consumed. Color removal
was observed at 4 wavelengths measured, but an increase in color was observed
at 470 nm for VII and at 500 nm for IX.
Both IV and XI (colorless before ozonation) became colored after ozonation,
but lost some organic carbon. VI increased in color at all 4 wavelengths
during the first 300 sec of ozonation, but after 600 sec the color had begun
to fade. The color of X was almost completely removed after 600 sec (3.8-6.8
moles ozone/min/mole of X). Ill was only slightly less colored after 600 sec
84
-------
of ozonation than before. Samples of I and II lost considerable color after
600 sec of ozonation, and the pH dropped from 9.9 to 8.1 (probably caused by
loss of ammonia).
The following changes in organic carbon content (in mg/1) were observed
upon ozonation 300 seconds: V, pH 6 or 8, 102 to 81"mg/1; V, pH 10, 102 to
90; VII, pH 8, 99 to 80.5 mg/1; pH 10, 99 to 83; VIII, pH 8, 97 to 79.5 mg/1;
pH 10, 97 to 75; IX, pH 8, 100 to 74 mg/1; pH 10, 100 to 75.5; IV, pH 8, 97.5
to 84 mg/1; pH 10, 97.5 to 82.
OC-22
Title: "Experimental Investigation of the Elimination of Carcinogenic
Hydrocarbons"
Author: II'nitskii, A.P.
Source: Gig. y Sanit. (Hygiene and Sanitation) 9:26-29 (1969).
Review; The methods of elimination of carcinogenic polycyclic aromatic
hydrocarbons from water were investigated, including flocculation, filtering,
chlorination, UV irradiation, and ozonation. Benzpyrene was destroyed by
ozone so rapidly that its concentration was reduced approximately 200 times
in 5 min, from an original concentration of 3.7 x 10~8 to 1.2 x 10~6 g/ml.
Unmodified benzpyrene could no longer be detected after 7.5 minutes.
Procedure: An acetone solution of benzpyrene was poured into 1-liter jars.
After the solvent was evaporated, a jar was filled with 1 liter of pond water
(40 to 50 mg/1 of suspended matter; pH 7.4; temperature 15 to 18°C), and the
contents were mixed on a rocker for 30 min. The ozone-oxygen mixture was
bubbled through the solution for both 5 and 7.5 min. The effect of ozone was
then stopped by the addition of 0.1N sodium hyposulflte.
References: 6
"Ozonation as a Method of Decontaminating Water Contaminated by
Chemical Compounds"
Author: A.A. Korolov
Source: Gig. i Sanit. 37:78-82 (1972)
Review: A literature review, concentrating on the effects of ozone on differ-
ent kinds of chemical compounds in industrial wastewater. The topics covered
include:
85
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1) Phenols. Using ozone doses from 1 to 1.84 g/1, the concentrations of
phenol in aqueous solution were lowered from 95-440 mg/1 to 0.05-0.08
mg/1. COD levels were reduced 10 to 20 times (V.I. Khanagbeyev). For
effective disintegration of high concentrations of phenol, huge ozone
doses (of 1 to 2.5 g/1) were necessary. Complete oxidation may prove
economically unfeasible (H.R. Eisenhauer), with 98% disintegration of
phenols in water using 4.5 moles ozone/mole of phenol. The relative
amounts of ozone needed increased with the degree of phenol destruction:
40% destruction requires 0.75 mg ozone/mg phenol, 90% destruction - 1.85
mg ozone/mg phenol, and 98% destruction - 2.35 mg ozone/mg phenol (R.O.
Gabovich). Ozonation of aqueous phenol results in initial cleavage of
the benzene ring (3 moles ozone/mole phenol), followed by direct oxidation
forming glyoxylic, acetic, maleic, oxalic, carbonic and other acids (2.5
moles oxygen/mole phenol) (H. Bauch et al.).
2) Petroleum Products. Petroleum products from refining plants in concentra-
tions of 300 mg/1 experienced 50% destruction from an ozone dosage of 75
mg/1 (N.V. Sokolova). Long periods of time were needed for treatment
(M.A. Popov). With a concentration of 20 to 30 mg/1 of petroleum products
passing preliminary purification in buffer ponds, 2 to 3 hrs of ozonation
were required.
3) Cyanides. The effectiveness of CN~ destruction significantly increased
under the influence of catalysts, Cu in particular (Sondak & Dodge).
The effectiveness especially increased at pH 12.0.
4) Organophosphorus Pesticides. Ozone actively oxidized carbophos, methaphos,
M-81, and trichlormethaphos-3. Complete destruction of carbophos at a
concentration of 10 mg/1 occurs using 26 mg/1 doses of ozone. Net 8 to
10 mg/1 doses of ozone reduce initially equal concentrations of trichlor-
methaphos-3, methaphos, and M-81 to 0.7, 0.1, and 0.0 mg/1, resp. (R.D.
Gabovich & I.L. Kurinnyi).
5) Varied Organic Synthetic Compounds. Dimethylamine in an alkaline waste-
water was ozonized to HCHO, formic and carbonic acids, nitrites and
nitrates, and under certain conditions, to only 0)3 and nitrates (G.I.
Rogozhkin). 90 min of ozonation of cyclohexane at a concentration of 50
mg/1, using 5 to 7 mg ozone/mg cyclohexane, and at pH 11.5 to 12.5,
resulted in a COD decrease from 120 mg/1 to 5.95-13 mg/1, with the
cyclohexane being oxidized almost completely to C0~.
References: 50
OC-29
Title: "Ozonization of Industrial Wastewater"
Authors: B.P. Krasnov, D.L. Pakul & T.V. Kirillova
86
-------
Source: Khim. prom. 1:28-30(1974). English translation in Intl. Chem.
Engrg. 14(4):747-750 (1974).
Ozonation of ethanol (a model compound for aliphatic alcohols) was
studied in dilute aqueous solutions. Glass columns 40 and 60 mm_in diameter
and 400 mm tall were used. Ozonized air was cleaned of nitrogen"oxides by
passing through a dilute alkaline absorber, then entered the contact column
through a 40-50 u pore size filter. The mixture contained 33 mg/1 of ozone.
Oxidation products were measured by gas chromatography.
In all cases except MeOH (EtOH, BuOH and octanol) the final oxidation
products were alcohols, which were formed from aldehyde intermediates. CO?
was not observed to form in any case. The rate of oxidation increased with
increasing pH, and the rates of oxidation of all alcohols are practically
identical for various initial and almost equal final pH values.
Ozonation of secondary alcohols gave organic acids, but with ketones as
intermediates, and HoO^ is formed at the same time. The intermediate oxidation
products were lower boiling than the original materials and were readily
transferred to the gaseous phase.
Because of the low bond energy of oxygen atoms in ozone (24 kcal/mole),
the reactions are assumed to proceed through free radical mechanisms. Formed
hydroxy radicals produce hydroperoxides which are unstable and decompose to
aldehydes (in the case of primary alcohols) or ketones (secondary alcohols).
Aldehydes are oxidized to peracids which, in dilute aqueous solution, decompose
to organic acids and \\2®2- Material balances showed that ozone consumption
is higher at alkaline pH and H202 does not build up.
The limiting stage of oxidation is initiation, and its rate rises in
alkaline media, due to the increased formation of radicals. Formation of
peroxides upon ozonation of wastewater (which decompose to radicals) thus is
a positive factor. Production of acids also is a positive factor, since they
(and other partially oxidized intermediates) are more readily biodegraded
than the initial alcohols. Thus a decrease in COD and an increase in BOD
should be expected.
Gases exiting the contactor should be cleaned of volatile oxidation
products before release to the atmosphere.
"Ozonation as a Method of Final Purification and Disinfection of
Wastewaters That have Undergone Biological Treatment"
Authors: V.A. Livke, S.I. Velushchak and A. A. Plysynk
Source: The Soviet Chemical Industry 3:156-158 (1972)
87
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Laboratory and pilot ozonation studies were conducted on wastewaters
from organic chemicals manufacture which had been subjected to secondary
biological treatment.
Ozone was generated from air or from oxygen and the gas was fed through
a porous plate. Wastewaters from caprolactam synthesis (Shchekino and Servero-
donetsk Chemical Works) after secondary treatment and after ozonation had the
properties listed in Tables 5 and 6.
TABLE 5. OZONE TREATMENT OF SERVERODONETSK CHEMICAL WORKS, BIOLOGICALLY
TREATED WASTEWATERS
parameter
COD(mg 09/1)
BOD d
after
secondary
treatment
92
11
BOD-5(mg 0,/1) 78
DO L
NH3
nitrites
nitrates
microbe no.
1 Oj os/ml
Col i form tite
5.2
0.25
4.5
24
6.2
r 0.004
after ozone treatment
ozone consumption (mg/1)
IU
82
13
30
5.0
0.05
4.6
13
5.0
0.04
Ib
74
16
30
4.5
traces
4.8
9
3.0
0.43
68
24
25
4
not detected
5.1
traces
2.4
0.43
TABLE 6. OZONE TREATMENT OF SHCHEKINO CHEMICAL WORKS, BIOLOGICALLY
TREATED WASTEWATERS
Parameter
COD(mg 02/1)
BOD-5(mg 02/1)
DO mg/1
NH3, mg/1
nitrite mg/1
nitrates mg/1
urea mg/1
after
secondary
treatment
120
9.7
3.5
15.9
0.5
14.7
7.3
caprolactam mg/1 2.8
hydroxylamine mg/1 0.9
cyclohexanol mg/1 0.7
Microbe no,
1 03 os/ml
Col i form titer
30
0.004
after ozone treatment
ozone consumption (mg/l)
5
106
13
12.8
15.9
0.2
14.8
6.2
1.2
0.1
0.5
22
0.004
10
96
16
25.8
15.4
0.11
15.3
4.9
0.9
none
none
4
0.04
15
92
17
26.4
14.7
0.1
16.0
none
0.5
none
none
1.5
0.43
20
56
22
27.0
14.3
none
16.8
none
none
none
none
none
4.3
25
42
23
29.1
13.5
none
17.4
none
none
none
none
none
4.3
88
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Complete clarification of wastewaters Is achieved at an ozone consumption
of 10 mg/1. Increasing ozone consumption to 15 to 25 mg/1 contributes to
complete removal of resins as a result of oxidative decomposition to simpler
compounds. This is indicated by the fact that BOD increases while COD
decreases with increasing ozone consumption.
Following a period in biological ponds, the ozonized water can be
reused. The cost of ozonizing biochemically purified wastewaters for recycle
and reuse is about 15% of the cost of biochemical purification.
References: 6
OC-36
Title: "Ozone with Ultraviolet Light Provides Improved Chemical Oxidation
of Refractory Organics"
Authors: C.E. Mauk & H. W. Prengle, Jr.
Source: Pollution Engineering, Jan. 1976, 42-43.
Laboratory investigation of the ozone/UV oxidation of ethanol, glycerol,
acetic acid, glycine and ammonium paImitate (100 mg/1 and below in deionized
water) is reported.
The treatment system consists of 3 stirred staged reactors, each having
UV light added, in which solution flows countercurrent to the ozone flow.
In the absence of UV radiation, the ozone autodecomposition rate constant
was 0.2 Ib mole/cu ft-min and the equilibrium ozone concentration of 14 mg/1
was reached. When UV radiation was added the ozone autodecomposition rate
constant increased to 8 Ib mole/cu ft - min and the equilibrium ozone concen-
tration fell to 2 mg/1. TOCs of all test solutions were quickly reduced to
below the detectable limits (times not given). UV activates not only the
1st step but also the further oxidation of intermediate products.
There are several advantages of a multistage reaction system over a
single stage reactor. When each stage is optimized in terms of pH, mixing,
residence time, temperature and UV intensity, the total residence time will
be minimum, reducing total equipment size. Sufficient UV should be used to
increase the chemical reaction rate so that mass transfer of ozone becomes
the limiting factor.
OC-39
Title: "Oxidation of Alcohols in Dilute Aqueous Solutions By Ozone"
Authors: D.L. Pakul, A.M. Sazhina & B.P. Krasnov
89
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Source: J. Appl. Chem. USSR 47(l):34-37, 1974
Ozonization of wastewaters containing considerable amounts of various
alcohols has been studied. Ozonization of normal aliphatic alcohols in
aqueous solutions forms the corresponding aldehydes and acids. The surface
tension of alcohol solutions is 1 of the factors determining the oxidation
rate. The Ozonization method may be used for treatment of wastewaters contain-
ing butanol and higher alcohols.
References: 6
OC-40
Title: "Ozone/UV Process Effective Wastewater Treatment"
Author: Prengle, H. W. Jr., C. E. Mauk, R. W. Legan & C. 6. Hewes, 111
Source: Hydrocarbon Processing, Oct. 1975, 82-87
Combining UV radiation with ozone treatment produces a synergism which
allows normally refractory (to ozone oxidation) compounds to oxidize rapidly.
UV radiation enhances ozone reaction rates by 10* to l(r fold, and drives the
reactions to completion to C02, water, etc. Compounds whose oxidation
reaction rates are too slow to be economical (alcohols, acids, ami no-acids
and polyhydroxyaliphatic alcohols) with ozone alone now can be rapidly and
economically oxidized. Refractory toxic materials, such as K ferricyanide,
also are oxidized rapidly.
Oxidation reaction rates with ozone also can be increased by addition of
heat, but use of UV (6 watt/1 for acetic acid) is more effective than elevating
temperature, and requires less energy.
UV radiation of organics produces free radicals, and the rates of oxida-
tion of these are more rapid than those of the parent molecules. UV also
catalyzes the autodecomposition of ozone—-perhaps to more reactive oxygen
species.
Time of contact with ozone can be shortened significantly by addition of
UV radiation. This will save energy of generating ozone for the excess time
of contact, but will require a small increment of energy for the added UV
radiation.
Details of reactor design are not given. However, more easily oxidized
materials are treated in a single stage ozone/UV reactor, the more refractory
compounds are oxidized in a 2nd multi-staged reactor.
For example, a wastewater containing 900 mg/1 of TDS including free and_
complexed cyanides and refractory organics can be treated to reduce total CN"
to below detectable limits (<0.1 mg/1) and TOC to <1 mg/1 by coagulation with
alum, activated silica and polyelectrolyte, sedimentation, clarification and
90
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equalization. After adjusting the pH to 7 to 8, a single stage ozone/UV
reactor (operating on air) is followed by a multistage ozone/UV reactor. To
treat 500 tons/day (83.3 gpm) requires an installed plant cost of $590,000,
with operating costs, including amortization, of $500/day.
To treat 700 tons/day (117.4 gpm) of wastewater containing ammonia, CN"
and organic nitrogen compounds (1,000 mg/1 total N) to dischargable levels
requires pH adjustment (basic), steam stripping of ammonia, neutralization,
and treatment with ozone/UV in 2 stages.
The ozone generators use recycled oxygen. Installed plant cost is
$334,000, and operating costs are $225/day.
Refractory organics remaining in sewage after secondary treatment and
activated carbon can be removed using ozone/UV. A 1 mgd stream containing 10
mg/1 of TOC (to be reduced to below 0.1 mg/1 is treated in a multistage
ozone/UV reactor (ozone from air). Organics are converted to CO, and water.
Ozone concentration is adjusted automatically by an effluent monitor. Instal-
led plant cost is $505,000. Reactor staging allows more than 67% cost savings
over single stage treatment costs.
"Oxidation of Refractory Materials by Ozone with Ultraviolet
Radiation"
Authors: H.W. Prengle, Jr., C.G. Hewes, III & C.E. Mauk
Source: Proc. Sec. Intl. Symp. on Ozone Technology. R.G. Rice, P. Pichet
& M.-A. Vincent, Editors, Intl. Ozone Assoc., Cleveland, Ohio,
1976, p. 224-252.
Review: The authors studied the rates of oxidation of refractory chemical
species with ozone and UV light. These included ethanol, acetic acid,
glycine, glycerol and palmitic acid. The molecules were graded according to
difficulty of oxidation by a Refractory Index Scale (RFI), with a larger RFI
indicating more difficulty in oxidation. The specific compounds tested were
rated 245, 1,000, 19.7, 112 and 27.3, resp.
Ozone alone was not particularly effective as an oxidant for these
chemicals. The simultaneous use of UV radiation, however, increased the
oxidation rate 100 to 1,000 fold and drove the reactions to completion. With
a small amount of UV radiation the chemical reaction rates were the rate-
controlling factors; with larger amounts of UV, however, the reaction rates
became mass transfer controlled. More small free radicals were formed, which
were oxidized directly to such molecules as CO- and HJ).
Ozonation combined with UV radiation is theorized to be a 2-step process:
photochemical excitation by UV, followed by oxidation by ozone. EtOH was
oxidized to the intermediate HCHO, then to acetic acid, and finally to an
alcohol plus CO-. In the limiting case of 1-carbon chains, water was formed.
91
-------
The use of UV radiation led to substantially more free radicals being formed
than did the use of ozone alone, which radicals initiated many more propagation
chains.
Elevated temperatures enhanced the reaction rates, but not as dramatically
as did additional UV. The difference between the reaction at 30°C and at
50°C was not great and indicated that still higher temperatures would have
Ifttle effect.
Mass transfer data were independent of the chemical reaction. When the
reactor was operated with "complete mixing" (500 to 800 RPM), without UV, the
equimolar ozone concentration was 12 to 14 mg/1, the mass transfer coefficient
about 1.4 (Ib mols ozone/cu ft min), and the auto-decomposition constant in
the range of 5 to 20% of the mass transfer coefficient. With UV radiation,
under the same conditions, the equilibrium ozone concentration was about 2
mg/1, the mass transfer coefficient.
Ozone Generator: The ozone generator was not described.
Contact: A continuously sparged 9.92 1 batch stirred tank reactor, served as
the reaction vessel. The sparging gas was oxygen with 1 to 5 wt% of ozone.
The UV lamp used was a General Electric germicidal bulb. Part of the UV
energy emitted at a wavelength of 254 nm, and a useful UV output of 0.55
watt/1 of reactor liquid. UV light was irradiated into the stirred reaction
mixture at the same time that ozone was being sparged.
Economics: Economic factors were not discussed.
OC-55
Title: "Identification & Removal of Herbicides and Pesticides"
Author: E. A. Sigworth
Source: J. Am. Water Works Assoc. 57:1016-1022 (1965).
Reviews work of Robeck e_t aj_., J. AWWA 57:181 (1965) utilizing coagulation,
oxidation with chlorine, chlorine dioxide, ozone and KMnO,, and adsorption
with activated carbon.
Coagulation with alum and iron salts demonstrated partial removal of a
few products tested (DDT was removed very effectively). Oxidation studies
showed little merit in chlorination or KMnO^ Ozone was more effective
than chlorine dioxide on only a few of the products tested. In at least 1
case the oxidized product was "far more toxic" than the untreated insecticide.
The basis for this statement was not presented.
All studies to date have shown that activated carbon has been successful
-in reducing the concentration of the few herbicides and insecticides tested
to date, including benzene hexachloride, DDT, 2,4-D, toxaphene, dieldrin,
aldrin, chlordane, malathion and parathion.
92
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LITERATURE CITED (PAINT & VARNISH) (PV)
PV-01 ' Ballnus, W. & W. Leiss, 1968, "Verfahren zur Behandlung von Ab-
wSssern der Lackindustrie" (Procedures for Treating Wastewaters of
the Varnish Industry), Wasser, Luft und Betrieb 12(5):289, 292-
293.
PV-02* Bauch, H. & Burchard, H., 1970, "Experiments to Improve Highly
Odorous or Harmful Sewage with Ozone", Wasser, Luft & Betrieb,
14(4):134-137.
PV-03 Kroop, R.H., 1973, "Treatment of Phenolic Aircraft Paint Stripping
Wastewater", USAFWL Rept. 72-181, Jan., 98 pp. U.S. Air Force
Weapons Laboratory, Kirtland Air Force Base, New Mexico.
PV-04* Kroop, R.H., 1975, "Ozonation of Phenolic Aircraft Paint Stripping
Wastewater", in Proc. First Intl. Symp. pji Ozone for Water &^
Wastewater Treatment, R.G. Rice & M.E. Browning, Editors, Intl.
Ozone Assoc., Cleveland, Ohio, p. 660-673.
"Experiments to Improve Highly Odorous or Harmful Sewage with
Ozone"
Authors: H. Bauch & H. Burchard
Source: Wasser, Luft und Betrieb 14(4):134-137 (1970)
Wastewaters from a German paint and varnish plant were tested by
various techniques before discharge. Flocculation then filtration through
activated carbon was acceptable for small volumes of wastewater, but for
large volumes the cost of activated carbon was too high. Furthermore, it
could not be regenerated because of fouling by the adsorbed organics.
Treatment with H202 also was acceptable for small volumes of wastewater, but
also was too expensive for large volumes. Chlorine oxidation was unacceptable
because chlorinated organics were produced which interfered with biological
processes during later clarification.
Ozone Generator: GOTA (Gesellschaft fUr Ozon Technik und Andwendung GmbH,
DUsseldorf, Federal Republic of Germany). Ozone was prepared from air or
oxygen.
Contactor: A standing glass tube 2 m long, 40 mm diameter, with G-3 frit.
Volume of sample treated was 1.5 1.
Wastewater from a varnish plant was preclarified with FeCl3 and/or
Al pise*)*, then neutralized. Ozonation then was conducted by passing 20
mg/1 ozone in air for 30 min at 19°C. Results obtained are given in Table
93
-------
7. Sulfides and Fe(II) were oxidized, the organic odors were decreased
considerably, the residue on evaporation was decreased by 9% (210 mg/1) but
the residue upon ignition remained the same. These data indicate that
organics were oxidized to CO? by the ozone. In addition, KMnCfy oxidizability
was lowered from 1,940 to 340 mg/1, BOD-5 level was reduced from 1,400 to
190 mg/1 and volatile hydrocarbons, volatile phenols, non-volatile phenols
and fats and oils also were reduced in concentration.
Even better results were obtained when the wastewaters were pretreated
with chlorine, which was not as effective without subsequent ozonation (see
Tables 8 and 9). Ozonation will convert residual chlorine to perchlorate,
which also is a powerful oxidant. These tables also show experiments using
hot and cold aeration, which gave some improvement, but which was not suffi-
ciently effective.
TABLE 7. TREATMENT OF SEWAGE OF A VARNISH PLANT BY GASSING WITH OZONE
(20 MG 03 IN AIR) FOR 30 MINUTES AT 19°C
Analytical Parameters
Capable of settling after 2 hrs
Appearance after settling
Odor
Odor threshold
jH value
Conductivity in microsec
Residue on evaporation
Residue on ignition
Chlorides as Cl
Sulfate as $04
Sulfide as H2S
Overall hardness in ° dH
Calcium as CaO
Iron II
Iron III
Zinc as Zn
Lead as Pb
Copper as Cu
Volatile hydrocarbons
Volatile phenols
Nonvolatile phenols
Fats and Oils
Oxidizability (KMnO, consumption)
BOD-5 H
Before treatment
6 ml/1
slightly turbid,
yellow
intensively of
varnish
1:600
6.0
4,900
2,400 mg/1
1,010 mg/1
150 mg/1
320.0 mg/1
8.0 mg/1
15.6 mg/1
128.0 mg/1
20.0 mg/1
11.0 mg/1
131.0 mg/1
18.0 mg/1
3.5 mg/1
140.0 mg/1
24.0 mg/1
14.0 mg/1
62.0 mg/1
1,940.0 mg/1
1,400.0 mg/1
After treatment
6.3 ml/1
slightly turbid,
almost colorless
stale, faintly of
varnish
1:16
5.3
4,950
2,190 mg/1
1,040 mg/1
155 mg/1
335 mg/1
not traceable
14.2 mg/1
130.0 mg/1
not traceable
36.0 mg/1
135.0 mg/1
16.0 mg/1
3.0 mg/1
20.0 mg/1
4.0 rng/1
not traceable
32.0 mg/1
340.0 mg/1
190.0 mg/1
94
-------
10
en
TAULE 8. WAS1EUATER DISCHARGE OF A PAINT & VARNISH PLANT TREATED 25 MINUTES WITH OZONIZED AIR'
Untreated sewage
after 24 hrs
settling
Sewage acidified
with sulfuric acid
(pll 3.6) addition:
0.05 g iron as Fed,
t 0.05 aluminum as
Al2(S04h. neutral-
ized milk of lime
up to pH 8.1
Clarified sewage
gassed cold with
air
Clarified sewage
gassed hot with
air
Clarified sewage
treated with ozone
Clarified sewage
pre treated with C19,
then treated with
ozone
Appearance
milky turbid,
brownish
clear
yellowish
clear
yellowish
clear
yellowish
clear
yellowish
clear,
strongly
yellowish
* 20 nig ozone/liter of air
Odor
Intensively
of varnish
and esters
intensively
of varnish
and esters
intensively
of varnish
and ester
intensively
of varnish,
faintly of
ester
faintly of
varnish
stale,
somewhat of
benzene
Odor
Thresh-
old
1:1.000
1:900
1:500
1.150
1:18
1:8
KMnOij
Con-
sumption
2.850
2,800
•
2,400
1.400
110
120
BOD-5
mq/1
1.860
1.900
1.600
1.050
180
00
Lead
ma(\
40.0
—
—
__
__
..
Zinc
ma/1
200
—
..
__
__
-.
Volatile
Components
m.i/1
80
80
30
15
__
—
Fats &
Oils
ron/1
98
15
14
16
16
12
Source: Bauch & Burchard. 1970
-------
10
en
TABLE 9. WASTEHATER FROM THE CANAL NEAR THE OUTLET OF A PAINT & VARNISH MANUFACTURING PLANT.
PRE1REAKO BY PRECIPITATION AND TREATED Ullll OZONE* (30 MINUTES) AND CHLORINE
Untreated sewage
after 24 hrs
settling
Sewage acidified to
pll 5.0 with sulfuric
acid addition:
0.1 g/1 iron as
Fed], precipitated
with milk of lline at
pll 7.6
Clarified sewage
gassed cold with
air
Clarified sewage
gassed hot with
air
Clarified sewage
gassed cold with
ozonized air
Clarified sewage
pretreated cold
with excess C\2,
then ozonized air
Appearance
milky, turbid
clear
yellowish
clear
yellowish
clear
yellowish
clear, almost
colorless
clear, almost
colorless
* 20 mg ozone/liter of air
Odor
intensively
of varnish
intensively
of varnish
intensively
of varnish
intensively
of varnish
faintly of
varnish
stale.
indefinable
Odor
Thresh-
old
1:800
1:700
1:500
1:240
1:20
1:4
KMnO/|
Consuuiptic
mg/1
3,850
2.900
2.720
1.800
190
82
BOD- 5
n
mg/1
1.800
2.600
2.100
1.400
260
150
Lead
& Zn
mg/1
114.3
trace:
tracei
traces
traces
traces
Volatile
Portions
mg/1
110
70
60
10
--
Fats
and Oils
mg/1
80
18
16
19
16
5
Source: Bauch & Burchard. 1970
-------
PV-04
Title: "Ozonation of Phenolic Aircraft Paint Stripping Wastewater"
Author: R. H. Kroop
Source: Proc. First Intl. Symp. CM Ozone for Water &^ Wastewater Treatment,
R.G. Rice & M.E. Browning, editors. Intl. Ozone Assoc., Cleveland,
Ohio (1975), p. 660-673.
Aircraft paint stripping wastewaters contain 1,000 to 3,000 mg/1 of
phenols, 1,000 to 3,000 mg/1 of CH2Cl9, 5,000 to 30,000 mg/1 of COD, 50 to
200 mg/1 of Cr, 100 to 1,000 mg/1 of SS, 100 to 2,000 mg/1 of oils and have
pH in the 8.0 to 8.5 range. Some 71.5% of the COD is contributed by phenols.
In batch ozonation experiments with a wastewater containing 2,700 mg/1
phenol, 99.7% of the phenol was destroyed in 1 to 2 hrs, but COD values were
reduced only 57%. CO? formation was not substantial, (10% of stoichiometric)
thus intermediate oxidation products probably were formed which were not
detected by the 4-aminoantipyrine method for phenol. When the pH (8.1) was
not controlled, the ozone/phenol demand was 10.4 moles/mole or 5.30 g/g. At
an initial pH of 11.0, this ratio was lowered to 3.46 moles/mole or 1.77
g/g. Reduction of COD levels during the first 30 min of ozonation was
caused by air stripping of CHgClg. Concentrations of ozone were measured in
the gas phases before and after ozonation.
Continuous flow tests were made using 2-stage ozone contacting at an
influent pH of 11.5. Ozone feed rate to diffuser reactor #1 was 2,000
cc/min at 40 mg/min of ozone, and an additional 1,000 cc/min at 17 mg/min to
diffuser reactor #2. All 40 mg/min of ozone charged to reactor #1 was
consumed in reactor #1. Wastewater flowed through the 2 reactors consecu-
tively. To attain 99% destruction of phenol (first order reaction) required
approximately 200 min (30 mg/1 residual phenol) and to attain 99.9% de-
struction (3 mg/1 residual phenol) required approximately 300 minutes of
ozonation.
After 240 minutes of ozonation, even though the [phenol] was <20 mg/1,
the [COD] was 3,500 mg/1 (65% reduction). To attain 99% phenol removal
required 5.2 moles ozone/mole phenol (2.66 g/g); to attain 99.9% removal
required 8.0 moles/mole (4.50 g/g).
Costs: Capital and operating costs to treat 29,000 gpd of phenolic aircraft
paint stripping wastewater by ozonation were estimated for 2 different
levels of treatment as follows:
phenol]
20 mg/12.0 mg/1
Capital cost $389,000 $505,000
Operating cost $400/day $548/day
References: 10
97
-------
LITERATURE CITED (PETROLEUM REFINERIES) (RE)
RE-01 Alekseeva, V.A., 1965, "Use of Ozone in Purification of Waste-
water", Khim Tekhnol, Topliv i Masel.
RE-02* Alekseeva, V.A. & Ya.A. Karelin, 1963, "The Purification of Pet-
roleum Refinery Wastewaters with Ozone." Neftepererabotka i
Neftekhim., Nauchno-Teknicheskii Sbornik, 5:19-21.
RE-03* Anonymous, 1973, "Ozone Cleans Bug-Ridden Oil", New Scientist,
March, p. 548.
RE-04* Anonymous, 1974, "Disposal, Regeneration and Recovery of Used
Industrial Oils", Machine Moderne, Nov., p. 38-45.
RE-05 Anonymous, 1957, "Removal of Phenols From Refinery Wastes", Oil in
Canada, June 24, p. 26.
RE-06* Dabine, R.A., 1959, "Phenol Free Wastewater." Chem. Engrg., Aug.
24, p. 114-117.
RE-07* Diehl, D.S., R.T. Denbo, M.N. Bhatla & W.D. Sitman, 1971, "Eff-
luent Quality Control at a Large Oil Refinery." J. Water Poll.
Control Fed. 43:2254-2270.
RE-08 Diehl, D., 1976, "Ozone for Taste & Odor Control of a Refinery
Effluent", in Ozone: Analytical Aspects & Odor Control. R.G. Rice
& M.E. Browning, editors. Intl. Ozone Assoc., Cleveland, Ohio, p.
77-78.
RE-09 Filby, J., J. Hutcheon & R. Schutte, 1976, "Use of Ozone in the
Preparation of Industrial Boiler Feed Water", in Forum on Ozone
Disinfection. E.G. Fochtman, R.G. Rice & M.E. Browmng.Tds.,
Intl. Ozone Assoc., Cleveland, Ohio, p. 337-343.
RE-10* Gabovich, R.D. & I.L. Kurinnoi, 1967, "Ozonization of Water
Containing Petroleum Products, Aromatic Hydrocarbons, Nitro
Compounds and Chloro-organic Pesticides." Gig. Naselennykh Mest.,
(USSR) Izd. "Zdorov'ya", p. 31-35.
RE-11* Hoffman, T.W., D.R. Woods, K.L. Murphy & J.D. Norman, 1973,
"Simulation of a Petroleum Refinery Waste Treatment Process", J.
Water Poll. Control Fed. 45(11):2321-2334.
RE-12* loakimis, E.G., A.E. Kulikov, V.I. Nazasov, N.M. Podgoretskaya,
& S.O. Eigenson, 1975, "Use of Ozone in Treating Refinery Wastes",
Chem. Technol. Fuels Oils 11(3-4):188-192.
RE-13 Korolev, A.A., Yu.P. Tikhomirov & P.E. Shkodich, 1972, "Use of
Ozone for Decontamination of Carcinogenic Waste Waters Containing
98
-------
Petroleum Products." Vop. Profil Zagryazneniya Okruzhayushch.
Cheloveka Sredy Kantserogen. Veshchestvami, p. 72-75.
RE-14* Malkina, 1.1., 1971, "Ozone Oxidation of Demulsifiers Present in
Wastewaters From Petroleum Refineries and an Evaluation of the
Toxicity of the Treated Water". Sb. Tr., Mosk. Inzh. Stroit.
Inst. 87:133-136. Chem. Abstr. 78:151232p.
RE-15* McPhee, W.T. & A.R. Smith, 1962, "From Refinery Wastes to Pure
Water", Engrg. Bull., Purdue Univ. Engrg. Ext. Ser. 109:311-326.
RE-16* Murdock, H.R., 1951, "Ozone Provides an Economical Means for
Oxidizing Phenolic Compounds in Coke Oven Wastes", Indl. Engrg.
Chem. 43(11):125A, 126A, 128A.
RE-17 Niegowski, S.J. 1956, "Ozone Method for Destruction of Phenols in
Petroleum Wastewaters", Sewage & Indl. Wastes 28:1266-1272.
RE-18* Peppier, M.L. & G.R.tt. Fern, 1959, "A Laboratory Study on Ozone
Treatment of Refinery Phenolic Wastes". Oil in Canada 11(27):84-
90.
RE-19 Popov, M.A., 1970, "Purification of Petroleum Wastewaters by
Ozonization", Trudy Vses. Nauchno-Issled Dovatel'skii Inst. Vodo
Snab Sehenii Kanalizatsii, Gidrogeologii 2:45-48.
RE-20* Popov, M.A., 1960, "Use of Ozone for the Final Treatment of Eff-
luents From an Oil Refinery", Gig. y Sanit. 25(5):92-93.
RE-21 Schafer, C.J., 1977, "Petroleum Refining and Organic Chemicals:
Canada". U.S. Environmental Protection Agency, Effluent Guidelines
Division, Trip Report, March.
RE-22* Sease, W.S. & G.F. Connell, 1966, "Put Ozone to Work Treating
Plant Wastewater", Plant Engineering, Nov.
RE-23 Sharifov, R.R., Sh.I. Ismailov, S.S. Korf & A.R. Mamedova, 1976,
"Purification of Petroleum-Containing Formation Waters by Ozoniza-
tion and Sorption". Tr. Vnii Vodosnabzh, Kanaliz, Gidrotekhn.
Sooruzh. I Inzh. Gidrogeol. Bakin. Fil., 12:18-22.
RE-24 Sharifov, R.R., L.A. Mamed'yarova & E.V. Shul'ts, 1973, "Treatment
of Wastewater Containing Petroleum Products". Azer. Neft. Khoz.
53(4):36-38.
RE-25 Shevchenko, M.A., Yu.M. Kaliniichuk & R.S. Kas'yanchuk, 1964,
"Purification of Water from Phenols and Petroleum Products by
Ozonization." 'Kr Khim. Zh.
99
-------
RE-26* Tungfanghung Oil Refinery; Tsinghua Univ., 1975, (Res. Group
Treat. Oil Refinery Wastewater, Peking Chem. Works, Peking, Peoples
Rep. China). "Use of Ozonation in the Treatment of Wastewater From
Oil Refineries". Ch'ing Hua Pei Ta Li Kung Hsuch Pao 2(3):69, 87.
Chem. Abstr. 86:47053k.
RE-27* Zaidi, S.A. & F.L. Tollefson, 1976, "Physical-Chemical Treatment
of Sour Gas Plant Process Waste Waters". J. Can. Petrol. Technol.
15(2):39-47.
RE-02
Title: "The Purification of [Petroleum Refinery] Waste Waters With Ozone"
Authors: V.A. Alekseeva & Ya.A. Karelin
Source: Neftepererabotka i Neftekhim., Nauchn.-Tekhn.Sb. 5:19-21 (1963)
Soluble petroleum products present in refinery wastewaters are amenable
only to treatment by oxidation, e.g., with ozone. An ozonator (PO-3-500)
operating at a frequency of 500 Hertz at air pressures of 1.6 to 1.9 atm and
producing 1,540 g of ozone/hr, was used in treating a waste containing 20 to
50 mg/1 of oil residues, having a BOO of 180 to 259 mg/1 and no dissolved
oxygen, to produce an effluent containing 2 to 4 mg/1 of petroleum residues
having a BOD of 8 to 15 mg/1 and 1.8 to 2.7% DO.
RE-03
Title:
Author;
Source:
"Ozone Cleans Bug-Ridden Oil."
Anonymous
New Scientist, March, 1973, p. 548.
Describes ozonation for removal of micro-organisms from lubricating
oils. Filtration and ozonation at 50 g/hr allowed a French automobile
manufacturer to recycle cutting oil and obtain 1 yr of use, whereas oil had
been changed previously up to 7 times/yr.
Refers to an earlier Swiss report: Industrial Recovery, 19, #2.
RE-04
Title: "Disposal, Regeneration and Recovery of Used Industrial Oils"
Author: Anonymous
Source: Machine Moderne, p. 38-45, Nov. 1974
100
-------
State-of-the-art of the disposal of used industrial oils, and methods
for the regeneration and recovery of such oils are described. Some 15% of
the used oils collected are regenerated by vacuum distillation for the
explusion of volatile hydrocarbons, and hydrolyzed with sulfuric acid with
subsequent filtration and adsorption. The recovered oil is processed in a
refinery. Some of the used oil collected is incinerated in refineries or in
thermal power plants, although most of the used oil is disposed of in
sanitary landfills or else in an illegal manner.
According to a new method, cutting oil is regenerated by ozonization at
an ozone consumption of 50 g ozone/cu m of oil followed by filter pressing;
this permits the recovery of 5% fuel oil. In another process the emulsion
is broken by means of ferric chloride and polyelectrolyte. While the super-
natant oil can be removed easily, the water containing Fe salts is treated
with NaOH for flocculation. Lubricating oils are subjected to ultrafiltration
for the quantitative removal of insoluble components, using hexane solvent.
If regeneration no longer is possible, the used oil is refined by decantation
and filtration to recover fuel oil.
RE-06
Title: "Phenol Free Waste Water"
Author: R.A. Dabine
Source: Chem. Engrg., Aug. 24, 1959, p. 114-117.
Describes the wastewater treatment system at the Cities Service 20,000
bbl/day (now British Petroleum's 80,000 bbl/day) Trafalgar refinery in
Bronte, Ontario, Canada. The suggested local discharge standard is 0.015
mg/1 for refinery phenols. Biological treatment reduces phenol concentrations
from 55 mg/1 to 0.38 mg/1, after which ozonation drops this level to 0.012.
Addition of 2 mg/1 of activated carbon removes the last traces of impurities
and brightens the color. Sand filters remove the carbon before discharge to
Lake Ontario.
Contactor: A stainless steel vessel, 20 ft high and 15 ft diameter, with
perforated carborundum pipes at the vessel base.
Wastewater treatment plant capacity is 300 gpm, but it has handled up
to 600 gpm satisfactorily. Total ozone generating capacity is 190 Ibs/day,
and the 15,000 v generator produces ozone at 8 to 9 kwhr/lb. Cities Service
chose ozone over chlorine dioxide because of lower operating costs of
ozonation.
RE-07
Title: "Effluent Quality Control At A Large Oil Refinery"
101
-------
Authors; D.S. Diehl, R.T. Denbo, M.N. Bhata & W.D. Sitman
Source: J. Water Poll. Control Fed. 43:2254-2270 (1971)
In 1969 a study was conducted at the Baton Rouge Humble Oil Refinery
(450,000 bbls/day capacity) to define the refinery's taste and odor contribu-
tion to the Mississippi River. The project included discovering the major
contributors of odorous wastewater and studying methods of reducing odor 1n
various wastewater streams. As a part of this effort laboratory treatability
studies included biological treatment, air stripping, plain detention,
activated carbon adsorption and ozonation. The use of ozone was evaluated
on 3 wastewaters, and ozone was generally responsible for some reduction in
COD and BOD levels.
However, ozone was found to have an unusual effect on the threshold
odor of the wastewater streams tested. Whereas oxygenation of the control
wastewater caused the threshold odor to decrease continually, ozonation
caused the threshold odor to decrease to a certain level and then to increase.
In addition, the character of the odor changed from a hydrocarbon odor to a
sweet/sour odor similar to that of acetic acid.
No quantitative information is reported concerning the above statement,
nor is the method of experimentation discussed. (Abstractors' Note; It is
reasonable that acetic acid could accumulate as a reaction product, as it is
known to be a stable oxidation product of organic materials and only slowly
oxidized by ozone.)
"Ozonization of Water Containing Petroleum Products, Aromatic
Hydrocarbons, Nitro Compounds, and Chloro-organic Pesticides."
Authors; R.D. Gabovich & I.L. Kurinnoi
Source: Gig. Naselennykh Mest (USSR), Izd. "Zdorov'ya," 31-35 (1967).
Review: Ozonation broke down petroleum product contaminants, aromatic
hydrocarbons and nitro compounds. DDT, however, was quite inert to ozone.
Chlorination was not an effective method of water treatment for aromatic
hydrocarbons, nor for nitro compounds. The compounds tested included the
following:
1) Petroleum. About 0.45 mg of ozone was required to break down 1 mg of
petroleum at an original concentration of 10 mg/1.
2) Gasoline. 0.023 mg of ozone/mg of gasoline, in 1 min, decreased the
[gasoline] from 50 mg/1 to 1 mg/1. 5.1 mg/1 dosages of ozone fully
deodorized the water in 5 min.
102
-------
3) Benzene. Benzene (200 mg/1) was oxidized and water was fully deodorized
by 0.1 mg of ozone/mg of benzene.
4) Pi ethyl benzene (DEB). 0.7 to 1.0 mg/1 of ozone/mg of DEB reduced [DEB]
in water from 10-100 to 0.5-0.8 mg/1.
5) a,2,4-dinitrophenol. [DNP] was reduced from 50 mg/1 to 0.35 mg/1 by
doses of 2 mg of ozone/mg of DNP.
6) DDT. At 0.5 mg/1 of DDT, 55.2 mg of ozone/mg of DDT were needed to
halve the concentration.
Economics: Costs were not analyzed.
References: None
RE-11
Title: "Simulation of a Petroleum Refinery Waste Treatment Process."
Authors: T.W. Hoffman, D.R. Woods, K.L. Murphy & J.D. Norman
Source: J. Water Poll. Control Fed. 45(11):2321-2334 (1973).
Review: The strategy for computer simulation of the steady state operation
of the wastewater treatment process at the British Petroleum refinery at
Trafalgar, Ontario, Canada is given. Since 1960, this plant has been using
physical separation of immiscible oil and particulate matter in API separators
and by coagulation, biological removal of dissolved organics by trickling
filter and activated sludge, disposal of solids by aerobic digestion, and
terminal ozonation to remove trace amounts of dissolved organics (mostly
phenols) as well as trace amounts of bacteria and offensive colors, taste
and odors. The ozonized effluent is discharged to a lagoon, thence to a
lake.
Operational plant data were used to calculate reaction rate constants
for the ozonation reactions, assuming zero or first-order kinetics for both
a plug flow and continuous stirred tank reactor hypothesis. A first-order
reaction combined with a plug flow reactor gave the most consistent results.
The [phenol] in the effluent stream can be calculated from the model. The
flow rate of air to the ozonator is fixed and the fraction of different
components stripped and the fraction of the different components that are
oxidized by ozone all are specified.
No specific operational data are given in this paper.
RE-12
Title: "Use of Ozone in Treating Refinery Wastes"
103
-------
Authors: E.G. loakimis, A.E. Kulikov, V.I. Nazarov, N.M. Podgoretskaya &
S.O. Eigenson
Source: Chem. Technol. Fuels Oils 11(3-4):188-192 (1975)
Ozonation was studied in relation to the 3 groups of refinery waste
streams, i.e., a mixed waste before biochemical treatment, a contaminated
storm-drain effluent, and ELOU [desalter] waste after mechanical treatment.
The most effective method of ozonation is multistage contact of the reaction
gas with the waste streams. The maximum reduction in contamination (based
on COD) is 60%. When the refinery waste streams are ozonated in a counterflow
column, the COD and BOD decrease in all stages of the contacting, but the
original ratio of BOD/COD hardly changes at all. The first-order linear
differential equation chosen was tested in a Minsk-22 computer. Results
confirmed the hypothesis of the formation of intermediate products through
the interaction of ozone with the initial "contaminant".
References: 8
"Ozone Oxidation of Demulsifiers Present in Waste Waters From
Petroleum Refineries and an Evaluation of the Toxicity of the
Treated Water"
I.I. Malkina
Sb.Tr., Mosk. Inzh.-Stroit. Inst. 87:133-6 (1971)
NChK, OP-10 and disolvane-4411 demulsifiers present in concentrations
up to 50 mg/1 were 92% to 99% oxidized. The ozonized wastes were not toxic
to Daphm'a magna.
RE-15
Title: "From Refinery Wastes To Pure Water"
Authors: W.T. McPhee & A.R. Smith
Source: Engineering Bull., Purdue Univ., Eng. Ext Ser. 109:311-326 (1962)
Describes data obtained after 2 yrs of operation of the full scale, 300
Igpm design flow (600 Igpm peak) wastewater treatment facility installed in
1957 for the 20,000 bbl/day integrated oil refinery of the Cities Service
Ltd (now BP) plant on the western shore of Lake Ontario near Bronte in
Trafalgar, Canada. Due to the wastewater outfall being relatively near the
Bronte water supply intake, the following rigid effluent standards were set
as objectives:
104
-------
Phenolics less than 20 ppb
Iron 17 mg/1
pH 5.5-10.6
Oil (Total) 15 mg/1
Floating Solids none
Settlable Solids none
Ozonation for removal of phenolics (made up of phenols, cresols plus
other aromatic fractions) was included as a part of a 10-stage treatment
process consisting of:
(1) stripping of sulfides and ammonia,
(2) oil and tank bottoms separation
(3) pH adjustment
(4) temperature adjustment
(5) chemical coagulation and precipitation
(6) 2-stage biological oxidation
(7) final settling
(8) ozonation
(9) adsorption
(10) filtration.
Tests were conducted during the summer of 1960 when the average flow
was 225 Igpm. The phenolic design loading was 200 Ibs/day at 56 mg/1 in the
wastewater.
Oil separators operate at removal efficiencies of 85% to 94%. The
aerated equalization basin lowers phenolic concentrations from ranges of 40
to 80 mg/1 to constant feeds of about 40 mg/1, as well as reducing oil
concentrations from 270-400 mg/1 to 50-100 mg/1. Flocculator-clarifier
units complete oil separation, lowering its concentration below 15 mg/1
using 2 g of alum/gal at pH 10.0. This also reduces [COD] from 2,350-1,200
mg/1 to 240-440 mg/1 and [BOD] from 1,600 mg/1 to 160-260 mg/1. Activated
sludge treatment (13 hrs) reduced [BOD] from an average of 200 mg/1 to
approximately 50 mg/1 and [COD] from an average of 400 to 150 mg/1. In 10
hrs of activated sludge treatment, phenolic concentrations were reduced from
40 to 1 mg/1 or less and, after an additional 3 hrs of aeration and passage
through a Dow-Pac filter, to about 0.35 mg/1.
Wastewater streams fed to the ozonation system contained phenolic
concentrations of 0.16 to 0.39 mg/1 which were oxidized to <0.003 mg/1 (3
ppb). Because ozonation treatment meets the established effluent discharge
standards, the use of activated carbon has not been necessary since steady
state operation of the wastewater treatment plant was attained. Activated
carbon was necessary after ozonation during the first 2 months following
startup. Rapid sand filtration removed any turbidity that may have been
present, and part of the effluent is used in an aquarium (10 ft diameter)
containing several species of trout.
105
-------
The plant effluent is "as good as the raw lake (Ontario) water",
except that total solids are higher (1,522 to 1,606 mg/1 vs 116 to 224 for
raw lake water).
Additional parameters of the final effluent include: ammonia 3.9 to
5.6 mg/1, nitrate 27 mg/1, SS 15 to 32 mg/1, settleable solids 0, DO 4 to 5
mg/1, pH 6.6 to 8.2. The dosages of ozone and reactor dimensions are not
given in this article, however some laboratory data developed by the Welsbach
Co. on biologically oxidized plant wastewaters are given in Table 10.
TABLE 10. LABORATORY DATA OBTAINED BY OZONATION OF REFINERY WASTEWATER
0^ Applied, mg/1
J 0
23
32
48
72
0, Absorbed, mg/1
3 0
21
27
41
55
Phenol ppb
800
30
16
11
13
It is apparent that refinery phenolics are less readily oxidized than
is phenol itself. Also, there is an initial rapid destruction of phenolics,
followed by a much slower reaction.
Abstractors' Note: This ozonation plant has been operating on full scale
since the pilot study was completed in 1960. In a recent review (Ozone
Chemistry and Technology: A Review of the Literature 1961-1974, The Franklin
Institute Press, 1975) E.W.J. Diaper reports that the reactor is a stainless
steel tank 20 ft high and 15 ft in diameter. Ozone is introduced at the
tank bottom through diffusers at the rate of 190 Ibs/day. At a flow of 300
gpm this would correspond to a dosage of 53 mg/1 with a detention time of
about 80 min. Diaper reports that the flow varies from 300 to 600 gpm with
an ozone dosage in the range of 20 to 40 mg/1.
"Ozone Provides an Economical Means for Oxidizing Phenolic Com-
pounds in Coke Oven Wastes"
H.R. Murdock
Indl. & Engrg. Chem. 43(11):125A, 126A, 128A (1951).
Laboratory and pilot studies were conducted on effluents from ammonia
stills following Koppers vapor recirculation type dephenolizers, and these
studies are detailed in the abstract of this article included under Iron &
Steel (I&S-10).
106
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Laboratory studies of treating refining wastes with ozone also are
mentioned. Wastewaters containing phenols and sulfides can be treated with
ozone, but pretreatment by aeration (to remove sulfides) followed by ozonation
(for oxidation of phenols) reduces the ozone demand.
For example, treating refinery wastewater containing 470 mg/1 of phenols
and sulfides with 1,500 mg/1 of ozone reduced the phenols content to zero
(at pH 12.0). Aeration of this same waste, followed by pH adjustment to
12.0, then ozonation, required only 1,200 mg/1 of ozone to reduce the
phenols content to zero.
"A Laboratory Study on Ozone Treatment of Refinery Phenolic
Wastes"
Authors: M.L. Peppier & G.R.H. Fern
Source; Oil in Canada 11(27):84-90 (1959)
A laboratory study was conducted to determine the feasibility of ozone
for treatment of refinery phenolic wastes at Imperial Oil Ltd., Sarnia,
Ontario, Canada. One gal samples of waste streams with various pH and
interfering substances were placed in a 5 liter cylindrical glass reactor
into which ozone was diffused through glass frits at the rate of about 3
g/hr. 150 ml samples were removed over the course of 1.5 hrs.
A Welsbach T-23 lab ozone generator was used. Ozone was prepared in
oxygen and determined by the KI method; phenol by the Gibbs method. Off-
gases were not analyzed for unreacted ozone.
Results are listed in Table 11.
Ozone demand of an unstripped cat cracker condensate containing 1,450
mg/1 S as H2S, 200 mg/1 S as mercaptans and 550 mg/1 of phenol was almost
negligible until sulfides were oxidized [consuming 1.33 g ozone/g ^S
(estimated from graph)]. Ozone demand of stripped condensate was approxi-
mately 5.5 g/g phenol removed. The pH of this sample dropped from 7.4 to
2.3 during ozonation.
An additional test was performed on the effluent from a biological
treatment plant: 345 mg/1 of ozone was required to reduce the phenol content
from 900 to 60 ppb. This corresponds to an ozone consumption of approximately
400 g ozone/g of phenol removed.
107
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TABLE 11. OZONATION OF REFINERY WASTEWATERS AT SARNIA. ONTARIO. CANADA
Sample
Pure Plant phenol in
distd water
do.
Treating Plant Wash Wat
do.
do.
Central Treating Plant
1. Stripped
2. Unstripped
Cat Cracker Condensate
1. As is
2. pH raised
Initial
phenol,
mg/1
492
525
er 288
296
260
Water
85
114
(Stripped)
114
114
Initial
PH
5.7
12.3
(buffered)
9.0
10.5
11.7
7.9
12.0
7.0
12.6
Final
PH
2.5
11.8
8.9
9.2
9.5
6.8
7.5
1.8
9.7
g ozone/
g phenol
removed
2.4
1.6
3.5
3.5
4.0
4.7
4.0
6.0
6.0
The following comparative costs (1959) are given for alternative
methods of phenol removal:
$/1b of phenol removed
Steam & flue gas stripping 0.91
Biological oxidation (800 Ibs/day of phenol) 0.24
Ozone at $0.273/lb ozone & 0.95 to 1.65
3.5 to 6 Ib ozone/lb phenol
These conclusions were drawn:
1. Ozone demand of the Sarnia refinery sour waters is in the range of 3.5
to 6 Ib of ozone/lb of phenol removed.
2. Stripping is necessary for cat cracker condensates, to remove sulfides
which are oxidized prior to phenols.
3. The pH decrease of refinery waste had little or no significant effect
(refinery phenolic waste pH normally is in the alkaline range).
4. Easily oxidized substances present in refinery effluent raise the ozone
demand.
5. Effluent from the biological oxidation plant had a very high ozone
demand. Thus, use of ozone as a polishing agent would not be economi-
cally attractive unless a particularly stringent phenol limit was
imposed on the effluent.
108
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RE-20
Title: "Use of Ozone for the Final Treatment of Effluents From An Oil
Refinery"
Author: M.A. Popov
Source: Gig. y Sanit. 25(5):92-3 (1960)
A mixture of ozone and air removed 75% to 80% of petroleum products
from the wastewater in 16 hrs. Air alone only removed about 60%. The
remaining material had little odor, and 4- to 5-fold dilution removed it
completely.
RE-22
Title: "Put Ozone To Work Treating Plant Wastewater"
Author: W. S. Sease and G. F.. Connell
Source: Plant Engineering, Nov 1966, 2 pages
Briefly discusses the generation of ozone and applications to water,
wastewater, and odor control. In discussing waste treatment possibilities,
reference is made to the Cities Service (now BP) refinery on Lake Ontario
that uses ozone to reduce phenol levels from 300 ppb to 3 ppb in a polishing
operation that follows biological oxidation.
Safety aspects are briefly discussed and a toxic exposure limits
diagram is included in the Figures.
RE-26
Title; "Use of Ozonation in the Treatment of Wastewater from Oil
Refineries"
Authors: Tungfanghung Oil Refinery; Tsinghua Univ.
Source: Ching Hua Pei Ta Li Kung Hsuch Pao 2(3):69,87 (1975)
Wastewater from an oil refinery, after desulfurizing, oil removal,
flotation, biological and aeration treatments, can be purified to surface
water quality by single or 3-stage ozonization. Good results also are
obtained by ozone treatment of the effluent from flotation tanks. This
shows the feasibility of replacing the biological treatment by a chemical
method.
109
-------
RE-27
Title: "Physical-Chemical Treatment of Sour Gas Plant Process Waste
Waters"
Authors: S.A. Zaidi & F.L. Tollefson
Source: J. Can. Petrol. Technol 15(2):39-47 (1976)
The feasibility of physical-chemical treatment of sour gas plant wastes
was studied on laboratory scale. Experimental data on (a) the adsorption of
organic pollutants on Culligan 1627-00 activated carbon, (b) the removal of
sulfides from sulfur plant aqueous waste and (c) the chemical clarification
of 2 waste streams are presented. Experimental data on the treatment of
sour gas plant wastewaters by physical-chemical methods indicate the need
for (a) segregation of various waste streams and (b) a combination of incine-
ration, steam stripping, clarification and activated carbon adsorption for
the treatment and disposal of different streams. Treatment of the sour gas
plant wastewater samples by chlorine-UV oxidation and by ozonation does not
appear to be capable of meeting the current waste quality standards.
References: 6
110
-------
LITERATURE CITED (PHARMACEUTICALS) (PC)
PC-01 P.B. Lederman, H.S. Skovronek & P.E. Des Roslers, 1975, Chem.
Engrg. Progress, 71(4):93-97.
PC-02 French Patent 10128W/06. Issued March 21, 1975.
Ill
-------
LITERATURE CITED (PHENOLS) (PH)
PH-01 Bauch, H. & H. Burchard, 1970, "Investigations Concerning the
Influence of Ozone on Water With Few Impurities", Wasser, Luft und
Betrieb 14(7):270-273.
PH-02* Bauch, H., H. Burchard & H.M. Arsovic, 1970, "Ozone as an Oxida-
tive Disintegrant for Phenols in Aqueous Solutions", Gesundheits-
Ingenieur 91(9):258-262.
PH-03 Bernatek, E. & C. Frengen, 1961, "Ozonolysis of Phenols. I. Ozono-
lysis of Phenol in Ethyl Acetate", Acta Chem. Scand. 15:158-170.
PH-04 Bernatek, E. & A. Vincze, 1962, "Ozonolysis of Phenols. Ill", Acta
Chem. Scand. 16(8):2054-2056.
PH-05 Bernatek, E. & A. Vincze, 1965, "Ozonolysis of Phenols. IV", Acta
Chem. Scand., 19(8):2007-2008.
PH-06* Chen, J.W. & G.V. Smith, 1971, "Feasibility Studies of Appli-
cations of Catalytic Oxidation in Wastewater", EPA Report 17020
ECI-11/71, 73 pages. U.S. Environmental Protection Agency, Washing-
ton, D.C.
PH-07* Chen, J.W., C. Hui, T. Keller & G.V. Smith, 1975, "Catalytic
Ozonation in Aqueous Systems", presented at 68th Meeting of Am.
Inst. Chem. Engrs., Los Angeles, CA, Nov. (27 pages). Am. Inst.
Chem. Engrs., New York, N.Y.
PH-08* Eisenhauer, H.R., 1968, "The Ozonation of Phenolic Wastes", J.
Water Poll. Control Fed. 40:1887-1899.
PH-09* Eisenhauer, H.R., 1971a, "Increased Rate and Efficiency of Pheno-
lic Waste Ozonization", J. Water Poll. Control Fed. 43(2):200-208.
PH-10* Eisenhauer, H.R., 1971b, "Dephenolization by Ozonolysis", Water
Rsch., 5:467-472.
PH-11 Gaboyich, R.D. & I.L. Kurennoi, 1966, "Ozonization of Water Con-
taining Humic Compounds, Phenols, and Pesticides", Vop. Kommunal
Gig., 6:11-19.
PH-12 Gilbert, E., 1976, "Ozonolysis of Chlorophenols and Maleic Acid in
Aqueous Solution", in Proc. Sec. Intl. Symp. On Ozone Techno!.,
R.G. Rice, P. Pichet & M.-A. Vincent, editors, Intl. Ozone Assoc.,
Cleveland, Ohio, p. 253-261.
PH-13 Gilbert, E., 1978, "Reactions of Ozone With Organic Compounds in
Dilute Aqueous Solution: Identification of Their Oxidation Products",
in Ozone/Chlorine Dioxide Oxidation Products of_ Organic Materials,
112
-------
R.G. Rice & J.A. Cotruvo, editors, Intl. Ozone Assoc., Cleveland,
Ohio, p. 227-242.
PH-14* Gould, J.P. & W.J. Weber, Jr., 1976, "Oxidation of Phenols by
Ozone", J. Water Poll. Control Fed. 48(1):47-60.
PH-15 Hann, V.A. & S.J. Niegowski, 1955, "Treatment of Phenolic Wastes
With Ozone", U.S. Patent #2,703,312, March 1.
PH-16 Hirota, D.I., 1970, "Physico-chemical Factors Affecting the
Oxidation of Phenolic Compounds by Ozone". Ph.D. Diss., Michigan
Univ., Ann Arbor, Mich. Accession 0W-73-00170, 162 p.
PH-17* Hill is, R., 1977, "The Treatment of Phenolic Wastes by Ozone",
Presented at 3rd Intl. Symp. on Ozone Technology, Paris, France,
May. Intl. Ozone Assoc., Cleveland, Ohio.
PH-18 Keay, R.E. & G.A. Hamilton, 1975, "Epoxidation of Alkenes and the
Hydroxylation of Phenols by an Intermediate in the Reaction of
Ozone with Alkynes".- J. Appl. Chem. & Biotechnol., 25(7).
PH-19 Leggett, 1920, U.S. Patent 1,341,913.
PH-20 Loffi, I.E. & E.A. Pedace, 1966, "Residual Liquids Containing
Phenols", Saneamiento (Buenos Aires) 30:108-117.
PH-21* Mallevialle, J., 1975, "Action de TOzone dans la Degradation des
Composes Phenoliques Simples et Polymerises: Application aux
MatiSres Humiques Contenues dans TEaux". T.S.M.-TEau, 70(3):107-
113.
PH-22 Marechal, 1905, French Patent 350,679.
PH-23 Nebel, C., R.D. Gottschling, J.L. Holmes & P.C. Unangst, 1976,
"Ozone Oxidation of Phenolic Effluents", in Proc. Sec. Intl. Symp.
on Ozone Technology, R.G. Rice, P. Pichet & M.-A. Vincent, Eds.,
Intl. Ozone Asscc/, Cleveland, Ohio. p. 374-392.
PH-24* Niegowski, S.J., 1953, "Destruction of Phenols by Oxidation with
Ozone". Indl. Engrg. Chem. 45(3):632-634.
PH-25 Pasynkiewicz, J. & A. Grossman, 1967, "The Use of Ozone for
Eliminating Phenols from Gas Works Effluents", Gas World 166(9):4324.
PH-26* Rosfjord, R.E., R.B. Trattner & P.M. Cheremisinoff, 1976, "Phenols:
A Water Pollution Control Assessment". Water & Sewage Works,
March, p. 96-99.
PH-27 Sharonova, N.F. & N.A. Kuz'mina, 1968, "Ozonation of Shale Tar
Water", Khim. Tekhnol Goryuch Prod. IKH Pererab.
113
-------
PH-28* Shuval, H. & M. Peleg, 1975, "Studies on Refractory Organic Matter
from Wastewater by Ozonation". Prog. Rpt. to Gesellschaft ftlr
Kernforschung, Karlsruhe, Germany and the National Council for
R&D, Jerusalem,, Israel, Dec., 23 pp.
PH-29* Smith, G.V., J.W. Chen & K. Seyffarth, 1972, "Catalytic Oxidations
of Aqueous Phenol", Proc. Fifth Intl. Congress on Catalysis,
August, p. 893-903.
PH-30 Spanggord, R.J. & V.J. McClurg, 1978, "Ozone Methods and Ozone
Chemistry of Selected Organics in Water I. Basic Chemistry", in
Ozone/Chlorine Dioxide Oxidation Products of Organic Materials,
R.G. Rice & J.A. Cotruvo, editors, Intl. Ozone Assoc., Cleveland,
Ohio, p. 115-125.
PH-31 Throop, W.M., 1975, "Perplexing Phenols. Alternative Methods for
Removal". Proc. Third Annual Pollution Control Conference,
WWEMA, p. 115-143. Water & Wastewater Equipment Mfgrs. Assoc.,
McLean, VA.
PH-32* Throop, W.M., 1977, "Alternative Methods of Phenol Wastewater
.Control", J. Hazardous Materials 1:319-329.
PH-02
Title: Ozone as an Oxidative Disintegrant for Phenols in Aqueous Solutions
Authors: H. Bauch, H. Burchard, & H. M. Arsovic
Source: Gesundheit-Ingenieur 91(9):258-262 (1970)
Review; Outlines laboratory reactions at 22°C and describes products of
ozonation of the following compounds: phenol; ortho-, meta- and para-cresols;
5 xylenols; chlorobenzene; various chlorophenols and chlorocresols; other
phenols; naphthols and phenols with more than 1 OH group.
Two reactions probably take place; both involving ring splitting: (1)
via the ozonide yielding smaller molecules and (2) via direct oxidation
(ozone decomposition, free oxygen) yielding larger end products. The former
is the initial reaction. Products found include: glyoxylic acid, propionic
acid, maleic acid, mesotartaric acid, glycolic acid, oxalic acid and carbon
dioxide. Treatment of chlorinated phenols produced HC1. Off-gases were
hydrocarbon-free. In general, more highly substituted compounds were more
reactive, especially if the OH groups were sterically unhindered. Oxidizable
decomposition products increased consumption of ozone. Compounds were found
to be 70% to 80% decomposed after application of 2 to 3 moles ozone/mole of
reactant; doubling ozone dosage brought decomposition to 100%. Decomposition
products were biologically non-toxic after sufficiently long ozone treatment.
114
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Ozone Generator: Supplied by Gesellschaft fdr Ozontechnik und Anwendung and
used a synthetic gas mixt of 21% oxygen and 79% nitrogen (to exclude influence
of air pollutants).
Ozone contactor: A 2-stage reactor with a 80 mm high lower stage and an
upper stage 200 mm high filled with Raschig rings. The upper stage was
unnecessary in most cases due to the readily reacting nature of phenols.
Ozone was fed in via a glass tube (35 mm diam x 700 mm). Ozone content was
determined iodometrically. All reactions were followed by gas chromatography.
In no cases were volatile hydrocarbons found.
Phenol can be decomposed by ozone at room temperature to the extent
that it cannot be detected either by gas chromatography or by p-nitroam'line.
Acids are formed during ozonation which are non-ring-containing, aliphatic
acids and the molecules are always smaller than the phenol molecule. Initial
phenol decomposition takes place almost exclusively via the ozonide, resulting
in monobasic acids. With increasing reaction time, other aromatic ring
scission products (polybasic acids) are formed. Phenol decomposition is 70%
complete at 3 moles ozone/mole of phenol, and is 100% complete at 5.5 moles
(200 g ozone/100 g phenol).
Cresols are decomposed significantly more easily than phenol. m-Cresol
decomposes more easily than o- or p-cresols, and the reaction takes place
significantly more rapidly in acid medium than in basic (80% decomposition
at 2 moles of ozone/mole of cresol ~ 85 g of ozone/100 g of cresol).
Ozonation of cresols produces glyoxylic acid, glyoxal and keto-aldenydes.
At first, the methyl group is oxidized, forming hydroxybenzoic acids (sali-
cylic acid has been identified upon ozonation of o-cresol), which oxidize
further to aliphatic mono- and dibasic acids [(maleic acid (I)], mesotartaric
acid by further oxidation of I, acetic acid, propionic acid, glycolic acid,
glyoxylic acid, oxalic acid) and C02- All 3 cresols (o-, m- and p-) produced
the same products upon ozonation — only the reaction rates differed.
Complete oxidation takes place with 4 moles of ozone/mole of cresol.
Xylenols with OH groups ortho or para to the methyl groups react fastest
with ozone, and all react faster than the cresols to produce the same oxida-
tion products as do the cresols. In addition, diacetyl is formed from
1,2,3- and 1,2,4-xylenols. Glyoxal is also formed, which disproportionate*
to glycolic acid in alkaline medium. Keto-aldehydes and hydroxyphthalic
acid also form, which oxidize further. Xylenol ozonation takes place more
rapidly in acid medium, about 80% being decomposed at an ozone/xylenol ratio
of 2/1.
Ozonation of chlorobenzene is slower than phenols, probably because of
its lower solubility, but it forms the same decomposition products as phenol,
plus HC1, chlorotartaric acid, o-, m- and p-chlorophenols. Chlorocresols
and chlorophenols behave similarly upon ozonation. Naphthols, thiophenols
and phenols with several OH groups decomposed by ring rupture as well.
115
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The authors conclude that phenolic decomposition takes place initially
via the ozonide, 3 moles of ozone being consumed/mole of phenol, and forming
3 moles of HoO^. Phenolic, oxidation products, in turn, consume ozone.
Direct oxidation also occurs via the oxygen liberated by ozone decomposition.
Economics: Not mentioned
"Feasibility Studies of Applications of Catalytic Oxidation in
Wastewater."
Authors; J.W. Chen & G.V. Smith
Source: EPA Report 17020 ECI-11/71 (1971), 73 pages. U.S. EPA,
Washington, D.C.
Review: Outlines the application of sonocatalysis to advanced wastewater
treatment. In addition to sonocatalytic oxidation, sonocatalytic ozonation
and catalytic ozonation using Raney Ni catalyst each were tested on treatment
plant effluent, on aqueous solutions of phenol and of o-cnloronitrobenzene
(OCNB).
Apparatus: Welsbach T23 (68 mg ozone/hr at 1.15 mg/1) and Welsbach T408 (10
g ozone/hr at 33 mg/1) ozone generators. The ozone reactor was a Pyrex
tube, 2.25 x 16 inches, with 2 2-mm ID glass tubes for sparging gas at the
bottom.. Sonics were applied by an 880 KHz macrosonic submersible piezocera-
mic transducer with 1.5 sq in surface area mounted at the center of the
bottom of the constant temperature jacket. A macrosonics 180-VF high frequen-
cy generator supplied power to the transducer.
Raney Ni Catalyst: was stirred magnetically in the reaction mixture.
Results; Wastewaters from the Carbondale, Illinois sewage treatment plant
(350 ml samples) showed 78% decrease in COD and 96% decrease in ODI (Oxygen
Demand Index) after 2 hrs insonation in the presence of activated Raney Ni
catalyst. At 800 Hz the fastest removal occurred at 18.2 watts/sq cm.
Sono-ozonation (68 mg/hr of ozone - 33.3 watts/sq cm) for 2 hrs reduced
[COD] by 7558. Raney Ni catalyzed ozonation (10 g/hr ozone, 14,300 mg/1
Raney Ni, without sonics) removed 85% of COD and 60% of TOC in 2 hrs.
Stirring of the Ni catalyst was required.
Aqueous solutions of phenol (500 mg/1 - 200 ml samples) were treated 3
hrs and samples withdrawn every 0.5 hr. Ozonation alone (65 mg/hr) decreased
[phenol] 31% in 3 hrs. Ultrasonics alone caused a 60% decrease in [phenol],
almost linearly. This decrease was unaffected by addition of 160 g of Raney
Ni. Combined sono-ozonation decreased [phenol] 91%, and addition of 160 g
of Raney Ni decreased [phenol] by 95%. Excess Raney Ni was less effective.
Of the ozone fed into the reaction system, 40% was consumed during catalytic
ozonation and 75% during sonocatalytic ozonation.
116
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Compounds identified by UV and TLC from oxidation of phenol were:
catechol, hydroquinone, quinone and pyrogallol. Oxidation times were 0.25
to 3.5 hrs. With either ozonation or Raney Ni catalyzed ozonation, some
hydroquinone and catechol were left in solution. However, in solutions
treated 6 hrs by sonocatalytic ozonation, those intermediates disappeared.
Saturated OCNB solutions in 200 ml distilled water (0.002M) and 2 g Al
powder or 2 g activated Raney Ni (solid OCNB present in all runs) were
irradiated with ultrasound at 800 KHz and sparged 24 hrs with ozone/oxygen.
All OCNB and its ozonation products were destroyed. In 6-hr experiments
using insonation alone, 3 intermediate oxidation products were formed,
isolated and tentatively identified as 2,2'-dichloroazoxybenzene, o-chloro-
phenyl-hydroxylamine and:
c N—N a
Economics: None mentioned.
References; 21
PH-07
Title: "Catalytic Ozonation in Aqueous Systems"
Authors: J.W. Chen, C. Hui, T. Keller & G.V. Smith
Source: Presented at 68th Mtg. of Am. Inst. Chem. Engrs., Los Angeles,
Calif., November, 1975, 27 pp. Am. Inst. Chem. Engrs., New York,
N.Y.
Review: Investigation of catalytic ozonation (using a special Fe203 catalyst)
compared the efficiency with results from ozonation and catalytic oxidation.
Substances oxidized were phenol, ethyl acetoacetate, and an industrial waste
from a chemical company. Variables were gas flow rate, [ozone], liquid
retention time and feed concentration.
Comment: Catalytic ozonation allows at least 2 oxygen atoms from each ozone
molecule to be utilized in the oxidation reaction with phenol. Steady state
was reached in 90 min using ozone alone and in 60 min using catalytic
ozonation. At initial [COD] up to 900 mg/1, 100% removal of COD was obtained
by catalytic ozonation, whereas in the same contact time only 65% (at 200
mg/1 initial COD) and 30% (at 900 mg/1 initial COD) of the initial COD was
removed by ozonation alone (0.2 I/ min; 30 mg/1 [ozone]. Increased contact
times produced increased removal efficiencies, and also could be correlated
to [ozone] in the feed gas.
117
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Ethyl acetoacetate is only slowly oxidized by ozone alone (<10% reduction
in [COD] in 2 hrs). With catalytic ozonation, however, 40% of the COD was
removed in 2 hrs.
Ozone Generator: The ozone generator was not mentioned.
Contactor: A packed bed reactor (glass beads) was used for the steady state
continuous operation, and at least 12 liquid retention times were employed
as contact times (25 min). The flow rate of oxygen or ozone was 0.1 to 0.2
1/min, and [ozone] was 16 to 30 mg/1.
Economics: No specific costs were given, however, the authors maintain that
this process makes ozonation economically feasible.
PH-08
Title: "The Ozonation of Phenolic Wastes."
Author: H.R. Eisenhauer
Source: J. Water Poll. Control Fed. 40:1887-1899 (1968)
Subject: A laboratory study of the oxidation of dilute solutions of pure
phenol. Information is generated on reaction rates, flow rates of ozone,
oxidation products of phenol and their reaction kinetics.
Equipment: Welsbach T-816 Ozonator, Welsbach PA-1 Dryer, Welsbach H-81
Ozone meter, No. 448-118, Lab-crest flowmeter tube, Beckman KD-ZA Spectro-
photometer. The contactor was a sintered dispersion tube in a 38 cm tall
cylinder, 70 mm OD.
Ozone Adsorption: Ozone content in the gas lines before and after reaction
was measured by reaction with potassium iodide and titrated with sodium
thiosulfate.
Major Conclusions:
The rate of phenol degradation may be increased by:
1) Increasing [ozone] in the feed stream
2) Increasing gas flow rate
(3) Reducing gas bubble frequency
(4) Increasing bubble frequency
(5) Increasing gas-liquid contact time.
The first phenol oxidation product was assumed to be catechol, but
hydroquinone also was found. After consumption of about 4 moles of ozone,
substantially all the phenol originally present had disappeared.
118
-------
During the reaction time cited (up to 1 hr), very little phenol was
oxidized completely to C02 + water. The above parameters also were found to
have little effect on reaction efficiency.
Calculations of ozone feed, unreacted ozone, effect of flow rate, and
catechol formation and degradation are contained in 3 appendices.
Cost data: none cited
References: 13
PH-09
Title: "Increased Rate and Efficiency of Phenolic Waste Ozonization.
Author: H. R. Eisenhauer
Source: J. Water Poll. Control Fed. 43(2):200-208 (1971a)
Dilute solutions of pure phenol were used in the experimental procedure,
and oxidized with ozone to produce its sequential oxidation products:
Phenol -» Catechol -»• o-Quinone + yet to be identified -»• COp + H20
Equipment: Welsbach T-816, Welsbach PA-1 Dryer, Beckman Carbon Analyzer.
Contactor: Porous frit in cylinder 70 mm diameter and 38 cm long.
Results: [Phenol] of 50 to 300 mg/1 were ozonized at initial pH values of 3
to 9 and reaction temperatures of 20° to 50°C. The rate of ozone consumption
up to 15 moles/mole of phenol was constant at about 57% of the ozone feed.
Then at about 22 moles/mole of phenol, all the ozone supplied to the reaction
mixture was consumed. The rate of phenol degradation in unbuffered solution
was virtually unaffected by pH, except at pH 11, at which the rate doubled.
As the reaction proceeded, the TOC of the solution decreased, but no
C02 formed until about 1.5 moles of ozone had been consumed, presumably
reflecting conversion of phenol to its first oxidation product, catechol.
C02 formation then began at a rate directly proportional to the ozone consump-
tion. When about 33% of the theoretical amount of the CO? had been formed,
C02 production ceased. Some mechanism of ozone decomposition became operative,
presumably being catalyzed by a phenol oxidation product.
At 50°C, initial reaction efficiency increased to about 65%, and a
greater proportion of phenol was oxidized to C02- At 15 moles of ozone/mole
of phenol at 50°C, C02 production continued, but at a much reduced rate.
If the mechanism of phenol ozonization were free radical or involved
the intermediate formation of 1^2, ferrous salts might be expected to
119
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catalyze the reaction. Instead, ferrous salts inhibited the ozonization.
The pH dependence of initial phenol oxidation suggests that the reaction is
ionic.
Conclusions:
1) Economical ozonation of phenol to COg and water is not feasible.
2) The initial efficiency advantage gained at pH 11 was lost as primary
oxidation products were produced.
(3) If the first stage of oxidation is sufficient to satisfy a pollution
control problem, 98% of the phenol can be removed using 5 moles of
ozone/mole of phenol.
Cost Factors:
At an ozone cost of $0.07/lb ($0.15/kg), a treatment cost of $0.18/lb
of phenol ($0.40/kg) is calculated (98% removal).
References: 5
PH-10
Title: "Dephenolization by Ozonolysis"
Author: H.R. Eisenhauer
Source: Water Research 5:467-472 (1971b)
Laboratory studies were conducted on solutions of phenol in water.
Contactor: Ozone (in air) was passed through a sintered glass dispersion
tube (70 mm diameter x 38 cm high) charged with 1,000 ml of phenol solution.
The gas stream entering and leaving the reactor was analyzed iodometrically
for ozone. Residual phenol in solution was followed by UV absorption.
Initial [phenol] was 50 to 300 mg/1, [ozone] in the gas stream was 15 to 30
mg/1 and ozone flow rates were 0.2 to 0.5 1/min.
Results; Phenol degradation efficiency increased with ozone dose rate and
contact time, and decreased with ozone gas bubble diameter.
Ozonation of neutral, unbuffered, dilute phenol solutions reduced the
pH to 3 to 3.5 rapidly. When the initial pH was adjusted to 3 to 9, the
rate of phenol degradation did not change. At an initial pH of 11, the
reaction rate more than doubled and the system remained basic.
No significant effect of temperature was observed (20° to 50°C) on the
rate of phenol ozonation, but increasing temperature did increase the rate
of complete oxidation to C02- Oxygen added to the ozonized air had no
effect upon the reaction rate. Both ferrous sulfate and ferrous ammonium
120
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sulfate inhibited the ozonation of phenol, indicating that the mechanism is
not free radical and/or does not involve the intermediate formation of
During exhaustive ozonation of phenol at 20°C, no C02 was formed until
1.5 moles of ozone had been consumed, presumably reflecting conversion to
its first oxidation product, catechol . C02 formation then began at a rate
directly proportional to the ozone consumption, 1 mole of C02 being formed
for each 7.3 moles of ozone consumed. Since 2.33 moles of ozone theoretically
should produce 1 mole of C02, the reaction efficiency was only 30%.
After about 33% of the theoretical amount of CO? had formed, the ratio
of C02 formed/ozone consumed changed dramatically and C0~ production ceased.
At 50°C, the initial reaction efficiency increased to about 65%, a
greater proportion was converted to C02 (less than double) and formation of
C02 continued with continued addition of ozone.
Conclusions: Complete oxidation of phenolic effluents cannot be achieved
economically with ozone alone. The initial efficiency advantage gained
at pH 11 disappears as soon as -most of the phenol has been oxidized to the
primary oxidation products. If this 1st stage of oxidation is sufficient to
satisfy a pollution control problem, then 98% of the phenol can be "destroyed"
using only 5 moles of ozone/mole of phenol. At an ozone cost of 7£/lb, this
is equivalent to a treatment cost of 18^/lb of phenol destroyed.
PH-14
Title: "Oxidation of Phenols by Ozone."
Authors: J.P. Gould & W.J. Weber, Jr.
Source: J. Water Poll. Control Fed. 48(1):47-60 (1976)
Study: Describes a laboratory study of the oxidation of phenol by ozonolysis
and delves heavily into the organic chemistry involved. Reactions of ozone
with phenol were investigated to determine (a) the rate at which phenol is
destroyed by ozone and (b) the specific products of ozonolysis of phenol and
their behavior under continued application of ozone.
Equipment: Welsbach T-23 Ozonator plus a 500 ml cylinder fitted with
coarse porosity sintered glass plate diffusers. [Ozone] was followed by the
KI procedure and gas flow rates were monitored. [Phenol] ranged from 1.4 to
1,106 mmoles/1 in phosphate buffered solution. Ozone dose rates were 0.774
to 8.076 moles/mole of phenol originally present.
Results: The rate constant (Kg) for overall disappearance of phenol (I)
from aqueous solutions is 0.132 mole of phenol/mole of ozone. Over a pH
range from 2.27 to 11.06, Ka ranged from 0.11 at low pH to 0.28 at high pH.
Most of this increase in Ka occurred between 4 and 7.5, and was essentially
121
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complete by pH 8. The bulk of change in Ka is completed long before a
significant degree of ionization of I has taken place.
During the early stages of ozonation of I, hydroquinone (II)'is present
at all times in substantially higher concentrations than is catechol (III).
The combined total concentration of II and III reaches a maximum level only
slightly above 10% of the initial concentration of I, indicating that hydroxy-
lation of I is not the most important mode of action of ozone in this system.
The concentrations of II and III pass through maxima during the first 5
minutes of reaction, then fall to relatively insignificant levels in about
10 minutes.
OH
phenol (I) hydroquinone(II) catechol (III)
Glyoxal (IV) and glyoxylic acid (V) account for the bulk "of the organic
carbon present in the reaction mixtures throughout the greater part of the
ozonization runs. [IV] increases to a maximum in the first 10 minutes,
followed by a smooth and gradual dropoff thereafter, reaching very low
values after 30 minutes. At its maximum concentrations, IV accounts for
over 25% of the TOC. Since this level is higher than that of II plus III,
ring cleavage is much preferred to hydroxylation.
[V] passes through a 1st peak after 5 minutes of ozonation (well
before the IV peak) and through a 2nd peak at about 18 minutes (well after
the IV maximum). Thus it is likely that V arises from both ring cleavage of
I and oxidation of IV. V accounts for virtually all organic carbon in the
mixtures after 20 minutes of ozonation.
[Oxalic acid] (VI) rises very slowly, reaching 3% of the organic
carbon originally present after 30 minutes of ozonization. This indicates
that V forms water and C02 without passing through VI.
•COOH —>HOOC-COOH
glyoxal (IV) glyoxylic oxalic acid (VI)
acid (V)
In the systems studied, addition of 24 moles of ozone/mole of I lowered
[COD] 77%. To lower [COO] by another 3% required 24 additional moles of
ozone/mole of I, and to attain 90% COD reduction would require >150 moles of
ozone/mole of I. Thus ozonation beyond the aromatic ring breakpoint is
uneconomical. However, IV and V are relatively inoffensive and readily
122
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biodegradable in comparison with I. Thus, a ratio of 4 to 6 moles of ozone/-
mole of I originally present will assure virtually complete removal of I and
its aromatic by-products. At this point about 33% of the initial organic
carbon will remain, being about evenly divided between IV and V, and a 70%
to 80% reduction in [COD] will have been achieved. [VI] will be <0.5 mg/1.
The aromatic breakpoint may be used as an indicator of optimum ozone dosage.
This can be followed with a COD or TOC monitor.
PH-17
Title: "The Treatment of Phenolic Wastes by Ozone"
Author: R. Hi 11 is
Source: Presented at 3rd Intl. Symp. on Ozone Technology, Paris, France,
May, 1977. Intl. Ozone Assoc., Cleveland, Ohio.
Ozonation of 14 phenols in water was studied over a pH range of 4.0 to
10.0. Ozone was prepared from oxygen, usually at 3.5 g/hr at concentrations
of 22 to 27 g/cu m. Three liters of phenol solution (30 mg/1 in water) were
ozonized in a 1 m tall, 80 mm diameter glass tube, using a sintered glass
disc. The amounts of ozone in feeds and in off-gases were determined to
calculate the amount of ozone consumed. Phenols were analyzed before and
after ozonation (Table 12).
After 10 minutes, [I] was 1.18 mg/1. UV spectrophotometry showed that
as I was being destroyed, another compound (unidentified) was being formed;
this unidentified compound was itself destroyed upon continued ozonation.
Destruction of II and III was faster at higher pH during the initial
period of reaction; however this pH effect became less important as [phenols]
became lower.
CODs of solutions of 6 phenols were studied before and after ozonation
(Table 13).
TABLE 13. EFFECTS OF OZONATION OF PHENOLS ON SOLUTION CODs
Phenol
Phenol
Phenol sul phonic acid
Hydroquinone
Pyrogallol
Pentachlorophenol
B-Naphthol
Time of ozone
treatment
(mins)
8
8
8
8
20
30
COD at start
(mg/1)
70
29
58
33
89
26
COD at
finish
(mg/1)
24
11
18
14
44
19
123
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TABLE 12. OZONATION OF PHENOLS
Phenol
Phenol (II)
Phenol sulfonic
Acid (III)
Hydroquinone
Pyrogallol
p-Chlorophenol
Pentachloro-
phenol (I)
m-Aminophenol
p-Nitrophenol
o-Cresol
m-Cresol
p-Cresol
2,6-Xylenol
e-Naphthol
Dichlorophen
Flow of
Ozonized
Oxygen
2.9
2.9
2.35
2.35
2.35
2.35
2.35
2.35
2.35
2.35
2.35
2.35
2.35
2.35
[Ozone]
(mg/D
27.59
27.59
23.91
21.36
22.26
24.48
25.96
25.02
24.98
24.29
26.02
27.09
27.06
22.76
Treatment
Time
(minutes)
8
8
12
8
10
35
6
10
8
10
8
6
4
10
Residual
Phenol (mg/1
as Phenol)
0.10
0.10
0.13
0.20
N.O. '
0.38
0.01
0.05
0.10
0.05
0.5
N.D.
0.10(a)
0.05(b)
q Ozone/g Phenol
(as phenol except
where noted) to
reduce 30 mg/1 of
phenol to <0.5 mg/1
2.5
2.7
3.0
2.0
2.5
3.8
2.2
2.5
2.5
2.5
2.3
1.9
4.2(a)
2.5(b)
N.D. None detected
(a) Analyzed as 3-naphthol
(b) Analyzed as dichlorophen
ro
-------
In the 1st 4 cases, the COO was destroyed steadily, but In the last 2
cases there was an initial rise in COD during the 1st few minutes, followed
by a steady reduction in COD value.
At higher [ozone] (22 g/cu m), the rate of phenol oxidation was much
faster than at lower concentrations (4.9 g/cu m). Furthermore, the ozonation
time required to attain lower phenol levels also decreased with increasing
[ozone].
Under these treatment conditions, 10 minutes ozonation time reduced
[phenol] from 30 mg/1 to <0.5 (in many cases <0.1) mg/1, except for I. The
g of ozone consumed/g of phenol was 2.0 to 3.0, or 4 to 6 moles of ozone/mole
of phenol. COD values were lowered 50% to 67%, but were not eliminated by
these ozone dosages, indicating that organic compounds remained after
ozonation.
Oxidation products of these phenols were not identified.
For effluent treatment purposes, pH adjustment (to 8.5 to 10) would be
justified only if residual [phenol] of 1 mg/1 is desired.
The effect of pH upon ozonation times was determined for I and III
(Table 14).
TABLE 14. EFFECT OF pH ON OZONATION OF A 30 MG/L SOLUTION OF PHENOL
PH
4.0
7.0
8.5
10.0
Time (mins) to reduce phenol concentration to
5 mg/1
4.0
3.6
2.5
1.2
1 mg/1
5.7
5.4
4.7
2.8
less than 0.1 mg/1
^8.0
^8.0
-v-8.0
^8.0
When considering ozonation of coke oven effluents from the Iron and
Steel industry, for example, ozone will destroy thiocyanates (which are
oxidized to cyanide, then to cyanate, which hydrolyzes to carbonate and
ammonium ions). Thus total ozone demand of such a waste will depend upon
concentrations both of phenols and thiocyanate compounds. Ozonation should
be a good polishing step for effluents which have received primary treatment
by other methods.
125
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PH-21
Title: "Action of Ozone in the Degradation of Simple and Polymeric
Phenolic Compounds. Application to Humic Materials Contained in
Waters".
Author: J. Mallevialle
Source: T.S.M. TEau 70(3):107-113 (1975)
Review: Ozonation of phenol (I), salicylic acid (II) and humic acids (III)
was studied. The contact chamber (2.5 1 volume) was 65 x 750 mm, operated
as a closed system, with ozone in oxygen fed at an average rate of 30 1/hr.
Homogenization of gas and liquid was effected by means of a peristaltic pump
at the base of the column.
Relatively concentrated solutions were used (100 to 200 mg/1) and gas
dosages of 1.1 1/min, containing 25 mg/1 of ozone. Absorption at 210, 270
and 420 nm, [phenol] and total acidity were measured.
Ozonation of I produced catechol and o-quinone (as expected by the
mechanisms of Eisenhauer), but also hydroquinone and p-benzoquinone. These
results confirm the mechanism proposed by Eisenhauer: electrophilic attack
of ozone at the ortho and para positions in I.
In ozonation of II, the TOC value remained constant during the 1st 10
minutes, but degradation of II proceeded faster than degradation of I.
Phenol, catechol and 3 other still unidentified phenolic compounds were
isolated, and 2,3-dihydroxybenzoic acid was shown to be absent. A little
more than 3 moles of ozone were required to degrade 1 mole of II, at which
point no traces of II could be detected by infrared absorption. Strong ab-
sorptions for OH and COOH were observed, indicating that a mixture of car-
boxylic acids had been formed. Ozonation of II was shown to be first-order
for reduction of TOC and TOD values.
Natural waters containing 100 to 200 mg/1 of III were ozonized. Color
decreased rapidly (90% reduced in 10 min), corresponding to a rapid depolymeri-
zation. After 20 minutes, a violet color appeared, due to oxidation of
decomplexed Mn. Chromatographic studies showed the presence of phenolic
compounds as intermediates, but these were not identified. The presence of
formic acid was indicated. These results might also be obtained by ozonizing
synthetic solutions of pesticides and phthalates complexed by humic acids.
In effect, it is possible to increase the concentrations of these complex
compounds by insufficient ozonation.
The authors conclude that for treatment of drinking waters containing
phenolic materials, one must be careful to use a minimum quantity of ozone.
I and salicylic acid initially form other phenolic derivatives upon ozonation,
and these new derivatives require a new and equally large dose of ozone to
degrade them. Waters containing 525 mg of humic acids require 100 mg of
126
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ozone to destroy 95% of the color and 320 mg to destroy 95% of the polyhydroxy-
aromatic derivatives. Thus it is necessary to add 380 and 500 mg of ozone
to lower 75% of the COD and TOC values, respectively.
Therefore, if ozone is used as a water sterilant, one must consider
that phenolic intermediate oxidation products will be formed unless a suffi-
cient amount of ozone is added to degrade these as well. When ozone is used
as the last stage of a water treatment process, the contact time should not
be decreased below that required for virucidal or bactericidal action (0.4
mg/1 — 6 min). One can also use more efficient contacting systems or
follow ozonation with activated carbon filtration.
PH-24
Title: "Destruction of Phenols by Oxidation with Ozone."
Author: S.J. Niegowski
Source: Industrial & Engineering Chemistry, 45(3):632-634 (1953)
Experimental: 500 ml samples were ozonized in a gas washing bottle. Ozone
concentrations 1% to 2% ozone by weight were used, generated by a Welsbach
T-23 generator. A 2nd gas washing bottle was used to collect excess ozone
in a 2% KI solution to determine the relative amount of ozone that had
passed through the sample.
Results: Solutions of 100 mg/1 of phenol and distilled water were adjusted
to pH 12 and ozonized (Table 15).
Solutions of various phenolic wastes were oxidized to 99% removal
(Table 16).
pH Effect: Elevated pH (about 11.8) tended to favor phenol removal.
Oxidation of thiocyanate: 3 parts of ozone were required to oxidize 1 part
of SCN- to CM".
Effect of Sulfide; Prior aeration to remove sulfides reduced the ozone
demand during phenol oxidationn.
Reduction of COD and Color Levels: Oxidation of 1,000 mg/1 of pure phenol
in water at pH 12 is presented in graphic form.
Toxicity of Oxidation Products: An initial [phenol] of 200 mg/1 was ozonized
to 0.1 mg/1. Safe phenol dosage for exposure of blue gills, diatoms and
mayfly larvae was found to be 2.1 mg/1. The ozonated phenol solution had no
toxic effects on any of the organisms tested.
Cost Information: none cited.
References 18
127
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TABLE 15. OZONATION OF PHENOL. o-CRESOL AND p-CRESOL
Phenol
Ozone
dosage
(mg/D
0
54
no
180
220
260
Phenol
remaining,
(mg/1)
96
47
12
0.4
0.2
0.1
o-Cresol
Ozone
dosage
(mg/1)
0
49
100
150
200
240
o-Cresol
remaining,
(mg/1)
99
49
11
1.7
0.2
0.1
m-Cresol
Ozone
dosage,
(mg/1 )
0
57
no
150
200
260
m-Cresol
remaining,
(mg/1))
99
41
2.7
0.4
0.0
0.0
TABLE 16. OZONATION OF PHENOLIC WASTES TO 99% REMOVAL
Source
Coke plant A
Coke plant B
Coke plant C
Coke plant D
Coke plant E
Coke plant F
Coke plant G
Coke plant H
Chemical plant*
Refinery A
Refinery B
Initial
Phenols
(mg/1)
1,240
800
330
140
127
102
51
38
290
605
11,600
Ozone
Demand
(mg/1)
2,500
1,200
1,700
950
550
900
1,000
700
400
750
11,000
Ozone/
Phenol
(mg/1)
2.0
1.5
5.2
6.8
4.3
8.8
20.0
18.0
1.4
1.3
1.0
Residual
Phenols
(mg/1 )
1.2
0.6
1.0
0.1
0.2
0.0
0.4
0.1
0.3
0.3
2.5
* This waste contained 2,4-dichlorophenol. Results are expressed as
2,4-dichlorophenol.
128
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PH-26
Title: "Phenols: A Water Pollution Control Assessment."
Authors: R.E. Rosfjord, R.B. Trattner, & P.M. Cheremisinoff.
Source: Water & Sewage Works, March 1976, 96-99
Review: A comprehensive review of the known methods of treating phenolic
wastes. Ozone is mentioned briefly and labelled as uneconomical.
Cost Equation: One reference cited lists ozone operating cost as $0.75/lb
of phenol removed. Operating costs and capital depreciation are computed
via the following equation:
0 = (330)QXP + (90,000)(F/100)0.6F > 20
and
0 = 330QXP + (350,000)F < 20
Q = daily phenol rate (Ibs of phenol/day)
X = ozone requirement (2 Ibs of ozone/lb of phenol)
P = price of ozone ($0.25/lb)
(includes capital cost)
F = flow rate (gal/min)
References: 74 (only 4 dealing with ozone, and none of these are primary
references).
Abstractor's Comment: An incomplete review of the published literature on
ozone treatment of phenolics.
PH-28
Title:
"Studies on Refractory Organic Matter from Wastewater by Ozoni-
zation."
Authors: H. Shuval & M. Pel eg
Source: Prog. Rept. to Gesellschaft fUr Kernforschung, Karlsruhe, Federal
Republic of Germany and the National Council for R&D, Jerusalem,
Israel, Dec. 1975, 23 pp.
Review: A progress report of the study of ozonation of organic compounds,
as measured by COD; emphasis was placed on the effect of the pH level.
Synthetic solutions of phenol, chlorophenol and wastewater effluents from
municipal sources and from a high rate oxidation pond were ozonized to study
the effects of the following parameters on ozonation at different pH values:
TOC, nitrogen-containing compounds, ether extractives, carbohydrates,
129
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tannins, proteins, fulvic acid, humic acid, hymethomelanic acid, carboxylic
acids and organochloro compounds. Mention is made of virus destruction,
which is somewhat hindered due to the clumping action of viruses.
The reaction rate of ozone with chlorophenol was markedly influenced by
the solution pH, being faster at a basic pH than at an acidic pH. Starting
at pH 10, the reaction was more rapid when the pH was maintained at 10 than
when it was not controlled. Where the pH was allowed to decrease, it reached
a value of about 2.5, at which stage the reaction could not be followed at a
measurable rate. At the same pH, almost the same reaction rate was obtained
in the ozonation of both phenol and o-chlorophenol. When the oxygen flow
rate was varied from 20 1/hr to 40 1/hr (ozone supply of 4.3 and 7.3 mmoles/20
mfn., resp.), the reactions were propagated at almost the same rate. The
rate of C02 formation increased with increasing pH. 80% of the organic
chlorine from o-chlorophenol was converted into chloride ion; the formation
of chloride ion continued even after all the o-chlorophenol had reacted.
Although chlorophenol was destroyed upon ozonation (40 min), total carbon
remained nearly constant at pH 8 and decreased by about 30% at pH 4. Organic
oxidation products were not isolated and identified.
For both types of actual wastewaters, the primary decrease in organic
pollution occurred in the 1st hr of ozonation, after which it proceeded at
a very slow rate. About 3 g/hr of ozone was needed to oxidize the carbon
and nitrogen compounds to C02 and nitrate, resp. Doubling of the oxygen
flow rate from 20 to 40 1/hr did not significantly affect the kinetics of
the degradation of chlorophenols; the steady state [ozone], rather than the
flow, seemed to affect the ozonation reaction rates. The dissolved [ozone]
seemed to be related to pH changes, decreasing after the maximum concentration
had been reached, as the pH increased. At the same time the organic content
decreased, thus decreasing the ozone demand of the pollutants. Nitrogen was
oxidized finally to nitrate in both types of wastewater.
Ozone Generation; A flow rate of 40 1/hr of dry oxygen was used to produce
20 mg/min of ozone. The applied amperage was 200 to 215 ma.
Contacting: Two ozonation techniques were used. In the 1st, ozone was
bubbled through the test soln contained in a 1-liter beaker at the rate of
500 ml/hr, by means of a sintered glass frit. The mixture was stirred at
about 100 rpm with a magnetic stirrer. 0.1N NaOH was used to maintain a
constant pH. In the 2nd method, no stirring was used; instead, ozone bubbles
were spread by a 90 mm diameter sintered glass frit.
The ozonation of wastewater effluents was carried out in a reaction
vessel of 6.5 cm diameter and 52 cm height, with a fritted glass filter at
the bottom. A continuous flow of ozone was passed through the solution.
References: None cited.
130
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PH-29
Title: "Catalytic and Sonocatalytic Oxidations of Aqueous Phenol"
Authors: G.V. Smith, J.W. Chen & K. Seyffarth
Source: Proc. 5th Intl. Congress on Catalysis, Palm Beach, FL, Aug. 21-25,
1972, p. 893-903
Review: Addresses the oxidation of aqueous solutions of phenols (catechol,
hydroquinone, resorcinol, quinone, and pyrogallol) via various combinations
of high frequency ultrasound, Raney Ni and air with ozone.
Ozone Generation and Contacting: Ozone was generated from air using a
Welsbach Ozonator T23 at a rate of 65 mg/hr. The contacting apparatus was
a flat-bottomed tube, 2.25 in diameter x 16 in high, having a transducer
mounted under the bottom. Ozone was bubbled through 200 ml (500 mg phenol/-
liter) of aqueous phenol solutions over 3 hrs. Ultrasonics equipment was
an 800 KHz Macrosonics Aerosol Generator Model 180-VF. Acoustic power
output was 33 watts (average)..
Discussion: No change in [phenol] is seen in the presence of activated
Raney Ni and air without ultrasound. However, when about 65 mg of ozone/hr
(1.15 mg/1) are bubbled through the phenol solution, a 28% decrease in
[phenol] occurs. With insonation alone, an almost linear decrease of 63% in
[phenol] occurs, and the combination of ultrasonic irradiation and ozone
results in a decrease in [phenol] of 94%.
Combining Raney Ni and ultrasound (air atmosphere) causes approximately
the same change as ultrasonic irradiation alone (60% decrease), but Raney Ni
together with ozone decreases [phenol] 68%, compared with 28% for ozone
alone. The lowest [phenol] after 3 hrs treatment (decrease of 95%) was
reached by a combination of ultrasonic irradiation, ozone and activated
Raney Ni. The combination of ozone and Raney Ni results in substantial loss
of carbon, which suggests that this combination is effective in converting
phenol to COg while the other treatments (with the probable exception of
ozone, Raney Ni and ultrasound for which there were no data) merely produce
more highly oxidized species.
In the ozone experiments, the order of increasing reactivity is always
03
-------
polyhydroxybenzenes but do not readily facilitate steps 2 and 3. Raney Ni
must offer a lower energy surface pathway for step 3 and/or step 2 — and it
may also catalyze the decomposition of ozone.
References: 6.
PH-32
Title: "Alternative Methods of Phenol Wastewater Control"
Author: W.M. Throop
Source: J. Hazardous Materials 1:319-329 (1977)
Reviews methods for removing phenol (I) from large volume flow effluents
by biological and chemical oxidation. Adsorption by activated carbon produces
the lowest level of I in the final effluent, but is the most expensive
treatment process. Oxidation by chlorine is effective, but needs careful
control. C102 may be a practical alternative. For very large effluent
flows, ozonation is the least costly of the 3 oxidants which includes
ozone, H202 and KMn04, but at small flows, all 3 are competitive in cost.
Biological treatment of I has a great number of operating problems
(need for pH, N and P adjustment, temperature, sensitivity to shock loads,
need to supply oxygen) and it is questionable whether concentrations <500
ppb can be produced consistently.
Activated carbon produces effluents with <1 ppb I, but the process
requires 3,300 parts of carbon/part of phenol removed. Operational costs
(1976 dollars) to treat 9 MM cu m/yr of wastewater to attain <1 ppb of I are
estimated to be 15$/cu m.
Chlorination requires a minimum dosage of 12 mg/1 at pH 7.0 to 8.3
(Cl/I ratio 98/1) to produce an effluent containing non-detectable I. To
treat a 25 cu m/day waste flow with chlorine would cost $50,000/hr, plus the
capital cost for a chlorinator and chlorine contact chambers. Underchlorina-
tion produces chlorophenols.
[I] of 3 ppb have been attained from 500 mg/1 concentrations using 4/1
H202/I at 49°, pH 5.5 and with 30 minutes retention time. But h^Og must be
treated with ferrous salt catalyst at pH 1.5, then raised to pH 11 to
remove I.
At pH 8.5 to 9.5, KMn04 oxidizes I in 1 to 3 hrs (almost 90% oxidized
in the first 10 minutes. An actual wastewater (25,000 cu m/day) having 123
ppb initial [I] was treated with 1, 5 and 10 mg/1 doses of KMn04 over 20
minutes. A dosage of 10 mg/1 (or a ratio of 80/1) KMnO^/I was required to
remove I. At 1976 prices, the cost to reach 1 ppb [I] in this wastewater is
0.8£/cu m.
132
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Ozonation experiments were conducted on a foundry waste (9MM cu m/yr)
which had been presettled using an anionic polyelectrolyte and decanted (110
ppb [I]). With contact times of 5 minutes at 24°C, ozone dosages of 5.32
mg/1 (03/1 ratio 48/1), non-detectable levels of I were attained in the
effluent. Only at an ozone dosage of 25.5 mg/1 (03/I ratio of 200/1) was a
trace amount of ozone residual detected, however. This indicates that
compounds other than I are produced initially upon ozonation, which themselves
are further oxidized during further ozonation.
Based on a power cost of 3
-------
LITERATURE CITED (PHOTOPROCESSING) (PF)
PF-01 Anonymous, 1975, Kankocho Kogai Senmon Shiryo 10(4):63-74.
PF-02* Bober, T.W. & T.J. Dagon, 1974, "The Regeneration of Ferricyanide
Bleach Using Ozone", Image Technology, Aug/Sept, p. 19-24.
PF-03* Bober, T.W. & T.J. Dagon, 1975, "Ozonation of Photographic Pro-
cessing Wastes", J. Water Poll. Control Fed. 47(8):2114-2129.
PF-04* Dougherty, J.H., J.R. Ghia, W.D. Sitman & K.M. Peil, 1976, "Develop-
ment Document for Interim Final Effluent Limitations Guidelines
and Proposed New Source Performance Standards for the Photographic
Processing Subcategory of the Photographic Point Source Category",
Rept. No. EPA 440/1-76/060 1, Group II, July. U.S. EPA, Effluent
Guidelines Div., Washington, D.C. 20460.
PF-05* Garrison, R.L., C.E. Mauk & H.W. Prengle, Jr., 1974, "Cyanide
Disposal by Ozone Oxidation", AFWL Report TR-73-212. Final Report
for Period April 1972 - Nov. 1973. U.S. Air Force Weapons Labora-
tory, Kirtland Air Force Base, N. Mexico 87117.
PF-06 Garrison, R.L., C.E. Mauk & H.W. Prengle, Jr., 1975, "Advanced
Ozone Oxidation System for Complexed Cyanides", in Proc 1st Intl.
Symp. on Ozone for Water & Wastewater Treatment, R.G. Rice & M.E.
Browning, editors. Intl. Ozone Assoc., Cleveland, Ohio, p. 551-
577.
PF-07* Gorbenko-Germanov, D.S., N.M. Vodop'yanova, N.M. Kharina, M.M.
Gorodnov, V.A. Zaitsev, A.N. Koldashov & Yu. M. Murav'ev, 1975,
"Ozonation of Silver-Containing Wastewaters From Enterprises
Producing Photographic Chemicals", Khim. Prom. 2:21-23.
PF-08* Hendrickson, T.N., 1975, "Economical Application of Recovery &
Pollution Control in the Photographic Film Processing Industry",
in Proc. First Intl. Symp. CM Ozone for Water &^ Wastewater Treatment,
R.G. Rice & M.E. Browning, Editors. Intl. Ozone Assoc., Cleveland,
Ohio, p. 578-586.
PF-09* Hendrickson, T.N. & L.G. Daignault, 1973a, "Treatment of Complex
Cyanide Compounds for Reuse or Disposal." EPA Report No. EPA-R2-
73-269, June. U.S. EPA, Washington, D.C. 20460.
PF-10* Hendrickson, T.N. & L.G. Daignault, 1973b, "Treatment of Photo-
graphic Ferrocyanide-type Bleach Solutions for Reuse and Disposal",
J. Soc. Motion Picture & Television Engrs. 82(9):727-731.
PF-11 Lotz, R.E., 1972, "Chemical Wastes Generated by Air Force Photo-
graphic Operations", Air Force Weapons Lab Report No. AFWL-TR-72-
125, September. U.S. Air Force Weapons Laboratory, Kirtland Air
Force Base, N. Mexico.
134
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PF-12 Mauk, C.E. & H.W. Prengle, Jr., 1976, "Ozone with Ultraviolet
Light Provides Improved Chemical Oxidation of Refractory Organics",
Pollution Engrg., Jan. p. 42-43.
•
PF-02
Title: "The Regeneration of Ferricyanide Bleach Using Ozone"
Authors: T.W. Bober & T.J. Dagon
Source: Image Technology, 14(5):19-24 (1974)
Review: A method was developed using ozone gas to regenerate ferricyanide
bleach overflow. The appreciable salt build-up commonly resulting from
traditional persulfate treatment was eliminated, resulting in less waste.
If a processing lab operates 5.5 days/week, a total of 465 Ibs of Na
ferrocyanide would have to be regenerated/week, which would require 224 Ibs
of K persulfate or 39 Ibs ozone/week, assuming 100% efficiency in both
cases.
Capital costs for the ozone system are $18,700 (1970 prices) and opera-
ting costs are $650/year. Persulfate regenerating costs are $4,070/yr, at
20
-------
of certain refractory developer components - such as color developing
agents, Phenidone, EOTA, and hydroxylamine sulfate - producing more rapid
and more complete breakdown. More complete degradation also was achieved
with Kodak El on developing agent, thiocyanate ion, and formate ion. Ozone
had no significant effect on acetic acid, acetate ion or glydne, and ferri-
cyanide ion degradation was slow and therefore impractical. Methanol was
more rapidly broken down by biological treatment. Compounds degraded more
or less equally by either process included hydroquinone, thiosulfate, sulfite,
formalin, benzyl alcohol and ethylene glycol.
Contactor: Ozone (OREC generator, producing 70 g/hr) was bubbled through a
cylindrical contact chamber (8 columns each 70 mm OD x 38 cm) via a sintered
glass diffuser. Excess ozone was measured in a KI solution. Normally, 1
liter samples were ozonized. In most cases tests were conducted using 3-
liter volumes. Additional experiments were run using a 62-inch high tank
with a built-in gas dispersion apparatus and a 100-gal capacity, in which 80
gal batches of both activated sludge effluent and synthetic processing
wastes were ozonated.
Results: Pure solutions of specific photographic chemicals were ozonized
and the reduction in COO values determined. Pertinent data are given in
Table 17. No attempt was made to optimize conditions for efficient ozone
use with each solution. The purpose of these tests was to treat those
chemicals not amenable to biological treatment with ozone.
Several synthetic photoprocessing effluents were prepared and ozonized.
Pertinent results are listed in Table 18.
TABLE 17. OZONATION OF SYNTHETIC PHOTOPROCESSING EFFLUENTS (SAMPLE VOLUME
= 3 LITERS)
Effluent
Eastman Color Print Film
Ektaprint 3 chemicals
(with bleach-fix regen.)
Kodak ME-4 process
Initial
COD, mq/1
Calcd Actual
2852
2600
4832
2750
2325
4700
Ozonation
dose time
g/hr (hrs)
0.47
1.53
1.53
1.5
5
8
24
4
gas
flow
rate
(1/min)
1
3
3
3
Reduction
in COD
value
50%
47%
75%
41%(a)
(a) no significant additional reduction resulted with longer treatment.
Ozone disinfection of effluent from an activated sludge plant treating
only photographic processing waste also was studied. Complete disinfection
was obtained with 30 minute contact time at ozone dosages of 1.5 mg/l/min
fed to each of 8 consecutive columns. Residual [COO] was reduced from 50 to
30 rng/1, while 1 hr treatment reduced it to 17 mg/1.
136
-------
OJ
TAIil E 18. 020NAT10N OF I'llOTOPROCCSSING CllfMICALS
Compound
cthylene glycol (a)
hydroxylanine sulfate
benzyl alcohol
acetic acid
N.N-diethyl-p-phcnylenediamine
fflono-IICl (CD-I)
2-ainino-S-diethylamino toluene
mono-»ICl(CO-2) (b)
14-amino-N-etliyl -N- (6-niethane
Original
Concn
1 ml/1
1.0 g/1
1 9/1
1.0 g/1
1.0 g/1
1.0 g/1
1.0 g/1
sulfonauiidoethyl)-in-tolu1diiie 1.0 g/l
sesquisulfate oionohydrate]
(CO-3)
4-ainino-3-uielhyl-N-ethyl-N-(a-
hydroxyethyl ] aniline
sulfate (CO-4)
Na thiosulfate
Ha thiosulfate
(jlycine
Na sulfite
hydroqulnone
H
U
p-Me thy 1 ami nophenol
sulfate (Elon)
1 -phenyl -3-pyrazol Idinone
di sodium b'OTA
dmnonluin ferric EOT A
Na formate
formalin
inaleic acid
11
niethanol
K ferricyanidu (e)
u
KCHS
n
u
1.0 g/1
1.0 g/1
10 9/1
5 g/1
1.0 g/1
6.2
1.0
1.0
10.0
2.0 g/1
1.0 g/1
1.0 g/1
0.5 g/1
2.0
5.0
.
-
1.0
11.0
11.0
1.0
1.0
5.0
Oioiidtion
Time(hrs)
a
12-16
24
24
43
16
0.25
8(c)
2
a
Ib
24
24
2
16
4
4
16
22
24
B
16
24
24
4
24
2
100
2
16
8
Ozonation
Oose(g/hr)
0.5
1 88
1.6
2.45
1.6
0.7
1.3
1.3
2.2
2.2
1.39
' 0.42
.0
.9
.55
.55
.9
.4
0.63
1.23
0.45
1.4
2.28
2.44
2.44
2.12
.0
.0
.55
.55
.45
Degree of [COOJ
Reduction
30-3bX
77-782
85-90%
OX
70*
60*
decolorized
SIX
512
67*
90i
9&Z
OX
97X(d)
96X
54X
mx
701
90*
70S
50X
98*
53X
95X
SBi
37X
IX
30X
86X
96X
94*
(a) No further analysis observed upon add 16 hrs trtnt with
excess ozone. Utilization of ozone — 30Z.
(b) Degradation products resisted further breakdown.
ic) Ozone utilization --37X.
Id The same result was obtained using air alone.
(e) Ozonation of K ferrocyanide regenerates K ferrlcyanide, which
can be reused in the bleaching step.
-------
PF-04
Title: "Development Document for Interim Final Effluent Limitations
Guidelines and Proposed New Source Performance Standards for the
Photographic Processing Subcategory of the Photographic Point
Source Category"
Authors: J.H. Dougherty, J.R. Ghia, W.D. Sitman & K.M. Peil
Source: U.S. EPA Report No. EPA 440/1-76/060 1 (Group II) July, 1976, 187
pp. U.S. Environmental Protection Agency, Washington, D.C. 20460
Review: Effluent limitations and guidelines and standards of performance
for photographic processing are set forth, along with supporting data and
rationales for their development. Included are discussions of in-plant
ferricam'de bleach regeneration by ozonation and of end-of-pipe ozone
treatment of various organic compounds.
Ferricyanide bleach regeneration by ozone proceeds by the following
stoichiometric reaction:
2[Fe(CN)6]~4 + H20 + 03 * 2[Fe(CN)g]'3 + 2(OH)~ + 02
The pH of the system increases as the reaction proceeds. HBr can be
added, furnishing both hydrogen ions and bromide, which is required in the
bleaching process. Theoretically, 1 bromide ion is required/ferrocyanide
ion that is oxidized to ferricyanide. Small amounts of sulfuric acid can be
added if slight build-up of bromide ion occurs.
Waste destruction using ozone was successful for many compounds,
including hydroxylamine sulfate, benzyl alcohol, color developer agent,
thiosulfate, hydroquinone, Kodak Elon Developer Agent, Phenidone, EDTA,
ferric EDTA, formate ion, formalin, maleic acid, Eastman Color Print effluent,
Ektaprint 3 effluent, Flexicolor effluent and synthetic effluent from combined
processes. Acetate and glycine do not respond to ozone treatment, and
ethylene glycol, methanol, ferricyanide and ethylene diamine were only
marginally treatable.
Ozone decomposition of ferrocyanide involves a number of competing
reactions; free cyanide breaks down readily in the presence of ozone, to
cyanate ion. This is apparently broken down by a combination of reactions,
including both hydrolysis and oxidation.
Economics: A detailed analysis of total costs incurred in various wastewater
treatments is included, but specific examples of costs of ozone treatment
are not.
References: 99
138
-------
PF-05
Title: "Cyanide Disposal by Ozone Oxidation"
Authors: R.L. Garrison, C.E. Mauk & H.W. Prengle, Jr.
Source: AFWL Report TR-73-212. Final Report for Period April 1972-Nov.
1973 (Feb. 1974). U.S. Air Force Weapons Laboratory, Kirtland Air
Force Base, N. Mexico 87117
Review: A process was developed for complete destruction of total cyanide
in influents as high as 100,000 mg/1, or below 1 mg/1, to produce effluents
with total cyanide below the limits of detection. Influents were aqueous
cyanide and complexed metal cyanide wastes from Air Force electroplating
operations and color photographic film processing.
Laboratory studies showed that destruction of concentrated cyanide is
limited by mass transfer of ozone, and destruction of dilute cyanide is
limited by chemical reaction rate. Ozone at slightly elevated temperatures
in the liquid (150°F) was more-effective than ozone alone, but ozone with UV
light was effective enough to permit design of a successful system. A 4
watt, 253.7 nm UV bulb,-submerged in the liquid in the reactor, was the UV
source.
A pilot scale prototype was designed, constructed and operated to
destroy cyanide wastes to below the detectable limit. The conceptual
design of a full scale system is included.
Vlastewaters Studied: included Ni stripping, Cu plating, Cd plating, photo-
graphic bleach and photographic fixer, each treated by UV/ozone in low and
high concentrations. In all cases, total [cyanide] in the effluents was
below the detectable limit.
Experimental Details: Acrylic plastic was used for the reactor (it is
transparent) and stainless steel and Al were used for portions of the
system in contact with the dry gas phase. Synthetic wastes were studied
first. Ozonation at pH 11.0 converted all CN- to cyanate, after which
acidification to pH 4 immediately hydrolyzed cyanate. Three Ibs of ozone
were found to react with 1 Ib of free CN~, except for Cu-containing solutions,
in which the ratio was 2.5/1. Similar results were obtained using actual
plating and photoprocessing wastes.
Prototype Reactor: 3 vertical countercurrent contact stages were used, each
containing UV light sources and 420 RPM agitation. UV light was used only
when the [CN~] was expected to be <50 mg/1 or when Fe cyanide complexes were
present. The prototype was designed to treat 0.5 gal/8 hrs of waste contain-
ing 40,000 mg/1 of CN , or 15 gal/24 hrs of waste containing 4,000 mg/1 of
CN", or lower.
Each contacting stage was 12 inches in diameter and 16.5 inches tall.
Six 15-watt tubular UV lamps (253.7 nm) were mounted vertically in each
139
-------
stage, 1 inch from the reactor sidewalls. A W.R. Grace LG-2-L2 ozone
generator (oxygen feed) was used, producing 3.2% (by wt) ozone.
Prototype Results: With dilute cyanide wastes (photo bleach, photo fixer,
Cu plating and Ni strip) containing 10 mg/1 CN~, at waste feed rates of 20
gal/day and UV lamps on in all 3 reactor stages, no CN~ was detectable in
the second or third stages for any runs.
Four additional runs were made on concentrated wastes. For Cu plating
waste, UV and heat (150°F) were used in the 3rd stage only (ozone only in
the 1st and 2nd stages). The liquid feed contained 4,000 mg/1 of CN~ (pH
11.5); the pH in stage 3 was controlled at 7 to 8 using sulfuric acid; the
effluent contained <0.1 mg/1 of CN". 2.4 wt % ozone was fed to the 3rd and
2nd stages (0.14 Ib/day and 1.96 Ibs/day, resp.) and off-gases from these
stages were fed to the 1st stage (2.1 Ibs ozone/day total). Approximately
1,600 mg/1 of SS were formed. Over 99.5% of the CN~ was destroyed in the
1st stage, leaving only Fe-complexed cyanide.
Ni strip (4,000 mg/1 of CN) was treated similarly with similar results.
(0.16, 0.26 and 1.68 Ibs/day of ozone were fed to the 3rd, 2nd and 1st
stages, resp.). 97% to 99% of the CN" was removed in the 1st stage. The
treated effluent contained 130 mg/1 of SS.
With photo fixer (700 mg/1 of CN"), 0.43, 0.43 and 1.23 Ibs/day of
ozone were fed to the 3rd, 2nd and 1st stages, resp. UV was used in stage 3
only, but 150°F was maintained in all 3 stages. The pH in stage 1 was
controlled at 7 with NaOH. [CN~] was reduced to 550 mg/1 in stage 1, to 70
mg/1 in stage 2 and to <0.2 mg/1 in stage 3. Treated water contained 625
mg/1 of SS.
Photo bleach (4,000 mg/1 of cyanide complexed with Fe) was treated in
6 stages and 5.9% ozone was employed. 0.50, 0.38, 0.38, 0.50, 0.38 and 0.38
Ibs/day of ozone were fed to the six 6 stages. _UV was used in stages 5 and
6, and 150°F was maintained in all stages. [CN"] leaving the 6 successive
stages, resp., were 2,680, 1,630, 710, 105, 13 and <0.3 mg/1. About 1,900
mg/1 of SS were produced.
In all 4 concentrated wastewater runs, 93% to 99% of the CNO" also was
destroyed.
Cost Estimates: A 3-staged system to treat 5 gpm of cyanide (50,000 mg/1
total CM"), allowing 10.7 hrs/contact stage and using UV and pH control in
the 3rd stage only, and 7,560 Ibs/day of ozone (from oxygen) is estimated to
cost $2.5 MM (plus liquid oxygen storage) and will use 1.35 megawatts of
electricity. This unit would operate 24 hrs/day - 7 days/week.
For treating 1,000 gal/week in 5 24-hr days, ozone (210 Ibs/day) would
be generated from air and the installed cost is estimated at $217,000.
Operating costs would be 8 man hrs/week, 60 Kw of electrical power and
$5,000/yr in replacement UV lights.
140
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PF-07
Title: "Ozonation of Silver Containing Wastewaters from Enterprises
Producing Photographic Chemicals"
Authors: Gorbenko-Germanov, D.S., N.M. Vodop'yanova, N.M. Kharina, M.M.
Gorodnov, V.A. Zaitsev, A.N. Koldashov, & Yu. M. Murav'ev
Source: Khim. Prom. 2:21-23 (1975)
The results of laboratory tests on the destruction of AgBr colloids and
the complete oxidation of gelatin by ozone in dilute aqueous solutions are
cited. Data are presented concerning the ozonation of model solutions of
AgBr colloids and of solutions of photoemulsion produced by 2 Soviet chemical
plants which simulate real wastewaters. On the basis of the data obtained,
an economic estimate is made of a proposed method of ozonation of Ag-contain-
ing wastewaters in which >99% of the Ag is extracted with practically complete
oxidation of the gelatin.
"Economic Application of Ozone for Chemical Recovery and Pollution
Control in the Photographic Film Process Industry"
Author: T.N. Hendrickson
Source: Proc. 1st Intl. Symp. 0£ Ozone for Water and Wastewater Treatment,
R.G. Rice & M.E. Browning, Editors, Intl. Ozone Assoc., Cleveland,
Ohio, 1975, p. 578-586.
Review: Ozone application in the treatment and the regeneration of ferri-
cyanide bleach and bleach-fix is discussed, as well as ozone destruction of
other photographic processing wastes that may violate effluent discharge
limitations. Several case histories are described, including successful
ozone treatment and regeneration of bleach by Photographic Corp of America
(PCA), Berkey Photo, CBS Televison, and JOSR-TV (Nagano City, Japan).
Ozone Generator; The equipment (OzPAC) was designed by CPAC, Inc., Leicester,
N.Y.The system has a capacity of 100 g/hr of ozone at 1.0 to 1.5X of ozone
in air; this could be modified to supply up to 200 g/hr of ozone, with a
concentration range from 0.75 to 1.5% in air.
Contact: Ceramic spargers with a pore size of approximately 100 u located
in the bottom of the waste treatment tanks. The same batch system was used
for both waste treatment and ferricyanide bleach regeneration.
Results: Stoichiometrically, 20.2 Ibs of sodium ferrocyanide decahydrate
could be regenerated to 11.7 Ibs of sodium ferricyanide by 1 Ib of ozone.
Bench top and pilot plant tests showed ozone oxidation efficiency to be
nearly 100% for [ferrocyanide] >1.0 g/1. Destruction of complex cyanide
141
-------
compounds was not practical at room temperature. At Berkey Photo, about 220
consecutive 100-gal batch regnerations of the same ferrlcyanide bleaches
have taken place, with the solution recycled.
When ozone was used in the laboratory rather than air to oxidize ferrous
iron to ferric iron in bleach-fix (iron/EDTA) prior to reuse in the process
bath, aeration time was reduced 50%. No degradation of the various miscel-
laneous organic additives in the "bleach-fix" soln was observed.
For chemical destruction, thiosulfate and sulfite were easily oxidized
to sulfate by ozone. Sulfide compds produced in the process could precipitate
traces of heavy metal ions, and toxicity was reduced by the oxidation of
hydroquinone and Elon. Na, acetate, K acetate, and acetic acid were not
effectively treated with ozone.
Case histories are given showing BOD and COD, removal of heavy metal
ions, and decreased concentrations of metal chelating agents and of complex
cyanides. [BOD-5] in JOSR-TV waste effluents were reduced from 1,500 mg/1
to about 12 mg/1, and Fe, CN, Zn, Ag, and Cd levels lowered to within toxic
level standards by ozone treatment.
Economics: Total investment at JOSR-TV was $34,000; at a savings of $6,000/yr,
this will be repaid within 6 yrs by chemical savings. Berkey Photo bought 2
ozone generating units for about $41,000 (plus installation) with annual
savings resulting from overall recovery of ferrocyanide, thiosulfate, sulfite,
and silver amounting to about $25,000. CBS-TV showed a 2.5 to 3 yr payoff
time.
For an average film processing laboratory, an OzPAC unit, sized for
bleach regeneration only, could return the entire investment in about 24
months; for both chemical recovery and waste treatment, a 60-month payoff
time would be expected.
References: None cited.
PF-09
Title: "Treatment of Complex Cyanide Compounds for Reuse or Disposal"
Authors: T.N. Hendrickson & L.G. Daignault
Source: U.S. EPA Report EPA-R2-73-269, June, 1973. U.S. EPA, Washington,
D.C. 20460
Review: Ozone was evaluated versus other alternates for treating photofinish-
ing solutions and wastes and was compared to electrolysis for ferrocyanide
(bleach) regeneration, and precipitation and chlorination for treatment of
effluents from color photoprocessing wastes.
142
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Ozone Generator: Purification Sciences Incorporated, Geneva, N.Y., Model
LOA-2; Flow: 0 to 20 SCFH; Output: 0 to 3 g/hr with pure oxygen.
Contacting Systems
1. For bench top regeneration the reactor was a hydrometer column; 18.5
inches high x 2.5 inches 00 x 1/8 inch wall thickness and the sparger,
Labpor gas dispersion tubes, polyethylene candles, medium porosity
(Bal-Art Products, Pequannock, NJ).
2. For pilot plant regeneration the reactor was a clear Plexiglass column:
52 inches high x 3.5 inches ID x 0.25 inch wall thickness, together
with a pump (March Manufacturing Co.; Model LC-2A, 115 volts, 60 cycle)
and a flow meter (F.W. Dwyer Manufacturing Co.; Type VFA-34-BV, range
20 to 200 ml/min).
3. For bench top destruction the reactor was a Kimax 1 liter beaker and
hot plate (Dylatherm Model 24202, 500 watts). Sparger was a Labpor gas
dispersion tube, polyethylene candles, medium porosity. Reactor: Kimax
Beaker, 1,000 ml, Hot Plate: Dylatherm Model 25202, 500 watts.
Results; Runs were made using simulated wastes (i.e., using laboratory
grade reagents and photo bleaches from Ektachrome ME-4 & Kodachrome K-12
processors, with the results given in Table 19.
Cost: Cost of regeneration was estimated at $7,200 for equipment, labor and
maintenance. Daily savings amounted to $22.90 or about 2.85^/roll of film
processed. Cost of destruction was estimated at $25,680 for equipment,
labor and maintenance. Daily chemical costs were estimated at $7.65. An
increase of 2
-------
TABLE 19. OZONATION OF SPENT PHOTOGRAPHIC FERROCYANIDE BLEACH SOLUTIONS
)peration
bench top
regeneration
pilot plant
regeneration
bench top
destruction
Ferrocyanide
Concn. Initial
10 ± 0.01 g/1
(1 liter)
30 g/1
(50 gal)
0.01 M
(500 ml)
Ozone
Feed
2.36 g/hr
5 SCFH
2% vol.
5 SCFH
5 SCFH
Reaction
Conditions
pH adjusted
w/HCl; run
until ozone
odor in
off-gas
50-150 m/min
flow rate
1) no pH or
Results
20.2 wt units ferrocyanide
converted to 11.7 wt units
ferri cyanide (100%
efficiency)
for concn <1 g/1, rate of
conversion is indirectly
proportional to ozone flow
(Oo flow const.); no other
data given
little destruction
temp control
2) 5 g steel
wool , 20 ml
HC1
3) 20 ml HC1,
70°-90°C
some destruction at pH <3
temp <80°C - destruction to
0.003 in 30 min at >80°C -
destruction to 0.001 in 18 min.
-------
Review: Methods to recover or destroy the complex cyanides found in photo-
graphic wastewater effluents were evaluated in laboratory studies by electroly-
sis, ozonation, chlorination, and heavy metal ion precipitation.
Recovery processes, directed toward producing a recovered bleach
solution free from by-products that might affect bleaching, were carried out
on the overflow of the concentrated working bleach tank. These resulted in
20.2 g of sodium ferrocyanide decahydrate being converted to 11.7 g of
sodium ferricyanide with 1 g of ozone. There was a direct linear relation-
ship between ozonation time and % conversion. Changes in pH did not affect
the ozonation reaction rate. Ozone oxidation efficiency was near 100% for
[ferrocyanide] >1.0 g/1.
The destruction of ferrocyanide was directed toward reducing the total
[cyanide] to <2 mg/1, while producing only inert end-products. The diluted
solution resulting from the carryover, on the emulsion, of bleach into the
next process bath, as well as the tank overflow mentioned above, received
this treatment. A combination of reactions was observed, with both oxidation
and hydrolysis occurring. Cyanide molecules broke down into formate and
ammonia, or C02 and nitrogen. The pentaferrate [Fe(CN)s] remaining from
ferrocyanide hydrolysis was considered unstable, and should break down into
ferric hydroxide. A nitroprusside intermediate was formed under slightly
acidic conditions.
Ozone Generator: Ozone was generated at a rate of 10 g/hr for bleach
regeneration processes, and 200 g/hr for cyanide destruction.
Contact: Ozonized air was sparged through the bleach from the bottom of the
contact vessel (of which no further description was offered).
Procedure: Synthetic solutions were used to test the following 3 reaction
procedures:
1) Ozone was bubbled into the sample with no pH adjustment or temperature
control. Only slight changes in [ferricyanide] occurred.
2) The test solution was highly acidified (20 ml HC1); 5 g of steel wool
catalyst was present. The complex cyanide underwent some decomposition,
but the reaction was strongly pH-dependent. At pH 3.0, iron hydroxide
and cyanate were produced, but very little decomposition occurred at pH
3.0.
3) The test solution was acidified with HC1 (pH 1.5) and heated. Tempera-
tures ranged from 70 to 90° C. Ozonation promoted a more complete de-
struction of the complex cyanide than did simple heating and aerating.
Precipitation of the complex cyanides proceeded faster than their
decomposition.
145
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Economics: Costs were analyzed on the basis of a single hypothetical
"combined average" processor*. Ozone generators, which produce 10 g/hr and
200 g/hr, cost $2,000 and $14,000, resp., in 1973.
An estimated savings of 2.8
-------
PL-01
PL-02*
PL-03*
PL-04*
LITERATURE CITED —PLASTICS & RESINS (PL)
Bauch, H. & H. Burchard, 1970, "Experiments to Improve Highly
Odorous or Harmful Sewage With Ozone", Wasser Luft u. Betreib
14(4):134-137.
Chen, K.Y. & R.W. Okey, 1977, "Ozone Effect on Synthetic Rubber
Waste Treatment", Industrial Wastes, March/April, p. 46-48.
Kwie, W.W., 1969, "Ozone Treats Wastestreams From Polymer Plant",
Water & Sewage Works, Feb., p. 74-78.
Linevich, S.N., I.M. Arutyunov, R.M. Siganashvin & V.A. Golos-
nitskaya, 1972, "Ozonization of Phenol- and Formaldehyde-Containing
Wastewaters", Tr. Novocherkassk. Politekh. Inst. 249:12-20. Ref.
Zh., Khim. (1972). Abstr. No. 201346.
PL-02
Title: "Ozone Effect on Synthetic Rubber Waste Treatment"
Authors; K.Y. Chen & R.W. Okey
Source; Industrial Wastes, March/April 1977, 46-48
A 10 gpm pilot plant study using actual wastes is described. Wastewaters
from emulsion polymerized GR-S rubber production (containing butadiene,
styrene, K rosin soap, detergent, Na phosphate, NaOH, Cerelose, ferrous
sulfate, KgP207, cumene hydroperoxide, tertiary mercaptans, hydroquinone and
N-phenyl-2-napnthylamine), primarily from the latex filtering step following
coagulation with alum and settling, were studied (BOO 70 mg/1; COD 365
mg/1). The wastes were only slightly biodegradable (about 20%).
Ozone Generator: A laboratory model operating on air at a flow rate of 1.5
and 1.0 std cu ft/hr. [Ozone] was not specified.
Contactor: Bubbler type. Size unspecified.
Results: At 1.5 scfm, plant effluent [COD] was reduced from 365 mg/1 to 160
in 40 minutes. With 350 mg/1 added Na bicarbonate (effluent sample size not
specified) [COD] was reduced to 85 mg/1 in 40 minutes of ozonation. At 1.0
scfm of ozone, plant effluent [COD] was reduced 47%, but in buffered solution
(with Na bicarbonate), reduction of [COD] was 70%.
Decomposition of ozone in water is very rapid above pH 8, and the
efficiency of ozonation is reduced at low pH. Thus the optimum pH range for
ozonation of these wastes is recommended at 6.0 to 8.5.
Ozone treated effluents had substantial influence on oxygen uptake,
whereas untreated effluent had little. This indicates that ozonation of
147
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persistent organic compounds followed by conventional biological treatment
would be the better way to treat many non-biodegradable organic compounds.
Upon ozonation, the distinct odor of butadiene-styrene was replaced by
a milder scent of a "different kind". Turbid solutions became clear and
suspended matter settled within 10 to 20 minutes of ozonation.
PL-03
Title: "Ozone Treats Waste Streams From Polymer Plant"
Author: W.W. Kwie
Source: Water & Sewage Works, Feb. 1969, p. 74-78
This is a laboratory study, with wastes from a synthetic polymer plant
(plant products not identified) containing unsaturated organics and some Na
8-alkylnaphthalene sulfonate-2 (SANS), which is very resistant to biodegrada-
tion.
Ozone Generator: Welsbach Ozonator using oxygen
Contactor; 100 ml bubbler
Results: (1) COD of the monomer plant wastewater (3,340 to 910 mg/1) was
reduced only when unsaturated wastes that react readily with ozone were
used. Absorption of 5,400 mg/1 ozone gave 90% COD removal in unspecified
contact time.
(2) Additional reduction in COD values of ozonated samples was noted with
time. A sample having 1,380 mg/1 immediately after ozonation had 450 mg/1
after 7 days of storage.
(3) Foaming ability, color and odor of these wastewaters were reduced after
ozonation. Colloidal orange substances were transformed by ozone into an
easily settling sludge.
(4) One aromatic ring of SANS was cleaved, however, the remaining aromatic
ring was resistant to further ozonation. Ozonation did not increase the
biodegradability of SANS.
References: 15
PL-04
Ti tle: "Ozonization of Phenol- and Formaldehyde-Containing Wastewaters"
Author: Linevich, S.N., I.M. Arutyunov, R.M. Siganashvin & V.A. Golosnit-
skaya
148
-------
Source: Tr. Novocherkassk. Politekh. Inst. 249:12-20 (1972). Ref. Zh.,
Khim (1972). Abstr. No. 201346
Phenol and formaldehyde In wastewaters were ozonized. Humic acids were
determined in the ozonized solns by UV and IR spectroscopy.
149
-------
LITERATURE CITED (PULP & PAPER) (PU)
PU-01* Abadie-Maumert, F.A., B. Fritzvold & N. Soteland, 1977, "The
• Norwegian Semi-Industrial Pilot Plant for Processing of Paper Pulp
by Ozone". Presented at 3rd Intl. Symp. on Ozone Technol., Paris,
France, May. Intl. Ozone Assoc., Cleveland, Ohio.
PU-02 Ancelle, B. & M. Plancon, 1966, "Bleaching Wood Pulp", French
Patent 1,441,787, June 10. Chem. Abstr. 66:20152s.
PU-03* Anonymous, 1974, "Ozone Bleaching Pilot Plant Called Success",
Paper Trade J., Feb. 4, p. 9.
PU-04* Bauman, H.D. & L.R. Lutz, 1974, "Ozonation of a Kraft Mill Eff-
luent", TAPPI 57(5):116-119.
PU-05* Buley, V.F., 1973, "Potential Oxygen Application in the Pulp &
Paper Industry", TAPPI 56(7):101-104.
PU-06 Clayton, D.W., N. Liebergott & T. Joachimides, 1971, "Evaluation
of Ozone Treatment of Mechanical Pulp", Pulp & Paper Rsch. Inst.
of Canada, Prog. Rept. 39, Oct. 1, p. 106-115.
PU-07* Furgason, R.R., H.L. Harding & M.A. Smith, 1973, "Ozone Treatment
of Waste Effluent." Research Completion Report, OWRR Project No.
A-037-IDA, Water Resources Inst., Univ. of Idaho, April. NTIS
Report No. PB-220,008.
PU-08 Furgason, R.R., H.L. Harding, A.W. Langeland & M.A. Smith, 1974,
"Use of Ozone in the Treatment of Kraft Pulp Mill Liquid Wastes.
Part I. Color, Odor and COO Reduction". Am. Inst. Chem. Engrs.
Symp. Series 70:139.
PU-09 Furgason, R.R., M.A. Smith & H.L. Harding, 1973, "Ozone Treat-
ment of Pulp Mill Wastes", presented at Nat!. Am. Inst. Chem.
Engrs. Mtg., Vancouver, B.C., Sept.
PU-10* Hatakeyama, H., T. Tonooka, J. Nakano & N. Migita, 1967, "Ozonol-
ysis of Lignin Model Compounds", Kogyo Kagaku Zasshi 70(12):148-
152, 2348-2352.
PU-11* Hatateyama, H., T. Tonooka, J. Nakano & N. Migita, 1968, "Degrada-
tion of Lignin with Ozone." Chem. Abstr. 70:12768 (1969). Kogyo
Kagaku Zasshi 71(8):1214-1217.
PU-12* Hosokawa, J., T. Kobayashi & T. Kubo, 1975, "Bleaching of Pulp",
Japan. Kokai 76,139,903, Dec. 2, 1976, Appl. 75/62,661,
26 May. Chem. Abstr. 86:57076 (1977).
150
-------
PU-13 Huriet, B. & P. Gelly, 1970, "Improvements to Processes for the
Decoloring of Effluents From Kraft Pulping", French Patent 1,599,588
(July 15.); Abstr. Bull. Inst. Paper Chem. 42:4413 (1971).
PU-14* Jackowski, J., 1970, "Ozone Treatment of Pulp and Paper Mill
Effluents", Private Communication, Nov. 1970 to I. Gellman. Noted
in Nat'l. Council of the Pulp and Paper Industry for Air and
Stream Improvement, Tech. Bull. #269, Jan. 1974, by R.C. Whittemore
(P. 2).
PU-15 Josephson, J., 1974, "Cleaning Up: Paper Industry's Mess", Env.
Sci. & Technol. 8(l):22-24.
PU-16 Jurgensen, M.F. & J.T. Patton, 1977, "Energy and Protein Produc-
tion From Pulp Mill Wastes", Annual Rept., 6/15/76-6/15/77 under
U.S. ERDA Contract E(ll-l)-2983. See also Progress Reports for
the periods 6/15/77-9/15/77 and 9/15/77-12/15/77 under same contract.
PU-17 Jurgensen, M.F. & J.T. Patton, 1977a, "Energy and Protein Produc-
tion From Pulp Mill Wastes", Prog. Rept. (Dec. 15, 1976-Mar. 15,
1977) under Contract EY-76-S-02-2983, U.S. Dept. of Energy,
Washington, D.C.
PU-18 Jurgensen, M.F. & J.T. Patton, 1977b "Energy and Protein Produc-
tion From Pulp Mill Wastes", Annual Rept. (June 15, 1976-June 15,
1977) under Contract EY-76-S-02-2983, U.S. Dept. of Energy,
Washington, D.C.
PU-19 Jurgensen, M.F. & J.T. Patton, 1977c, "Energy and Protein Produc-
tion From Pulp Mill Wastes", Prog. Rept. (June 15, 1977-Sept. 15,
1977) under Contract EY-76-S-02-2983, U.S. Dept. of Energy,
Washington, D.C.
PU-20 Jurgensen, M.F. & J.T. Patton, 1977d, "Energy and Protein Produc-
tion From Pulp Mill Wastes", Prog. Rept. (Sept. 15, 1977-Dec. 15,
1977) under Contract EY-76-S-02-2983, U.S. Dept. of Energy,
Washington, D.C.
PU-21* Kamishima, H. & I. Akamatsu, 1973, "Attempts to Modify the Acti-
vated Sludge Process for Sulfite Pulp Wastewater", Japanese TAPPI
27(9):449. Abstr. Bull. Inst. Paper Chem. 44(10): 10878 (1974);
44(8):368 (1974).
PU-22* Kamishima, H. & I. Akamatsu, 1974a, "Ozone-Activated Sludge Treat-
ment of Sulfite Pulp Wastewater. Mechanism of BOD Removal,
Treatment conditions and Sequential Treatment". Japanese
TAPPI, 28(8):35-44.
151
-------
PU-23 Kamishima, H. & I. Akamatsu, 1974b, "Ozone-Activated Sludge Treat-
ment of Sulfite Pulp Wastewater". Japanese TAPPI 28(8):368.
Abstr. Bull. Inst. Paper Chem. 45(5):4865 (1974).
PU-24 Katai, A.A. & C. Schuerch, 1966, "Mechanism of Ozone Attack on a
Methyl Glucoside and Cellulosic Materials." J. Poly. Sci., Part A-
1, 4:2683-2703.
PU-25* Katuscak, S., A. Hrivik & M. Mahdalik, 1971a, "Ozonization of
Lignin, Pt. I. Activation of Lignin with Ozone", Papper och Tr3
9:519-523.
PU-26* Katuscak, S., I. Rybarik, E. Paulinyoya & M. Mahdalik, 1971b,
"Ozonation of Lignin, Pt. II. Investigation of Changes in the
Structure of Methanol Lignin During Ozonation." Papper och Tr3
11:665-670.
PU-27* Kiryushina, M.F. & D.V. Tishchenko, 1968, "Soda Lignin III.
Lignin-Carbohydrate Bond in Soda Lignin From Hardwoods", Zhur.
Priklad. Khim. (Leningrad) 41(8):1848-1853. Chem. Abstr. 70:12767p
(1969).
PU-28* Kobayashi, T., J. Hosokawa & T. Kubo, 1976, "Bleaching of Pulp
With Ozone", Japan. Kokai 76,139,902, Dec. 2, Appl. 75/62,660, May
26, 1975.
PU-29 Lantican, D.M., W.A. Cote, Jr. & C. Skaar, 1965, "Effect of Ozone
Treatment on the Hygroscopicity, Permeability and Ultrastructure
of the Heartwood of Western Red Cedar", Indl. Engrg. Chem., Prod
R&D 4(2):66-70.
PU-30 Liebergott, N., ca. 1969, "Paprizone Treatment. A New Technique
for Brightening and Strengthening Mechanical Pulps." Publication
Not Identified.
PU-31 Liebergott, N., 1975, "Use of Ozone in the Pulp & Paper Industry
for Pulp Bleaching." in Ozone for Water & Wastewater Treatment,
R.G. Rice & M.E. Browning, Eds., Intl. Ozone Assoc., Cleveland,
Ohio, p. 614-624.
PU-32 Melnyk, P.B. & A. Netzer, 1976, "Reactions of Ozone With Chromo-
genic Lignins in Pulp and Paper Mill Wastewater", in Proc. Sec.
Intl. Symp. on Ozone Techno]., R.G. Rice, P. Pichet & M.-A.TTncent,
Eds. Intl. OTone Assoc., Cleveland, Ohio, p. 321-335.
PU-33 Moergeli, B., 1973, "Possible Uses of Filtration in the Clarifica-
tion of Residual Wastewater." Wochenbl. Papierfabr. 101(22):875.
Chem. Abstr. 80(12):63609c (1974).
152
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PU-34* Moore, W.E., M. Effland, 8. Sinha, M.P. Burdick & C. Schuerch,
1966, "The Resistance of Henri celluloses in Wood Fiber to Degrada-
tion by Ozone", TAPPI 49(5):206-209.
PU-35 Mueller, J.C. & C.C. Walden, 1970, "Microbiological Utilization of
Sulfite Liquor", British Columbia Research Report 323.
PU-36 Nakano, J. & N. Migita, 1968, "Degradation of Lignin With Ozone",
Kogyo Kagaku Zasshi 71(8):1214-1217. Chem. Abstr. 70:12761n
(1969).
PU-37 Nebel, C. e_t a_L_, 1974a, "Ozone Decolorization of Effluents From
Secondary Effluents", Paper Trade J. 158(4):24.
PU-38* Nebel, C., R. Gottschling & H.J. O'Neill, 1974b, "Ozone: A New
Method to Remove Color in Secondary Effluents". Pulp & Paper
48(10):142-145.
PU-39* Nebel, C., R.D. Gottschling & H.J. O'Neill, 1974c, "Ozone Decolori-
zation of Pulp and Paper Mill Secondary Effluents", in Prpc. 7th
Mid-Atlantic Indl. Wastes Conf.. Drexel Univ., Philadelphia, Pa.
p. 161-187.
PU-40 Nebel, C., R.D. Gottschling & H.J. O'Neill, 1975, "Ozone Decolori-
zation of Secondary Pulp & Paper Mill Effluents." in Ozone for
Water & Wastewater Treatment, R.G. Rice & M.E. Browning, Eds.,
Intl. Ozone Assoc., Cleveland, Ohio, p. 625-651.
PU-41* Neimo, L., H. Sihtola, 0. Harva & A. Sivola, 1967, "Graft Copolymers
of Cellulose. Polymerization Initiated by Decomposition of
Cellulose Peroxides." Papper och Tra" 8:509-516.
PU-42 Ng, K.S., J.C. Mueller & C.C. Walden, 1978, "Ozone Treatment of
Kraft Mill Wastes", J. Water Poll. Control Fed. 50(7):1742-1749.
PU-43 Osawa, Z. & C. Schuerch, 1963a, "The Action of Gaseous Reagents on
Cellulosic Materials. I. Ozonization and Reduction of Unbleached
Kraft Pulp", TAPPI 46(2):79-84.
PU-44* Osawa, Z., W.A. Erby, K.V. Sarkanen, E. Carpenter & C. Schuerch,
1963b, "The Action of Gaseous Reagents on Cellulosic Material. II.
Pulping of Wood with Ozone". TAPPI 46(2):84-88.
PU-45* Ottman, R., 1972, "Ozonation of Kraft Pulp & Paper Effluents",
Private Communication.
PU-46* Pristupa, A.M., 1974, "Treatment of Industrial Effluents and
Gaseous Discharges in U.S. Industries", Bumazhn. Promy. (Moscow)
12:23-26.
153
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PU-47 Samuel son, 0., G. GrangSrd, K. Jonsson & K. Schramm, 1953. Svensk.
Papperstidn. 56:779-784.
PU-48 Secrist, R.B. & R.P. Singh, 1971, TAPPI 54(4):581.
PU-49 Smith, M.A. & R.R. Furgason, 1976, "Use of Ozone in the Treatment
of Kraft Pulp Mill Liquid Wastes. Part II. Biodegradation", in
Proc. Sec. Intl. Symp. on Ozone Techno!., R.G. Rice, P. Pichet &
M.-A. Vincent, Eds., IntT. Ozone Assoc., Cleveland, Ohio, p. 309-
320.
PU-50 Soteland, N. & K. Kringstad, 1968, "The Effect of Ozone on Some
Properties of High Yield Pulps". Norsk Skogindustri 22(2):46-52.
PU-51 Soteland, N., 1971, "The Effect of Ozone on Some Properties of
Groundwoods of Four Species. Part 1." Norsk Skogindustri 25(3):61-
66.
PU-52 Soteland, N., 1974, "Bleaching of Chemical Pulps with Oxygen and
Ozone", Pulp & Paper Mag. of Canada 76(4):91-96.
PU-53 Soteland, N. & V. Loras, 1974, "The Effect of Ozone on Mechanical
Pulps", Norsk Skogindustri 28(6):165-169.
PU-54 Stern, A.M. & L.L. Gasner, 1974, "Degradation of Lignin by Com-
bined Chemical and Biological Treatment", Biotech. Bioengrg.
16:789-805.
PU-55 Tuggle, M.L., 1972, "Reactions of Ozone With Reduced Sulfur Com-
pounds Present in Kraft Mill Gaseous Emissions", Nat!. Council of
the Paper Industry for Air & Stream Improvement, Tech. Bull. No. 58,
Feb.
PU-56 Tyuftina, V.I., 1971, "Reduction of Effluent Color Intensity by
Ozonization", Sb. Tr. VNII Gidroliza Rast. Mater. (USSR) 19:209.
Abstr. Bull. Inst. Paper Chem. 42:11444 (1972).
PU-57* Watkins, S.H., 1973, "Coliform Bacteria Growth and Control in
Aerated Stabilization Basins". EPA Report No. EPA/660/2-73-029,
Dec., p. 220-221.
PU-58* Whittemore, R.C. & J.J. McKeown, 1974, "Preliminary Laboratory
Studies of the Decolorization and Bactericidal Properties of Ozone
in Pulp and Paper Mill Effluents." Nat'l Council of the Paper
Industry for Air & Stream Improvement, Inc., Technical Bulletin
#269, January (40 pages).
PU-59 Wigren, G.A., 1965, "Bleaching of Pulp in a Chlorine-containing
Bath Treated with Ozone", German Patent #1,293,875, January.
154
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PU-01
Title: "The Norwegian Semi-Industrial Pilot Plant for Processing of Paper
Pulp by Ozone".
Authors: F.A. Abadie-Maumert, B. Fritzvold & N. Soteland
Source: Presented at 3rd Intl. Symp. on Ozone Technol., Paris, France,
May 1977. Intl. Ozone Assoc., Cleveland, Ohio.
Although the 1st research on the use of ozone for processing paper pulp
dates from 1912, it is only since 1967 and the publication of the first work
of the Norwegian Institute of Paper Research that laboratories in the major
industrial countries have started to take an active interest in the possibili-
ties of using ozone in the paper industry.
In 2 fields - the improvement of mechanical properties of mechanical
pulps and the bleaching of chemical pulps - excellent laboratory results
have been obtained, which open wide perspectives from the points of view of
technology and the environment, for methods using ozone are considerably
less polluting than traditional methods.
The results of laboratory research have been so promising that the
Norwegian Institute for Paper Research, 5 of the biggest Norwegian paper
companies, and the mechanical engineering company Myrens Verksted have
collaborated in the construction of a semi-industrial plant for the processing
of paper pulp by ozone.
The plant processes a maximum of 200 kg of mechanical or chemical
pulp/hr with 6 kg of ozone. It is integrated into an existing paper pulp
factory, which enables the processed pulp to be treated under industrial
conditions. Oxygen is used for the production of ozone. The processing of
the pulp takes place in a reactor, which operates continuously at ambient
temperatures, and without overpressure, a prototype of a future industrial
plant.
As this is a case of application of an entirely new technique to a
traditional industry, particular attention has been paid to safety and
control. The method adopted for destruction of the last residues of ozone
has proved to be satisfactory.
The plant has been in operation since May 1976, and is at present
undergoing its 2nd test campaign. It has provided a means of verifying the
promising results obtained in the laboratory on a semi-industrial scale. In
some cases results even better than those obtained in the laboratory were
achieved.
The use of ozone-treated mechanical pulp has provided, among other
things, for production of newspaper without chemical pulp and its printing
on rapid rotary presses.
155
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Since it was started up, the plant has been in regular service for
tests, not only for its promoters but also for foreign paper companies.
It opens up interesting prospects for the production of bleached bisulfite
pulps and semi-bleached sulfate pulps without the use of chlorine, as well
as for the development of use of different types of mechanical pulps for the
production of printing paper, absorbent paper and cardboard.
The paper pulp industry represents a considerable potential market for
ozone. The future of its use in the paper industry depends on the construc-
tion of ozone production plants of sufficient capacity, and above all on
the possibilities of producing ozone at a cost such that it becomes competi-
tive with other techniques used at present.
PU-03
Title: "Ozone Bleaching Pilot Plant Called Success"
Author: Anonymous
Source: Paper Trade J., Feb. 4, 1974, p. 9.
Ozone bleaching of wood pulp is said to be a step closer to commerciali-
zation now that successful pilot plant work has been completed in a joint
effort by Scott Paper, W.R. Grace & Co., and Improved Machinery.
A single-stage 15 ton/day continuous reactor was operated using mixed
hardwood kraft pulp at Scott's pulp mill at Muskegon, Mich. Ozone in oxygen
carrier gas was passed through a fluffed moving bed of pulp where the ozone
was stripped out and the carrier gas then recycled to the ozone generator.
The kinetics of the reaction of ozone with pulp lignin were established
as well as purification requirements of the carrier gas for re-entry to the
ozone generator.
The economics as well as the pollution abatement potential of ozone
bleaching appear to make the process an attractive alternate for conventional
hardwood bleaching.
"Ozonation of a Kraft Mill Effluent."
H.D. Bauman & L.R. Lutz
TAPPI 57(5):116-119 (1974)
The P.M. Glatfelter Co. plant at Spring Grove PA produces about 500
tons/day of fully bleached kraft pulp from both hard and soft woods and
about 600 tons/day of fine papers. Wastewaters from the pulp mill, bleach
156
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plant and paper plant are combined and given primary treatment and contact
stabilization, activated sludge secondary treatment. Ozonation studies were
conducted only on the secondary effluent because the high BOD before secondary
treatment greatly increased ozone demand.
The secondary effluent (15 mgd) is consistently low in BOD (10 to 2
mg/1, average 5) and SS (50 to 12 mg/1, 25 average), but high in COD (typi-
cally 225 mg/1).
Ozone Generator: A Cochrane Div. of Crane Co., vertical tube unit produced
80 g/hr of ozone from oxygen and 40 g/hr from air. Using oxygen feed, power
costs to produce ozone were 3.5 kwhr/lb of ozone, consistently.
Contact Towers: 4 13-ft high towers fabricated from 8-inch schedule 40
steel pipe. Ozone was introduced through 2-inch stainless steel spargers,
one/tower, about 1 ft above the bottom of each tower. The liquid columns
were 11 ft deep, and foam overflow outlets were provided. However, foaming
was never a problem and no excess ozone was wasted from the vents. Most of
the study was done at 4 gpm flow rates, which resulted in 30 minute total
retention time, or about 7 min/tower. Gas flow was divided and regulated so
that 40% of the ozone was applied in Tower 1, 30% in Tower 2, 20% in Tower 3
and 10% jn Tower 4.
In preliminary studies which were up to 1 day of continuous ozonation,
allowing up to 2 hrs continuous running at each level of ozone applied, it
was found that nothing was gained by exceeding a total ozone dosage of 40
mg/1, and very little by exceeding 30 mg/1. SS were removed by flotation
and foam removal. Almost no bacteria were killed at ozone doses up to 20
mg/1. However when bactericidal action began, coliform organisms appeared
to be selectively destroyed. At 30 mg/1 ozone, 60% to 80% reduction in
coliform organisms was achieved, and essentially 100% at 40 mg/1; however,
the total bacterial count remained surprisingly high (numbers not presented).
During preliminary studies with 5-u mean pore size spargers and air
feed, the spargers became plugged with CaCO? after a few hrs of running
time. They could be cleaned with dilute HCI, but this would have prevented
extended runs. Spargers with 20-y mean pore sizes were substituted, which
extended the running time to at least 72 hrs before plugging occurred.
Using oxygen feed to the generator, even the 20-y spargers plugged with
CaC03 in about 24 hrs. The only solution to this problem was daily acid
cleaning.
Eight replicate ozonation runs using 20-y spargers produced 60% to 65%
color reduction at 30 to 40 mg/1 ozone dosages. Dosages of 20 to 30 mg/1
caused 100% increases in BOD. When oxygen was used as feed gas, the effluent
contained nearly 40 mg/1 of dissolved oxygen, which was usually double the
BOD of the ozonized effluent. Air feed increased the effluent BOD, but not
the DO.
157
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In other experiments, the [ozone] in the gas streams introduced to the
contacting towers was varied (0.45% at 10 mg/1 of applied ozone, 0.90% at 18
mg/1, 1.35% at 30 mg/1 and 1.8% at 38 mg/1). Color reduction depended on
the amount of ozone applied and was nearly independent of dose gas concentra-
tion.
Multiple regression analyses indicated that the only significant
variables affecting color removal are: [applied ozone], initial color, COD,
SS and units of color lost.
In an extended ozonation run, 80% color reduction was attained after 80
mg/1 of ozone dosage, but about 30 mg/1 of color remained even after 300
mg/1 of ozone dosage. The BOD rose from 10 to 24 mg/1 at 40 mg/1 of ozone,
remained at 20 to 25 mg/1 up to 200 mg/1 of ozone dosage, and decreased to
10 mg/1 at 280 mg/1 ozone dosage. About 99% of the coliform bacteria were
killed by 40 mg/1 of ozone and 99% of the total bacteria were killed by 100
mg/1 of ozone.
Capital costs to treat 15 mgd with up to 40 mg/1 of ozone (from oxygen)
are estimated at $1 to 1.5 mil-lion. The ozonation plant would require about
5 kwhr/lb of ozone and would produce ozone at $0.25/lb.
With 15 mgd of an effluent whose color is <1,000 mg/1, COD 200 mg/1, SS
<50 mg/1 from 500 tons/day pulp plant and assuming electrical power at
$0.015/kwhr, the operating costs at various ozone dosages are as follows:
Color of Operating Cost
Ozonated
mg/1 Ozone Effluent Yearly
10 300-450 $121,500
20 250-350 $243,000
30 150-200 $364,500
40 125-175 $486,000
>er Ton
of Pulp
$0.675
$1.35
$2.03
$2.70
PU-05
Title: "Potential Oxygen Application in the Pulp and Paper Industry"
Author: V.F. Buley
Source: TAPPI 56(7):101-104 (1973).
High purity oxygen is on the fringes of numerous process applications
in the pulp and paper industry. Interest in oxygen continues to be strong
as new and old processes in the mills come under renewed investigation.
This paper describes several developments in oxygen processes suitable for
pulp mill applications. Specifically, weak black liquor oxidation, ozonation
of pulp mill wastes, and pipeline reactors for the treatment of pulp mill
liquor wastes are discussed.
158
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PU-07
Title: "Ozone Treatment of Waste Effluent"
Authors: R.R. Furgason, H.L. Harding & M.A. Smith
Source: Research Technical Completion Report, OWRR Project No. A-037-IDA,
Water Resources Research Inst., University of Idaho, April 1973.
NTIS Rept. No. PB-220,008.
Review: The report describes a portable ozone test unit and several field
tests made with the unit. Details of the portable test unit are as follows:
Reactor Volume
Reactor Residence
Feed Rate
Ozone Production
Contactor
time
2 gal
1-20 min
0-1.5 gpm
12 g/hr
Venturi type
Experimental: The unit was light and easily moved in a van or pickup truck
and required only 110 v of electricity, cooling water and the material to be
treated for its operation.
Effluents from the Potlatch Forests Inc. kraft pulp mill at Lewiston,
Idaho were treated. Waste streams from the bleach plant, total plant,
primary clarifier and the extended aeration secondary system were tested.
Since few differences were noted in color and reductions in [COD] or odor
removals, the bulk of the data was taken on the primary clarifier output.
Color of the sulfite liquor changed dramatically from dark chocolate
brown to light straw yellow in 5 min. At the same time the strong S-laden
odor disappeared entirely. Reduction in [COD], however, was far less spec-
tacular, being 10% to 15% in 5 min (sometimes up to 30%). The ozonized
organic material was more biodegradable. Thus ozonation should precede
secondary biological treatment and should not be used as a post- or tertiary
treatment (alone).
Conclusions: The portable ozone unit has demonstrated its ability to
obtain information, but a larger ozonator should be incorporated into the
unit; other methods of contacting, however, should also be considered.
Economics: Preliminary estimates indicated costs to be 30^/1,000 gal for
decolorization and deodorization with a full sized plant (size not specified)
but the authors recommend further tests on larger scale to refine these
estimates.
"Ozonolysis of Lignin Model Compounds."
159
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Authors: H. Hatakeyama, T. Tonooka, J. Nakano, & N. Migita
Source: Kogyo Kagaku Zasshi, 70(12):148-152, 2348-2352 (1967)
Review: The mechanism of degradation of the guaiacyl nucleus of lignin is
discussed on the basis of the ozonolysis reaction products obtained from
model experiments, using vanillyl alcohol and veratryl alcohol. These
corresponded to the terminal and internal guaiacyl groups of the lignin
structure. Paper chromatography and thin layer chromatography were used to
separate the reaction products.
When free phenolic hydroxyl groups were present, the main ozonolysis
reaction involved opening of the aromatic ring to give a muconic acid
derivative; this was further degraded to maleic acid or oxalic acid. Where
the phenolic OH groups in non-terminal positions were blocked, the ether
group in the position para to the side chain was thought to be broken
before the aromatic ring was opened.
Ozone Generator: Ozone was generated by introducing about 300 ml of oxygen/-
min into an ozone generator at an applied voltage of 15,000 v. The ozone was
produced at a concentration of about 3 vol %.
Contact: The reactions were performed under both acidic and alkaline
conditions. Vanillyl or veratryl alcohol was dissolved in a 3-necked flask,
and ozone passed into the flask with cooling in ice and stirring. Reaction
time was 5 hrs under acidic conditions, 2 hrs under alkaline conditions.
References: 6
PU-11
Title: "Degradation of Lignin with Ozone"
Authors; H. Hatakeyama, T. Tonooka, J. Nakano & N. Migita
Source: Kogyo Kagaku Zasshi 71(8):1214-1217 (1968). Chem. Abstr. 70:-
12766n (1969)
Four g of Ca lignosulfonate (I) in 50 ml HgO was oxidized at 0° with 3
vol % of oxygen. Amounts of carbonyl, COgH, phenol and methoxyl (~OMe) were
determined on oxidized I. With oxidation, CO and ^H increased and PhOH
and "OMe decreased. The decrease in PhOH and "OMe was accounted for by the
postulate that the catechols resulting from demethylation of guaiacyls are
immediately oxidized to muconic acid-type structures. Decomposition rates
of the aromatic nucleus of I at each oxidation time under the above condi-
tions were as follows: 18.5 (0.25), 34.5 (0.5), 38.7 (1.0), 41.6 (2.0),
46.3 (3.0), 48.9 (4.0) and 53.0% (5.0 hrs). About 90% of the C02H present
in I oxidized at 0° for 5 hrs was that derived from the aromatic-nucleus
scission of I.
160
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PU-12
Title: "Bleaching of Pulp"
Authors: J. Hosokawa, T. Kobayashi & T. Kubo
Source: Japanese Kokai 76,139,903, Dec. 2, 1976, Appl. 75/62,661,
26 May 1975. Chem. Abstr. 86:57076 (1977)
Water containing pulp was bleached rapidly with ozone in CCl*. Thus,
30 g kraft pulp sheet was sprayed with 45% water, suspended in 450 ml of
0014, and treated with oxygen containing 1% (vol) of ozone at 30° and 200
ml/min to prepare 94% pulp having a whiteness degree of 80%.
PU-14
Title: "Ozone Treatment of Pulp and Paper Mill Effluents"
Author: J. Jackowski
Source: Private Communication, Nov. 1970, to I. Gel 1 man. Noted in
Natl. Council of the Pul'p and Paper Industry for Air & Stream
Improvement, Tech. Bull. #269, Jan. 1974, by R.C. WhUtemore
(P. 2)
"500 mg/1 of ozone added to a waste resulted in very little reduction
in [BOD], but greater than 50% reduction in color from both a paper mill and
a pulp mill effluent."
PU-21
Title: "Attempts to Modify the Activated Sludge Process for Sulfite
Pulp Wastewater"
Authors: H. Kamishima & I. Akamatsu
Source: Jap. J. Technical Assoc. Pulp & Paper Indus., 27(9):449 (1973).
Review: Removals of TOC, COD, lignin and color of activated sludge (AS)
treated alkaline extraction effluents from the bleaching of kraft pulp were
improved by ozonation of the effluent. Subsequent AS treatment resulted in
adequate BOD removal. Very little lignin was adsorbed from the ozonated
effluent by activated carbon.
161
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PU-22
Title: "Ozone Activated Sludge Treatment of Sulfite Pulp Wastewater.
Mechanism of BOD Removal, Treatment Conditions and Sequential
Treatment"
Authors: H. Kamishima & I. Akamatsu
Source: Japanese TAPPI, 28(8):35-44 (1974).
Review: Deals with BOD removal and treatment conditions in activated sludge
treatment of the ozonized liquor of diluted black liquor. Results obtained
were as follows:
(a) BOD removal rate was illustrated by the 2-phase theory of the equation.
When initial BOD was around 600 mg/1, the reaction rate of BOD was
first order, and when initial BOD was from 100 to 200 mg/1, it followed
second order kinetics.
(b) BOD removal efficiency of more than 90% was achieved at less than 0.5
kg of BOD/kg of MLVSS/day, as well as that of the other pulping wastes.
(c) Sludge yield was more or less the same as that of other pulping wastes.
(d) In ozonized liquor containing 4.0 to 15 mg of ozone, BOD removal effi-
ciency did not decrease at loadings of <0.4 kg of BOD/kg of MLVSS/day,
but largely decreased at the higher BOD loading.
Sequential ozone-activated sludge treatment of diluted black liquor was
studied and it was found that total removal efficiencies of COD (Mn) and BOD
depended upon removal efficiencies of ozone treatment and activated sludge
treatment.
When the remaining ozone in the effluent of stirring treatment and gas
supplied to the aeration tank were 0.4 mg/1 and 0.08 mg/1, resp, total
removal efficiencies of COD (Mn) and BOD were 66.6% and 87.5%, with nearly
satisfactory results.
Removal of lignin and color depended on ozone treatment and their total
removal efficiencies were 66.6% and 81.5%, resp.
Economics: None mentioned.
References: 13
PU-25
Title; "Ozonization of Lignin, Part 1. Activation of Lignin with Ozone"
Authors: S. Katuscak, A. Hrivak, & M. Mahdalik
162
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Source: Papper och Tra1 9:519-523 (1971a).
Review: Polymerization reactions are initiated by hydroperoxide groups
formed during the ozonation of various lignins. Th'e kinetics and chemical
natures of the functional groups formed by ozonation of lignins (in both
solid state and dissolved in organic solvents) were studied. The lignins
used included methanol-lignin (I), HCl-lignin (II), and CH9N«-methylated-
HCl-lignin. * '
The ozonation of I was more rapid than that of II, with the rate of
formation of active functional groups in I being 14 times greater than that
of II. The solvent used for ozonation influenced the content of active
functional groups, with low values being obtained in water, and higher
values in acetic acid and methanol. The increased active functional group
content was due solely to ozone. Active functional groups (not identified)
were less stable at elevated temperatures. The decomposition half-life in
the temperature range of 60° to 80°C varied from 2.5 to 20 minutes.
Ozone Generator: The source of ozone used was not described.
Contact: The lignins were ozonized either as dry solids or in suspension
with protogenic solvents, at an oxygen flow rate of 600 ml/min and [ozone]
of 39 mg/1. In the dry state the ozonation reaction occurred on a sintered
glass filter with a diameter of 7 cm, at 20°C.
References: 37
PU-26
Title: "Ozonation of Lignin, Part II. Investigation of Changes in the
Structure of Methanol Lignin During Ozonization."
Authors: S. Katuscak, I. Rybarik, E. Paulinyova, & M. Mahdalik
Source; Papper och Tra1 11:665-670 (1971b)
Review: Changes in structure of ligm'n macromols were investigated by
studying low molecular weight methanol-lignin during its reaction with ozone
in the dry state. Spectral methods and vapor pressure osmometry detected
changes in UV, IR and NMR spectra, and in average molecular weight of the
lignin.
Low molecular weight methanol-lignin was very reactive when treated
with ozone. The aromatic rings were the first to be attacked, producing
oxidation reaction products and causing a gradual decrease in the average
molecular weight. At least part of the active oxygen in the ozonized lignins
is bound as hydroperoxide groups because neither quinonoids nor ozonides can
initiate polymerization reactions.
163
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Rapid decrease in molecular weight occurs within the first 5 minutes of
ozonization (210 molecular weight units/min), after which the rate of decrease
is lowered 180-fold (1.1 molecular weight units/min).
Spectral measurements indicated destruction of the aromatic conjugated
system of methanol-lignin during ozonization. IR and NMR studies on original
and ozonized methanol-lignin showed reaction of ozone with aromatic rings,
production of carboxyl and aldehyde groups, formation of quinone moieties
and low molecular weight substances.
Ozone reacts with the aromatic rings at the highest rates during the
early stages, and is accompanied by the most rapid decrease in molecular
weight within the first 5 minutes.
Ozone Generator: The apparatus used for ozone production and the gas source
were not described.
Contact: The methanol-lignin was ozonized in the solid state on a sintered
glass filter 7 cm in diameter, in the stationary phase, at an ozonizing gas
flow rate of 600 ml/min, and at 20°C.
References: 24
"Soda Lignin III. Lignin-Carbohydrate Bond in Soda Lignin From
Hardwoods"
Authors: M.F. Kiryushina & D.V. Tishchenko
Source: Zhur. Priklad. Khim. (Leningrad) 41(8):1848-1853 (1968). Chem.
Abstr. 70:12767p (1969)
The acetone-insoluble fraction of maplewood soda lignin (I) (10.7% MeO
groups) was subjected to a 2nd soda cook at 170°. The MeO" group content of
the product (II) was increased to 12.85%; however it still contained 34.5%
carbohydrates (III). Hydrolysis of I with 1% HgSO* gave a product containing
18.45% MeO~ groups and no III. Also ozonization of soda lignin in EtOAc
separated III from I. The infrared spectrum of I had a band at 1740 cnr',
which was absent in acid-hydrolyzed I. This indicates that the lignin/carbo-
hydrate bonds are of the phenylglucoside type.
PU-28
Title: "Bleaching of Pulp With Ozone"
Authors: T. Kobayashi, J. Hosokawa & T. Kubo
164
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Source: Japan. Kokai 76,139,902, Dec. 2, 1976, Appl. 75/62,660, May 26,
1975. Chem. Abstr. 86:57076 (1977)
Pulp was bleached with ozone at <5° and washed with water alternately
to prevent viscosity decrease. Thus, 5 g Douglas fir kraft pulp was sprayed
with 45% water, treated with oxygen containing 1% (vol) of ozone at 0° to 5°
and 200 ml/min to a whiteness degree of 40%, and washed. The same process
was repeated twice to prepare pulp having viscosity of 6.4 cP, compared with
4.9 cP for pulp bleached at 30°.
PU-34
Title: "The Resistance of Hemicelluloses in Wood Fiber to Degradation
by Ozone."
Authors; W.E. Moore, M. Effland, B. Sinha, M.P. Burdick & C. Schuerch
Source: TAPPI, 49(5):206-209 (1966).
Review: To investigate the distribution of hemicelluloses within the
native plant cell wall, a study was made of the fate of the carbohydrate
fraction of wood substance upon extensive gas phase ozonation. The majority
of hemicelluloses were easily accessible to ozonation, while some hemicellu-
lose sugars, mannose in particular, were in extremely inacccessible fiber
regions. Some preferential attack was observed, with lignin being virtually
eliminated by oxidation.
Ozone Generator: A conventional corona discharge laboratory generator using
oxygen at a flow rate of 350 ml/min formed ozone at a concentration of 0.8
vol %.
Contactor: Initially, ozonized oxygen was passed through a bubbler containing
water, then through a column of wood shavings with 100% water. In some
cases never-dried green wood was used, with no significant differences being
observed. Pressure was usually about 1.25 atm. Alternatively, a fluctuating
pressure was induced by a solenoid valve and water pump, increasing pressure
from 230 to 760 mm in about 30 sec. Fresh gas continued to flow for 18 sec.
Gases were then maintained on the wood chips for 36 sec, and a vacuum applied
for a final 36 sec. Ozonation time was 10 to 30 hrs. Ozonized chips and
fibers were disintegrated in water suspension with a high speed metal stirrer.
Fibers were filtered and water soluble fractions were obtained by concentra-
ting the liquors and washings. Residual fibers were collected and further
ozonized as a loose mat or in suspension with water (0.1% concentration).
Results: Fiber fractions were analyzed for 5 sugars: galactose (I), glucose
(II), mannose (III), arabinose (IV), and xylose (V)], lignin (VI) and uronic
acid (VII). Values of VII were high because of C02 evolution from oxidized
carbohydrates. The % of fiber recoverable as identifiable sugars decreased
with ozonation time. The average degree of polymerization decreased to 250
to 400, before delignification. Of the sugars, II was the most resistant to
165
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ozonation, but the % of V was about one-half that present originally. There
was a regular decrease in the amount of xylan left in the fiber with increas-
ing ozonation time, but after 20 hrs poplar began to lose II more rapidly
than V. In softwoods, the relative proportion of III (the predominant
hemicellulose) was reduced by a factor of 2 early in the ozonation, but at
higher degrees of ozonation, II was lost more readily.
Fiber isolated after 10 hrs of ozonation was resuspended in water (1
g/100 ml) and re-ozonized for periods up to 3 hrs. Although the degree of
polymerization was ca 150, substantial amounts of V and III still were
present.
Analyses of the fiber fractions for carbonyl and carboxyl groups were
abandoned because of the multiplicity of oxidized functional groups and the
impossibility of distinguishing between those functions originally present
and those formed during ozonation. A small fraction (5%) of dioxane-soluble
material from 30 hrs of ozonation of maplewood, after hydrolysis, appeared
to be 2-0-4-0-methyl-a-D-glucopyranosylurom'c acid-D-xylose. A small amount
of fiber was converted to C02 and HCOOH during hydrolysis. Oxidized fragments
of original pentoses and hexoses were not identified.
Economics: Cost factors were not presented in this paper.
References: 20
PU-38
Title: "Ozone: A New Method to Remove Color in Secondary Effluents".
Authors: C. Nebel, R. Gottschling & H.J. O'Neill
Source: Pulp & Paper 48(10):142-145 (1974)
Ozone can be effectively used to remove color, reduce levels of COD and
turbidity and provide a high degree of disinfection in secondary pulp and
paper mill effluents. Since sludge is not generated during ozonization,
secondary clarification and dewatering are not required.
PU-39
Title: "Ozone Decolorization of Pulp and Paper Mill Secondary Effluents".
Authors: C. Nebel, R.D. Gottschling & H.J. O'Neill
Source: Proc. 7th Mid-Atlantic Indl. Wastes Conf., Drexel Univ., Phila-
delphia, Pa. (1974), p. 161-187
Analysis of various decolorization processes for pulp and paper mill
effluents indicate that there are 2 processes which deserve strong consider-
166
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ation: massive lime dosages and oxidation with ozone. Lime Is applied
prior to secondary treatment whereas ozone is applied after the secondary
process. The lime process is relatively expensive to operate. Experimental
data show that ozone treatment simultaneously brings about disinfection of
the effluent, thus further treatment is not necessary. The costs of color
removal from 4 different secondary pulp and paper mill effluents are in the
range of 2.8
-------
PU-44
Title: "The Action of Gaseous Reagents on Cellulosic Materials. II.
Pulping of Wood with Ozone."
Authors: Z. Osawa, W.A. Erby, K.V. Sarkanen, E. Carpenter & C. Schuerch
Source: J. Tech. Assoc. Pulp & Paper Industry, 46(2):84-88 (1963b)
Review: The effects of ozone on whole wood and factors influencing the
reactions were studied. Rates of attack on holocellulose and lignin were
investigated under the following conditions:
1) In a liquid system (water and nitromethane) at 0°C,
2) In a gas-phase system with constant and fluctuating pressures, and
3) On wood of various species, tissues, and particle sizes (mostly small
chips of Norway spruce, also veneer strips of gumwood and Douglas fir,
shavings of basswood, wheat straw, and small pieces of Douglas fir
bark).
Ozone acted as a rather indiscriminant reagent. Results depended
greatly on the permeability and rate of transfer of the ozone. Yields of
cellulose of 40% to 50% based on wood substance were obtained from certain
woods at degrees of polymerization of around 400. Water-soluble products
contained methanol and acetic and oxalic acids. 20% of lignin was removed
in about 3 hrs in nitromethane, and about 10 hrs in water. After the first
few hrs, though, little or nothing was gained in the specificity of attack
orr lignin by the use of nitromethane. The attack on carbohydrate was
slightly slower in nitromethane than in water.
Wood ozonized in air was strongly acid and smelled strongly of acetic
acid. With all samples, the reaction in the gas phase was faster and more
homogenous than in the liquid phase. Results were further improved by the
use of a fluctuating pressure. Reaction in the gas phase was markedly
influenced by the moisture content of the wood sample; the optimum moisture
content was near 100% in Norway sprucewood samples. The wood species influen-
ced the course of the reaction, with spruces being more difficult to affect
extensively than basswood. Plant structure also was an important factor:
springwood reacted much more rapidly than summerwood, and Douglas-fir bark
was completely impervious to gas transport and did not react at all at
atmospheric pressure.
Feedstock; Dry oxygen was used as the source for ozone generation.
Ozone Generator: A conventional laboratory ozonizer was used, consisting of
a Pyrex glass mercury well surrounded by a Pyrex glass tubing. The tubing
was wrapped in Al foil and exterior insulation, and oxygen was passed through
this. A potential of 10,000 v was used.
Contact: 1 g samples of Norway sprucewood meal were suspended in 10 ml of
sol vent'(water or nitromethane) and ozonized oxygen passed through the
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suspension at 75 ml/min. The substrate was placed in 5 small cells in
series; [ozone] was 10.9%. The suspensions of basswood shavings in water
and 10% nitromethane (about 10 g) were treated in a glass cylinder with
oxygen passing through a sintered glass plate at the bottom of the cylinder
and bubbling through the mixture at a flow rate of 283 ml/min and [ozone] of
3.4%. In all other reactions, 2 ozonators were used in series, with a rate
of oxygen flow of 1,250 ml/min, [ozone] of 1.0%. The pressure was fluctuated
between 1 and 1.4 atm by means of a magnetic solenoid valve opened 4 times/min.
The gas stream was passed through water before entering the reactor to
prevent drying of the wood chips.
Economics: The economics of the processes were not discussed.
References: 13
PU-45
"Ozonation of Kraft Pulp and Paper Effluents"
R. Ottman (U. of Illinois, Urbana, 111.)
Private Communication, August 1, 1972 to I. Gellman. Cited in
Natl. Council of the Paper Industry for Air and Stream Improve-
ment, Tech. Bull. #269, Jan. 1974, by R. C. Whittemore (p. 2).
"In a study of ozonation of kraft effluents, 50% of the color of a
total mill effluent was reduced with 190 mg/1 ozone over less than 15 min of
contact. Approximately 25% of the COD and less than 1% of the BOD were
removed during this period."
"Treatment of Industrial Effluents and Gaseous Discharges in U.S.
Industries".
Author: A.M. Pristupa
Source: Bumazhn. Promy. (Moscow) 12:23-26 (1974). Air Poll. Tech. Info.
Center No. 73936
A survey of pulp and paper mills in the USA concerning water protection
and air pollution prevention is presented. In the absence of Federal
standards on air pollutant emissions, dust and malodorous gaseous emissions
in plants situated in or near communities are limited by local regulations.
Soda reclamation plants are equipped with 2 or 3 electrostatic precipitators
and additional scrubbers. Venturi scrubbers are used for lime recovery
kilns. The use of oxygen and ozone in technical processes in place of other
chemicals constitutes a major contribution to air and water pollution
abatement.
169
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"CoHform Bacteria Growth and Control in Aerated Stabilization
Basins"
Author: S.H. Watkins
Source: EPA Report No. 660/2-73-028, 279 pages, Dec., 1973. Pages 220-221
deal with ozonation.
Review: This article was concerned with the effects of chlorination to
control coliform bacteria in secondary effluent from a pulp and paper mill
plant. A few experiments were made using ozone.
Ozone Generation: Ozone was generated by a Welsbach Model T23 laboratory
ozonator operated on tank oxygen. Ozone output was 525 mg/hr.
Ozone Contactor: A sparger was placed in the vertical section of a 3.8 cm
(1.5 in) 00 rubber hose carrying the waste.
Procedure: Effluent flow through the rubber hose was 5 gpm, and the ozone
dosage thus was 0.46 mg/1. Slowing the rate of effluent flow increased the
ozone dosage to a maximum of 4.6 mg/1.
Results: No effects on bacterial motility nor upon bacterial concentrations
were observed. No residual ozone was found in any of the samples.
Abstractors' Comment: Rubber is one of the most reactive materials with
ozone. Thus rubber should not have been used as a contactor. Since no
residual ozone was found, and since sulfite mill wastes are known to be
high in ozone demand, it is also clear that the ozone dosage was too low.
Thus the results of this work are meaningless.
References: 15 (1 dealing with ozone)
PU-58
Title: "Preliminary Laboratory Studies of the Decolorization and Bacteri-
cidal Properties of Ozone in Pulp and Paper Mill Effluents."
Authors: R.C. Whittemore & J.J. McKeown
Source: National Council of the Paper Industry for Air & Stream Improve-
ment, Inc., Technical Bulletin #269, January 1974.
Apparatus: An Ozonator Corp. Model 4,000 silent arc discharge generator was
used, capable of generating 0 to 30 mg/min of ozone from oxygen.
Contactor: A countercurrent, fritted glass disc, sparged column 90 cm
high, 5 cm in diameter, with an approximate volume of 1.8 liters.
170
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Classes of Effluents Studied:
(1) Unbleached kraft effluent synthesized from softwood kraft black liquor
diluted to a BOD-5 of 300 mg/1.
(2) Unbleached kraft effluent synthesized from hardwood kraft black liquor
diluted to a BOD-5 of 300 mg/1.
(3) Hardwood caustic stage washer bleach plant effluent.
(4) Softwood caustic stage washer bleach plant effluent.
(5) Hardwood chlorine-stage washer plant effluent.
(6) Softwood chlorine-stage washer bleach plant effluent.
(7) Neutral sulfite total mill effluent where recovery is practiced (sodium
and ammonia base).
(8) (1 to 6) above after lime decolorization.
(9) Biologically treated boxboard total mill effluent.
(10) Biologically treated sulfite total mill effluent.
Results: For unbleached kraft pulp mill effluent prepared from weak kraft
bleach liquors; hardwood bleaching effluents, softwood chlorination stage
bleaching effluents and biologically treated bleached kraft total mill
effluents, the effluent color decreased with increasing ozone use. However,
the amount of color removed was time-dependent, 45 min contact time resulting
in better than 80% color reduction, or residual color levels of <100 APHA
units. For a given effluent, more color was removed/unit weight of ozone at
the shorter contact times of 10 to 20 min.
To achieve 50%, 75% and 90% color reduction required variable amounts
of ozone from 1 effluent to another. Up to 10% color reversion (% return of
color 24 hrs after ozone treatment had ceased) occurred in many but not all
effluents, in the median range of 5% to 8%. This amount of reversion is
considered to be significant.
Total coliform counts in kraft total mill effluents showed a rapid
decrease with ozone dosages of <100 mg/1, followed by a slow decay to 0 at
high ozone dosages of several hundred mg/1. Boxboard mill effluents showed
total coliform densities reduced to 0 with [ozone] on the order of 25 mg/1.
Color of ozonized boxboard effluents averaged <200 APHA units, while
color of ozonized total mill kraft effluents ranged from 400 to 1,800 APHA
units.
Effluent color (as well as SS) appears to be a significant factor in
determining the amount of ozone required for disinfection. An increase in
171
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color of kraft mill effluent from 400 to 4,000 APHA units and dosing with
300 mg/1 of ozone reduced the induced color bacteria and total coliform
densities by 15% and 57%, resp. The sample containing fewer color bodies
produced 99% kill of total bacteria and 97% kill of total coliforms at lower
ozone dosage (190 mg/1).
Splitting a biologically treated kraft mill effluent, then filtering
one-half through Whatman No. 42 filter paper, then ozonizing each sample and
determining total coliforms showed that lowering levels of SS will result in
reduced ozone demand to achieve effluent disinfection (190 mg/1 vs. 75 to
120 mg/1 to attain 1% or less total coliforms).
In nearly all experiments, [COO] was reduced 0% to 30% upon ozonation,
although an occasional 50% reduction was observed. Significant increases in
[BOD] were observed, especially for ozonated boxboard and integrated kraft
aerated stabilization basin effluents and the Na base NSSC total mill effluent.
Some ozonated samples showed 0% to 10% or 0% to 20% reduction in [BOD]. It
is postulated that ozonation caused partial oxidation of organic COD compo-
nents, making them more biodegradable.
However, portions of 3 primary settled kraft total mill effluents were
ozonated to remove color, and the remainder of each effluent sample was set
aside as controls for biological oxidation studies. Each was seeded, forti-
fied with nutrients and aerated. The data show that ozonation for color
reduction up to 50% had no effect upon subsequent biological oxidation.
This implies that the nature of the biodegradable material is not affected
by ozonation.
In other experiments, data obtained showed that <3 Ibs of ozone are
required to remove 1 Ib of COD (average 1.61). Lime decolorized effluents
required an average of 1.72 Ibs of ozone/lb of COD.
172
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LITERATURE CITED (SOAPS & DETERGENTS) (SO)
SD-01* Baer, F.H., 1970, "Ozone Step Allows Recycle of Organic-Fouled
Water", Chem. Engrg., Aug., p. 42.
SD-02 Buescher, A., Jr. & D.W. Ryckman, 1961, "Reduction of Foaming of
ABS by Ozonation", Proc. 16th Ann. Purdue Indl. Waste Conf., p.
251-261.
SD-03* Evans, F.L., III & D.W. Ryckman, 1963, "Ozonated Treatment of
Wastes Containing ABS," Proc. 18th Indl. Waste Conf., Purdue
Univ., p. 141-157.
SD-04 Grossman, A., K. Kwiatkowska & M. Zdybiewska, 1970, "Use of Ozone
for the Decomposition of Organic Substances in Water." Zese. Nauk,
Politech. Slask., Inz. Sanit., (Politech, Slaka, Gliwice, Poland).
SD-05 Kandzas, P.F. & A.A. Mokina, 1969, "Use of Ozone for Removing
Synthetic Anionic Surface-Active Agents from Wastewaters". In the
book: Ochistka Proi-zvodstvennykh Stochnykh Vod. (Purification of
vennykn
, 4:76.
Industrial Sewage), Moscow
SD-06 Kandzas, P.F. & A.A. Mokina, 1968, Trudy Vsesoyuzn. Nauchno-
Issled. In-ta Vodosnabzheniya, Knalizatsii Gidrotekhnic heskikh
Sooruzheniy i Inzh. Gidrogeologii (Works of the All-Union Scientific
Research Institute of Water Supply, Sewage, Hydrotechnical Struc-
tures and Hydrogeological Engineering) 20:40.
SD-07 Kuiz, C.G., 1970, Grasas aceit. 21:91.
SD-08 Kwie, W.W., 1969, "Ozone Treats Waste Streams From Polymer Plant",
Water & Sewage Works 116:74-78.
SD-09 Mal'kina, I.I. & V.G. Perevalov, 1970, "Removal of Some Nonionic
Surface-Active Agents from Water by Ozone Treatment." Neft. Khoz.
SD-10* Marschall, K., 1973, "Process of Treating and Purifying Sewage,
Particularly of Sewage Contaminated with Detergents". U.S.
Patent 3,733,268, issued May 15.
SD-11* Marschall, K., 1974, "Process of Treating and Purifying Sewage,
Particularly of Sewage Contaminated with Detergents". U.S.
Patent 3,822,786, issued July 9.
SD-12 Verde, L., Meucci, F. & Vanini, G.C., 1969, Ing. Mod. 62:277.
173
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SD-01
"Ozone Step Allows Recycle of Organic-Fouled Water."
F.H. Baer
Source: Chem. Engrg., August, 1970, p. 42
Ozonation of carwash waste, including detergents, in Vienna, Austria,
Is discussed. The treatment process includes oil separation and skimming,
sedimentation (3 hrs with or without flocculation agents), gravel filter
(removes fine sediment) and ozonation (15 to 20 min reaction with recircula-
tion). Total system capacity is 19,915 gal/day. With this treatment system
for recycle, only 793 gal/day of fresh water needs to be added.
Ozone System: Not specific. A 4-column generator producing 4 g of ozone/hr
(12 to 15 kv electric field)
Cost: $23,000 for treatment process. This compares with a fresh water well
source costing $61,000, with no means of wastewater disposal provided.
SD-03
Title: "Ozonated Treatment of Wastes Containing ABS"
Authors: F.L. Evans, III & D.W. Ryckman
Source: Proc. 18th Indl. Waste Conference, Purdue Univ. (1963), p. 141-157
Review: ABS (alkyl benzene sulfonate) detergents are made more amenable to
biodegradation as a result of partial chemical oxidation by ozone.
Experimental: Sewage was employed from a treatment plant employing biological
primary and secondary treatment and which contained ABS. Sample sizes taken
were 45 gal. [ABS] was 6.4 mg/1 in the actual sewage and an amount of ABS
surfactant equivalent to 10 mg/1 was added to a portion of the plant effluent.
A 3rd sample of 50 mg/1 ABS in distilled water was prepared. All 3 samples
were ozonized and their biochemical behaviors were determined under simulated
stream conditions by observing the progression of BOD.
Ozonation System; A Welsbach T-23 generator operating on air which had been
passed through a glass wool/cotton grease and dirt trap, then activated
alumina to a -60°F dew point.
Contactor: A single 10 ft column consisting of 5 3-inch ID diameter Pyrex
glass sections, with a vertical mixing recirculating system in the lower
section, and sampling ports at various heights.
A 3.8 liter sample was placed in the column then ozonized for periods
of time ranging from 2 to 120 min. At the end of each run the volume of gas
174
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passed through the wet test meter was recorded, the amount of unreacted
ozone determined by titration and the ozonized liquids analyzed for ABS, COD
and BOD. Secondary effluent samples and those with 10 mg/1 added ABS were
ozonized in duplicate for 2, 5, 10, 20, 30, 45, 60, 90, and 120 min. The 50
mg/1 ABS in distilled water sample was ozonized at an ozone/air flow rate of
0.1 cfm for periods of time up to 120 min. BOD only was measured on these
samples after ozonation.
Results: Removal of ABS from fortified (with ABS) and unfortified samples
was rapid at first, then began to taper off at 45 mg/1 and 25 mg/1, resp, of
absorbed ozone. Reduction of [ABS] from 6.4 to 1.0 mg/1 (unfortified sample)
required 150 mg of ozone; reduction from 16.4 to 1.0 mg/1 (fortified sample)
required 250 mg of ozone. Thus, the additional 10 mg/1 of ABS required 100
mg of ozone; or 2.64 mg/1 of ozone was required to remove 1 mg/1 of ABS from
the samples.
The greater the starting [ABS], the greater the amount that could be
removed while maintaining the ozone transfer efficiency at a high enough
level (86% to 90%) for process practicality. As the quantity of ozone used
increased, the COD of all samples decreased.
BOD-5 of effluent samples was reduced to 0 by absorption of 180 mg/1
ozone, but twice as much ozone was required to reduce [BOD] of the fortified
sample to 1 mg/1. [BOD] of the fortified sample increased up to that point
of ozone absorption at which the [ABS] was no longer detectable. Thus at
low [ozone], ABS is converted to intermediates which are biodegradable. At
higher [ozone], the ozonized products are further oxidized such that they no
longer exert a BOD. While ozone lowered the COD of ABS, it increased the
amount of material which could be utilized by the microorganisms.
The 50 mg/1 ABS in distilled water sample showed an inhibitory effect
on activated sludge organisms. After 10 min of ozonation, inhibitory
action no longer was evident and ozonized ABS served as the sole food
source. By increasing the amount of applied ozone, the rate of biological
reaction increased. After 4 hrs in the Warburg respirometer, oxygen utiliza-
tion in the sample ozonized 15 min was 29 mg/1, but was 55 mg/1 in the
sample ozonized 120 min, an increase of 370%.
The authors postulate that when alkylbenzenes are ozonized, the alkyl
group is converted to a carboxyl group, the point of initial attack being
the carbon atom attached to the benzene ring. Upon continued ozonation, the
aromatic ring is ruptured.
Conclusions: 95% removal of 5.9 mg/1 ABS required 100 mg/1 of ozone (at 83%
utilization efficiency) and 95% removal of 15.6 mg/1 ABS in the fortified
sample required 75 mg/1 of ozone dosage (at 92% ozone transfer efficiency).
Ozonation reduced levels of both COD and BOD. Increasing dosages from
53 mg/1 of ozone (sufficient to eliminate foaming) to 100 mg/1 of ozone
produced a significant increase in [BOD]. Ozonation of 50 mg/1 of ABS in
distilled water destroyed its biological inertness. Ozonized ABS solution
175
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served as the oxidizable substitute for microbes, and an increase in ozone
dosage increased both the amount of material available for biological oxida-
tion and the biochemical oxidation rate.
References: 27
SD-10
Title: "Process of Treating and Purifying Sewage, Particularly of Sewage
Contaminated with Detergents"
Author: K. Marschall
Source: U.S. Patent 3,733,268, issued May 15, 1973, Filed Dec. 8, 1970
Car washing wastewater is passed through an oil separator for removal
of oil, grease, fat, solvents, etc. Air is bubbled through this container
to accelerate separation of oil and to strip volatile solvents. In a 2nd
container flocculating agents are metered in, the settled liquid passed
through a gravel filter to remove fine particles, then to countercurrent
ozonation in a steel or concrete contactor. An activated carbon filter can
be used to break down excess ozone in the exhaust gases, which then may be
used in air conditioning systems. The ozonized water also is passed through
an activated carbon filter prior to recycle and reuse.
Makeup water is supplied to the top of the gas-liquid contactor. Water
in the contact chamber is also recycled from the bottom to the top, by means
of a pump to increase efficiency of ozone contacting.
"Process of Treating and Purifying Sewage, Particularly of Sewage
Contaminated with Detergents"
Author: K. Marschall
Source; U.S. Patent 3,822,786, July 9, 1974; filed June 30, 1972
A division of U. S. Patent 3,733, 268, by the same inventor; identical
with 3,733,268, except that more patent claims are made.
176
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LITERATURE CITED (TEXTILES) (TX)
TX-01 Anonymous, 1973, "Japanese Develop Water Treatment", Daily News
Record 3(9):23.
TX-02* Anonymous, 1974a, "Ozone-Carbon Dye-Waste Treatment", Textile Ind.
138(10):43, 45.
TX-03 Anonymous, 1974b, Gijutsu to Kogai 4(4):22-28.
TX-04* Anonymous, 1975a, Kogai 10(4):20-27.
TX-05* Anonymous, 1975b, Kogai 10(4):34-48.
TX-06* Anonymous, 1975c, Kako Gijutsu 10(8):31-36.
TX-07* Anonymous, 1976a, Netherlands Patent NL 7506-370 (Dec 2, 1975).
Derwent Netherlands Patents Report W(51):D2, Jan 27.
TX-08* Anonymous, 1976b, Mizushori Gijutsu 17(l):53-62.
TX-09* Anonymous, 1976c, Textile World 126(11):108, 111, 113, 115, 116,
118, 121.
TX-10 Bauch, H. & H. Burchard, 1970, "Experiments to Improve Highly
Odorous or Harmful Sewage with Ozone", Wasser, Luft u. Betrieb
14(4):134-137.
TX-11 Best, G.A., 1974, "Water Pollution and Control", J. Soc. Dyers
& Colourists (Great Britain) 90:389-393.
TX-12 Horikawa, K., H. Wako & E. Sato, 1976, "Treatment of Dye Waste
Effluents by Ozonation with Ultraviolet Radiation", Kogyo Yosui
214:21-24.
TX-13 Ikehata, A., 1975, "Dye Works Wastewater Decolorization Treatment
Using Ozone", in Ozone for Water & Wastewater Treatment. R.G. Rice
& M.E. Browning, Eds., Intl. Ozone Assoc., Cleveland, Ohio, p.
688-711.
TX-14 Kawazaki et al., 1965, Water & Wastewater (Japan) 6:643-648, 778-
780.
TX-15 Maeda, M., Y. Hashimoto, T. Ozawa, T. Imamura, M. Matsuoka & N.
Tabata, 1972, "Ozone Treatment of Dyeing Wastewater", Mitsubishi
Denki Giho, 46(10):1110-1115.
TX-16* Maeda, S., 1974, "Studies on the Liquid Waste Treatment of Dye
Manufacturing Plants (II)", Gijutso to Kogai (Technology & Public
Nuisance) 4(4):22-28.
177
-------
TX-17 Maggiolo, A., F. Davis, N. Lowe & R. Montgomery, 1977, "Ozone
vs Chlorine in Treatment of Textile Chemical Wastes; Its Problems
and Possible Solutions", presented at 3rd Intl. Symp. on Ozone
Technology, Paris, France, May. Intl. Ozone Assoc., Cleveland,
Ohio.
TX-18* Matsuoka, H., 1973, "Ozone Treatment of Industrial Wastewater",
PPM 4(10):57-69.
TX-19 Mizumoto, K. & M. Horie, 1974, "Dyeing Wastewater Treatment by
Combination of Ozone and Activated Carbon", Japan Textile News
89:238.
TX-20* Nakayama, S. & M. Maeda, 1976, "Decoloring Mechanism of Dyes with
Ozone and the Effect of pH", Mizu Shori Gijutsu 17(2)157-161.
Chem. Abstr. 86:60133f.
TX-21 Nebel, C. & L.M. Stuber, 1976, "Ozone Decolorization of Secondary
Dye Laden Effluents" in Proc. Second Intl. Symp. oni Ozone Tech-
nology, R.G. Rice, P. Pichet & M.-A. Vincent, Eds., Intl. Ozone
Assoc., Cleveland, Ohio, p. 336-358.
TX-22* Netzer, A., 1976, "Advanced Physical-Chemical Treatment of Dye
Wastes", Progress in Water Technology 8(2-3):25-37.
TX-23 Netzer, A., S. Beszedits, P. Wilkinson & H.K. Miyamoto, 1976,
"Treatment of Dye Wastes by Ozonation", in Proc. Second Intl.
Symposium on Ozone Technology, R.G. Rice, P. Pichet & M.-A. Vincent,
moiog
:., Cl
Eds., Intl. Ozone Assoc., Cleveland, Ohio, p. 359-373.
TX-24* Rinker, T.L., 1975, "Treatment of Textile Wastewater by Activated
Sludge and Alum Coagulation". Blue Ridge-Winkler Textiles,
Bangor, PA., NTIS Report PB-248,142/2 WP. EPA Rept. No. EPA/600/2-
75-055, Oct., 216 pages.
TX-25* Sato, S., K. Yokoyama & T. Imamura, 1974, "Decomposition of Azo
Dyes by Ozone." Preprint, 31st fall Mtg., Chem. Soc. of Japan,
Oct. p. 614.
TX-26 Smirnova, L.V. et. al_., 1972, "Use of Ozone for Purification of
Effluent from Nitron Fibre Production", Khim. Volokna, (USSR)
14(1):70. World Textile Abs., 4:4016 (1972).
TX-27* Snider, E.H. & J.J. Porter, 1974, "Ozone Treatment of Dye Wastes",
J. Water Poll. Control Fed. 46(5):886-894.
TX-28* Stuber, L.M., 1973, "Tertiary Treatment of Carpet Dye Wastewater
Using Ozone Gas and Its Comparison to Activated Carbon", Special
Rsch. Prob., School of Civil Engrg., Georgia Inst. Tech., Atlanta,
GA, Aug., 17 pp.
178
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TX-29 Stuber, L.M., 1974, "Tertiary Treatment and Disinfection of Tufted
Carpet Dye Wastewater." Engrg. Bull., Purdue Univ. Ext. Ser.,
145(2):964-977.
TX-30 Stuber, L.M., 1975a,b,c, "Tufted Carpet Dye Wastewater Treatment,
& 31 Pt. I." Indl. Wastes, Jan/Feb 1975(a); "Pt. II", Mar/Apr 1975(b)
& 32 29-30; "Pt. Ill", May/June 1975(c) 13-14.
TX-33* Tsukabayashi, K., 1975, "Treatment of Wastewater from Textile
Dyeing Processes", Yuki Gosei Kagaku Kyokai-shi 33(5):377-383.
TX-34 Urushigawa, Y., G. Kurata & Y. Noji, 1974, "Treatment of Dyeing
Wastes by Trickling Filter and Ozone Treatment System", Kogai
(Poll. Contr.) 9(3):118-124.
TX-35 Yamashita, Y., H. Asai & K. Kitano, year unknown, "Treatment of
Dyeing and Finishing Effluent with Ozone" Sen'i Kako 25(5):289-
302.
TX-36 Tsukabayashi, K., 19.75, "Treatment of Wastewater from Textile
Dyeing Processes", Yuki Gosei Kagaku Kyokai-shi 33(5)377-383.
TX-02
Title: "Ozone-Carbon Dye Waste Treatment"
Author: Anonymous
Source: Textile Ind. 138(10):43,45 (1974a)
Review; Recently, waste dyeing water has been recognized as a part of
environmental pollution and research has commenced on several new treatment
techniques. One new technique is based on a combination of ozone and GAC.
Oxidation by ozone and adsorption by GAC to treat wastewater is well documen-
ted. Less well known is the synergistic effect of these methods when combined.
The combined use of ozone and GAC, as compared with the separate use of
each, often will produce a doubled effect and result in low investment
costs.
The ozone/GAC process is free of the disadvantages of sludge production
that occur with conventional processes such as coagulative/precipitation or
activated sludge. The process basically involves decomposing and decoloring
dyes in the wastewater by ozone, while decomposing dissolved organic substan-
ces and then removing dirt by GAC. The GAC is removed periodically after
use and regenerated at high temperatures.
The process has the following advantages: effective decoloration and
removal of organic substances in addition to increased treatment power of
the GAC; extremely high decoloration power of ozone; no foaming of treated
water because of surface active agents being decomposed; removal of noxious
179
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substances such as phenol; no sludge production; no particular location
requirement for the installation; only a small area needed for the installa-
tion because of its compact size; simplicity in automatic operation and ease
of maintenance; high performance and stability of the ozone generators;
high adsorption power and regeneration efficiency; a synergistic effect from
their combinatio; low operating costs; and no secondary pollution.
The Japanese plant described currently is treating 870,000 gpd at a
cost of about $0.34/1,000 gal, with few of the problems associated with
conventional processes. Ozone is produced easily, by silent discharge; the
6AC is regenerated at intervals for reuse. A process flow diagram, specifi-
cations of the installation, and examples of the treatment and results are
given.
TX-04
Title: Unknown
Author: Anonymous
Source: Kogai 10(4):20-27 (1975a)
Review: Oil/water emulsions frequently are used in the oiling process of
fiber dyeing. These emulsions produce high values of COO, BOD and n-hexane
extractives in the wastewater which, in turn, increase turbidities.
Various types of dyeing wastewater were treated by ozone with an inorganic
coagulant and the removal of the emulsions determined. The process could
remove ca 100% of the oil emulsion and colored organic compounds. The
sludge formed was 33% to 50% of the normal volume.
TX-05
Title: Unknown
Author: Anonymous
Source: Kogai 10(4):38-48 (1975b)
Studies were conducted on the treatment of wastewater from the towel
dyeing industry in Japan. To comply with the 1971 pollution regulations of
Japan, it was necessary to install an overall storage tank for wastewater
from various sources. During a detention time of about 0.5 day, the pH was
maintained in the range 6.5 to 8.0 by an automatic pH regulator. It was
also necessary to install an aeration basin capable of aerating the wastewater
for about 4 hrs in order to mix the wastewater with air and increase the
[DO].
Coagulation/sedimentation was investigated as a method for lowering
[COD]. Addition of 100 to 600 mg/1 of Al sulfate, a high polymer coagulant,
180
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and 2 ml/1 of an emulsion of Ca(OH)2 achieved removals of [COD] of nearly
50%. However, the method is not recommended because of the large amount of
sludge produced. Trickling filter and activated sludge were effective
methods for reducing [COD] to <100 mg/1.
Ozonation was effective for treating wastewaters from factories using
reactive dye, but was ineffective for those containing threne, naphthol
and/or sulfur dyes. However, since about 90% of the dye used in the towel
dyeing industry in the Ehime Prefecture is reactive dye, treatment with
ozone is a viable method for this area. Treatment with GAC also was effective
in the decolorization, which effect was greatly enhanced by the combined use
of GAC with ozone.
TX-06
Title: Unknown
Author; Anonymous
Source: Kako Gijutsu, 10(8):31-36 (1975c)
The general applications of ozone treatment for wastewaters containing
dyes include decolorization, decomposition of surfactants, and reduction of
[COD] and [BOD]. The amount of ozone required for decolorization is higher
for effluents containing disperse dyes than for wastes containing hydrophilic
dyes. The weight ratio of added ozone/dye ranges from 0.5 to 1.0 for wastes
containing hydrophilic dyes, but is >1 for wastes containing disperse dyes.
Disperse dyes which have a high solubility can be decolorized with a smaller
amount of ozone because of the higher contacting efficiency of dyes with
ozone during treatment.
If a pretreatment method, such as coagulation-precipitation is used
prior to ozone treatment, most of the disperse dyes will be removed from the
wastewater. However, the removal of hydrophilic dyes cannot be accomplished
by coagulation-precipitation. The strong oxidizing ability of ozone permits
the oxidation and decomposition of chromophoric groups in dyes, leading to
the decolorization of wastewaters containing such dyes.
The presence of reducing substances, such as dithionites, in wastewater
interferes with the decolorization of dyes because these substances will
consume the ozone present before dyes can react with the ozone. Therefore,
separation of these substances prior to ozone treatment is desired.
TX-07
Title: Unknown
Author: Anonymous
Source: Netherlands Patent NL 7506-370 (Dec 2, 1975). Derwent Netherlands
Patents Report, W(51):D2, Jan 27, 1976(a)
181
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Describes a method for treating dye-works effluents so that they are
suitable for recycling. Neutral wastewater containing organic dyes and
auxiliary agents is subjected to continuous oxidative degradation with ozone
in several stages with strong agitation. The amount of ozone applied is
adjusted according to the duration of treatment and the oxidation parameters
in each stage. This process provides for continuous operation with optimum
use of ozone. No supplemental purification steps are required for complete
degradation of the dyes and a wide range of dyes/auxiliaries can be degraded.
Economic efficiency is assured due to the optimal use of ozone.
TX-08
Ti tle: Unknown
Author: Anonymous
Source: Mizushori Gijutsu, 17(l):53-62 (1976b)
Wastewater treatment by immobilized activated sludge was studied and
its application for dyeing factory wastewater was tested. Fixation of
activated sludge on polyurethane sponge, polypropylene synthetic cotton,
polyethylene sponge and polyethylene thread was examined. All of the sub-
strates could retain >3,000 mg of sludge/1. Polypropylene synthetic cotton
retained the highest [sludge], ca 13,000 mg of sludge/1.
Wastewater from a dyeing factory was treated with activated sludge
fixed on polyurethane sponge. More than 24 hrs of aeration was required to
remove 90% of the 300 mg/1 [BOD] in the raw water; however, 3 hrs of aeration
was sufficient to obtain a 100 mg/1 level of BOD in the treated water. COD
removal efficiency was 40% and 70% after 1.5 and 48 hrs of aeration, resp.
The treated water had a pH of 7 to 8, compared to a raw water pH of 10.
The color intensity measured at 280 nm decreased to 10% to 60% of the color
intensity of the raw water; intensity at 500 nm decreased to 10% to 80% of
that of the original.
Decolorization efficiency increased with increased aeration time, but
not significantly. Although this treatment was sufficient to lower the
[BOD] to acceptable levels, it was necessary to inject ozone into the
aeration bath in order to achieve acceptable [COD] values.
TX-09
Ti tle: Unknown
Author: Anonymous
Source: Textile World, 126(11):108, 111, 113, 115, 116, 118, 121, Nov.,
1976c
182
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Several aspects of pollution and energy savings in the textile industry
were discussed. The problem of substances used in permanent press processing
of cotton which could produce carcinogens was investigated. A major concern
was the correction of water pollution caused by effluents from textile
works.
Tests were conducted on dye bath, scour and rinse waters from the
dyeing process. In several cases, high levels of BOD, TOC, or ammonia-N
were explained by known additions to the dye bath. [BOD] was reduced by
biological treatment, but [TOC] reduction was not as great, suggesting the
presence of materials which were not readily biodegradable. Biological
treatment was not successful in color removal, but a treatment which combined
alum and powdered activated carbon was quite effective. Lime was an effective
treatment for wastewater containing CaC03 forming levels of carbonate
alkalinity.
Reactive and basic dye colored water was successfully treated with
ozone, but it could not adequately decolorize wastewater colored by disperse
dyes. 1,2,4-Trichlorobenzene, a dye carrier, is biodegradable and 65% or
more of it can be removed in a well aerated basin.
For small plants a fixed bed adsorber system with no on-site regeneration
system was suggested. Larger plants were urged to incorporate a pulsed bed
system with an on-site regeneration system for recycling spent carbon.
Combined activated carbon and biological treatment systems are being tested.
TX-16
Title: "Studies on the Liquid Waste Treatment of Dye Manufacturing
Plants. (II)"
Author: S. Maeda
Source: Gijutsu to Kogai (Technology & Public Nuisance), 4(4):22-28 (1974)
Waste constituents to be treated include soluble organics (I) (p-
aminophenol, p-nitrophenol, their isomers and various intermediate products),
Na sulfide (II) and Na thiosulfate (III). [COD] values normally are 40,000
to 60,000 mg/1. I can be removed by polymerization with HCHO, which also
reduces [II] and [III] by about 10%, and results in about 50% reduction in
[COD] if applied as the 1st treatment step. II then can be removed by
reduction of pH to 3.0 to 3.5 and oxidation with air, S02 or chlorine (no pH
adjustment using chlorine) or by FeSO^ III then can be removed by ozone
oxidation or acidic decomposition, producing 83% to 85% overall reduction in
[COD] (to 6,000 to 10,000 mg/1). Subsequent neutralization and alkaline
ozone oxidation produces a final [COD] of 3,000 to 4,000 mg/1 (92% to 94%
total removal).
Na thiosulfate pentahydrate (60 g) in 6 1 of water containing 20 g of
NaOH was completely decomposed in 7 hrs with 25.87 g of ozone (1.47 g of III
183
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oxidized/g of ozone). In the acidic ozonation of III, only a small amount
of ozone is required. Thus 125 g, 250 g and 750 g of III in TOO ml of 1:1
H2$04 required 3.49 g, 5.29 g and 6.73 g, resp., of ozone for total destruction.
Without ozone, acidic decomposition of III was somewhat >80%.
Ozonation of 1 liter of alkaline dye waste liquid ([COD] 40,000 mg/1)
11.5 hrs with 42.5 g of ozone gave 80% reduction of [COD].
Formalin (10 ml) treatment of 1 liter of alkaline dye waste liquid,
followed by condensation and removal of I ([COD] now 45,000 mg/1) and 8 hrs
treatment with 29.6 g of ozone, gave 90.3% removal of COD.
A 4 1 sample of alkaline dye wastewater was treated with formalin to
remove I, FeSCty to remove II and acidic decomposition to remove III, then
(2,650 mg/1 COD) was treated by alkaline ozonation. In 2 hrs the [COD] was
reduced 57.8%, and in 7 hrs, 87.2% (to 981 mg/1).
Ozone Generator: Mitsubishi-Denki Model OS4, adjusted to produce 3.74 g/hr
from air at a flow rate of 3.74 1/min. KI was used to follow the amount of
ozone generated.
Contactor: 2 rigid PVC tanks were used, 1 19-cm in diameter X 70 cm high,
the 2nd 13.5 cm in diameter X 49 cm high. Both used porous dispersion tubes
at the base of the tanks.
Economics: Not mentioned
"Ozone Treatment of Industrial Wastewater"
Author: H. Matsuoka
Source: PPM 4(10):57-69 (1973)
Reviews the generation, properties and contacting of ozone, and its use
in treating drinking water and industrial wastewaters.
Cyanides are converted to cyanate (ozone/CN" ratio = 3) then to carbonate
(ozone/CNO" ratio = 2). Phenols can be removed from solution at an ozone/-
phenol ratio of 2.
Studies by Kawazaki e_t a_l_. are cited (TX-14) in which surface active
agents were more than 90% decomposed with a 5-fold excess of ozone. Kawazaki
also used activated carbon to adsorb surface active agents, then regenerated
the activated carbon with ozone (details not given). Studies by the present
author show that surface active agents are attacked only after dyestuffs are
decomposed and decolorized by ozone.
184
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Ammonium ion is oxidized quickly with ozone at pH 7.5 to 8.0 j[
t: Singer & Zilli [IC-10] found oxidation of ammonia occurs ont
Abstractors'
Note: Singer & Zilli [IC-10] found oxidation of ammonia occurs only above
pH 9). Zeolite acts as an effective catalyst for this reaction. Sulfite
and nitrite are easily ozonized, and organic mercury compounds can be conver-
ted to "inorganic substances."
7 Japanese dye manufacturing plants are using ozone for treating
wastewaters, as follows (date installed):
Mitsubishi-Denki: Press and float, ozonation [12,000 cu m/day, 16 kg/hr
ozone (Aug. 1973)].
Mitsubishi-Kurogawa Industries: Coagulation, ozonation [100 cu m/hr, 2.4
kg/hr ozone (Oct. 1971)J.
Kyoshenski-Mitsubishi: Filter, activated carbon, ozonation [50 cu m/hr, 1.2
kg/hr ozone (April 1973)].
Organo-Shobo (Ozone Fuji-Denki): ozonation, activated carbon [3,300 cu
m/day, 7.2 kg/hr ozone (summer 1973)].
Nishimo-Mitsubishi: Press and float, ozonation, activated sludge [200 cu
m/day, 1 kg/hr ozone (Jan. 1973)].
Ozonation using pretreatment with spray filter beds has been developed
by Fukui-Senkyoshi.
For water recycling, Mitsubishi-Juko (Ozone Mitsubishi-Denki) uses
secondary treatment, coagulation, sand filtration, ozonation and activated
carbon (1,800 cu m/day, 300 g/hr of ozone).
References: 13
TX-20
Title: "Decoloring Mechanism of Dyes with Ozone and the Effect of pH"
Authors: S. Nakayama & M. Maeda
Source: Mizu Shori Gijutsu (1976) 17(2):157-161; Chem. Abstr. 86:60133f
Aqueous solutions of Alizarin S (I) and Naphthol Yellow (II) were
reacted with ozone at 25°. Initial [I] of 50, 100 and 200 mg/1 were used to
determine the reaction order with respect to ozone. A first order reaction
was observed for the dye and ozone, individually. The decolorization rate
of I increased with increasing pH, but more ozone was required with increasing
pH, i.e., the efficiency of decolorization declined. For II, pH did not
appear to affect the rate, but the efficiency decreased with increasing pH.
The mechanism of decolorization of dyes with ozone is discussed in relation
to these results and quantum chemistry.
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TX-22
Title: "Advanced Physical-Chemical Treatment of Dye Wastes"
Author: A. Netzer
Source: Progress in Water Technology 8(2-3):25-37 (1976)
A research program was undertaken to characterize the effluents from
the dyehouses of various textile mills and to examine the success of color,
soluble organic and heavy metals removal from these wastes by massive lime
coagulation, activated carbon adsorption, ozonation, and polymeric adsorption.
In the lime dosage studies, 0.1, 0.3, 0.5, or 1.0 g of Ca(OH)p was added to
200 ml of dyebath effluent samples, the mixtures stirred rapidly 3 min, and
allowed to settle 1 hr. The supernatants were decanted, filtered, adjusted
to a pH of 7.6, refiltered and analyzed for color, TOC, and heavy metals.
Various amounts of activated carbon were added to 200 ml dyebath effluent
which then was stirred rapidly for 0.5 hr, filtered, and analyzed.
Compressed dry oxygen was fed to an ozonator at a rate to yield an
oxygen-ozone flow rate of 1 1/min containing 25 mg/1 of ozone. The oxygen-
ozone mixture was sparged into a 250 ml gas-washing bottle containing 100 ml
of dyebath effluent. After 20 min, the ozonation was stopped, and the
sample was filtered and analyzed. Five ml of hydrated resin was added to
150 mg/1 solutions of various dyes, the mixtures shaken 24 hr at 300 RPM,
the supernatants decanted and filtered, and the concentrations of dye remain-
ing in solution were determined by measuring the transmittance of the samples
and comparing the values with those on specially prepared calibration curves.
Lime coagulation gave excellent removals of free heavy metals and in
some cases very good color removals as well. Substantial reductions in
[soluble organics] and [color] were obtained by activated carbon and resin
adsorption. Ozonation was very potent for decreasing color intensity but
not for reducing [soluble organics].
TX-24
Title: "Treatment of Textile Wastewater by Activated Sludge and Alum
Coagulation"
Author: T.L. Rinker
Source: Blue Ridge-Winkler Textiles, Bangor, PA. NTIS Report PB-248,142/2
WP. EPA Rept. No. EPA/600/2-75-055, Oct. 1975, 216 pages
Reports treatment of wastewater from a textile mill producing synthetic
knit fabric for the apparel and automotive markets, with a system combining
biological (activated sludge) and chemical (alum coagulation) processes.
Treatment consisted of: heat recovery; equalization; completely mixed
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activated sludge with sedimentation and nutrient supplement; and alum coagula-
tion with sedimentation, polymer addition, and pH adjustment.
Activated sludge effectively removed degradable organics and ammonia-N.
Alum coagulation effectively removed colloidal organics, SS, orthophosphate,
and certain metals. Total treatment system removals for BOD, COD and color
were 92%, 73%, and 69%, resp. The capital cost of the system was $1.15 MM
with a yearly operating cost of $269,030, including capital depreciation.
Additional treatment was required to meet anticipated discharge limita-
tions. Research studies were conducted using carbon adsorption, resin
adsorption, and ozonation for residual, soluble color removal.
TX-25
Title: "Decomposition of Azo Dyes by Ozone."
Authors: S. Sato, K. Yokoyama & T. Imamura
Source: Preprint, 31st Fall Mtg., Chem. Soc. Japan, Oct. 2-5, 1974, p. 614
Scope: Determination of color removal from wastewaters containing azo dyes
with a secondary study of the degradation products after ozonation.
Method: Water soluble and insoluble dyes were tested. Methyl Orange was
used as a soluble dye and a 100 ml solution was ozonized in a 300 ml bottle.
With water insoluble dyes, 20 ml 0014 + 10 ml water was used. Ozone was fed
at a rate of 24 mg/l/min and its consumption was measured by KI.
Results: Major products of ozonation were identified by gas chromatography,
infrared spectrometry, mass spectrometry and various chemical methods and
results were as follows: from azobenzene: azoxybenzene, oxalic acid (I)
and glyoxylic acid (II); from p-aminoazobenzene and p-dimethylaminoazo-
benzene: nitrosoazobenzene, nitroazobenzene, I, II and nitrate; from p-
hydroxyazobenzene: I and II; from p-methoxyazobenzene: I, II and nitrate;
from Methyl Orange: I, II, nitrate and Na bisulfate. Minor oxidation products
also were detected by gas chromatography. p-Aminoazobenzene was 100%
destroyed by ozonation for 8 min.
TX-27
Title; "Ozone Treatment of Dye Wastes"
Authors: E.H. Snider & J.J. Porter
Source: J. Water Poll. Control Fed. 46(5):886-94 (1974)
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Ozone was used in a series of experiments to determine its ability to
degrade textile dye wastes. Dye wastes were analyzed for COD, color, total
solids, volatile solids and dissolved solids before and after they were
treated with ozone at 3 pH levels. Ozone reduced the color of the dye
wastes, but measurements were affected by high turbidity.
TX-28
Title: "Tertiary Treatment and Disinfection of Tufted Carpet Dye Waste-
water"
Author: L.M. Stuber
Source: Special Research Problem, School Of Civil Engrg., Ga. Inst. of
Technology, Atlanta, Ga. (Aug. 1973), 17 pp.
Review: Describes a study of ozonation as a tertiary treatment of carpet
dye wastewater following secondary biological processing.
Contacting: A 5.5 inch x 8 ft cylindrical Plexiglas column with ozone
supplied via a 60 y, high density polyethylene diffuser. Extra dry oxygen
was supplied to the ozone generator under pressure. Contact times were not
noted. Ozone was determined in the influent and effluent gases.
Results: After various doses of ozone were applied (graphical display for
each parameter tested) the following were observed:
1. COD levels: dramatically decreased up to 40% to 45% with 45 mg/1 of
ozone, then levelled off. SS did not significantly enhance reduction
of [COD].
2. Fecal Coliforms: not present at ozone dosages above 25 mg/1.
3. Total Coliforms: <100/100 ml at 45 mg/1 of ozone.
4. True color: reduced to <30 APHA units at 40 mg/1 of ozone. Reduction
in [SS] lowered the necessary ozone dosage to 26.5 mg/1.
5. [Soluble organic carbon] increased slightly with increasing ozone
dosages when SS were present, but eventually decreased at extremely
high dosages.
6. [SS] lowered 90%.
7. [BOD] increased 150% at 8 to 15 mg/1 of ozone, but was unchanged at
dosages >25 mg/1.
8. [Biphenyl] was reduced to 0.1 mg/1 from 2 mg/1 with 89 mg/1 of ozone.
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9. [Anionic detergent] was reduced to 0.1 mg/1 from 0.6 mg/1 with ozone
dosages of 15 mg/1.
10. Foaming problems were reduced and eliminated with ozone dosages of 50
to 100 mg/1.
11. DO residuals: 40 mg/1 when oxygen was used for ozone generation.
12. Ozone residuals dissipated totally after 20 min.
13. Transfer efficiency of ozone was 85% to 100% with dosages of up to 50
mg/1 of ozone.
References 20
TX-33
Title: "Treatment of Wastewater From Textile Dyeing Process"
Author: K. Tsukabayashi
Source: Yuki Gosei Kagaku Kyokai-shi 33(5):377-383 (1975)
Treatment methods for wastewater discharged from textile dyeing processes
are reviewed. These are coagulation-precipitation, flotation, filtration,
adsorption and biological methods. The coagulation-precipitation method
removes about 60% of the BOD and COD from the wastewater and 90% of the
color. However, the large quantity of sludge generated is one of the problems
with this method. The flotation method has a larger surface loading capacity
for wastewater treatment than coagulation-precipitation, permitting use of a
smaller facility with the flotation method to achieve the same results as a
larger coagulation-precipitation facility. Both these methods are very
effective in the decolorization of wastewater.
Selection of the appropriate coagulation agent will permit removal of
most dyes. The adsorption method by activated carbon or bauxite is suitable
as a secondary treatment method for wastewater rather than as a primary
method. The presence of Cr, Cu, Cl and aldehydes in wastewater can be toxic
to biological activity.
Ozone treatment is excellent but very expensive; it can be used as a
secondary treatment method. Any combination of these methods will produce
water which will meet water quality standards. A completely closed system
of water/wastewater is difficult to maintain in textile plants because of
the high quality of water that is needed in some of the individual processes.
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