WATER POLLUTION CONTROL RESEARCH SERIES
12010 EIE 11/68
A STATE -of-the- ART RE VIEW'of
METAL FINISHING WASTE TREATMENT
U.S. DEPARTMENT OF THE INTERIOR • FEDERAL WATER QUALITY ADMINISTRATION
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WA1 R POLLUTION CONTROL RESEARCH
The Water Pollution Control Research Reports describe
the results and progress in the control and abatement
of pollution in our Nation’s waters. They provide a
central source of information on the research, develop-
merit, and demonstration activities of the Federal Water
Quality Administration, Department of the Interior,
through inhouse research and grants and contracts with
Federal, State, and local agencies, research institu-
tions, and industrial organizations.
Inquiries pertaining to Water Pollution Control Research
reports should be sent to the Project Reports System,
Office of Research and Development, Federal Water Quality
Administ±ation, Room 1108, Washington, D. C. 202 2.
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A STATE -of-the- ART REVIEW of
METAL FINISHING WASTE TREATMENT
Sponsored by
FEDERAL WATER QUALITY ADMINISTRATION
U.S. DEPARTMENT OF THE INTERIOR
and
METAL FINISHERS FOUNDATION
Prepared by
BATTELLE MEMORIAL INSTITUTE
COLUMBUS LABORATORIES
505 KING AVENUE
COLUMBUS. OHIO 43201.
PROGRAM NO. 12010 EIE 11/68 GRANT NO. WPRD 201-01-68
NOVEMBER. 1968
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EWQA Review Notice
This report has been reviewed by the Federal
Water Quality Administration and approved for
publication. Approval does not signify that
the contents necessarily reflect the views
and policies of the Federal Water Quality
Administration, nor does mention of trade
names or commercial products constitute
endorsement or recommendation for use.
For sale by the Superintendent of Documents, U.S. Government Printing Office
Washington, D.C. 20402 - Price $1
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ABSTRACT
This state-of-the-art survey discusses information in the open literature
pertaining to waste treatment in the metal-finishing industry during the
last 25 years. The survey emphasizes such aspects as the nature of
electroplating and metal-finishing wastes; their impact on sewers, sewage
treatment plants, and natural water bodies; current restrictions on their
disposal; and conventional methods available for treatment of these
wastes.
The review of conventional treatment methods was intended to provide
facts for the guidance of the smaller plater in the selection of a waste
treatment process. It should be pointed out, however, that these methods
were developed more or less for use in larger electroplating plants
having large volumes of wastewater. The use of these methods for treat-
ing low volumes of wastewater would certainly be feasible, but could be
impractical or uneconomical for the smaller plater. .An evaluation of
these methods from this standpoint will be a major objective in subsequent
phases of the program.
This report was submitted by Battelle Memoi ial Institute, Columbus
Laboratories,in partial fulfillment of Grant Project WPRD 201-01-68 by the
Federal Water Quality Administration to the Metal Finishers’ Foundation.
Key Words: Electroplating wastes
Restrict ions
Waste treatment
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CONTENTS
Page
INTRODUCTION AND StDIMARY 1
ELECTROPLATING AND METAL FINISHING IN THE OVERALL WASTE PICTURE 3
The Nature of Electroplating and Metal Finishing Wastes 4
Where Wastewaters End Up 4
The Impact of Waste on Sewers 5
The Impact of Waste on Sewage Treatment Plants 5
The Impact of Waste on Streams, Lakes, Etc. 10
Restrictions 12
CHARACTERISTICS OF ELECTROPLATING AND METAL FINISHING WASTES 19
Sources 19
Quantities and Composition 19
Methods for Treating Rinse Waters 21
Conventional Methods for Cyanide Rinses 21
Complete Cyanide Destruction by Chlorine Gas 21
Complete Cyanide Destruction by Hypochiorites 22
Conversion of Cyanide to Cyanate by Chlorine Gas 23
Conversion of Cyanide to Cyanate by Hypochlorites 24
Conversion of Cyanide to Ferrocyanide by Ferrous
Sulfate 24
Conventional Methods for Chromium Rinses 24
Reduction of Hexavalent Chromium by Sulfur
Dioxide, Sulfites, and Ferrous Sulfate 24
Precipitation of Hexavalent Chromium by Barium
Compounds 26
Miscellaneous Methods for Treating Rinse Waters 27
Physical Methods for Treating Rinse Water 27
Other Approaches 29
Waste Reduction by In—Plant Control Measures 29
Selection of a Process 32
Costs 34
Sewer Rentals 39
Recovery 39
DISCUSSION 41
ACKNOWLEDGMENT 43
REFERENCES 45
APPENDIX A A-i
111
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FIGURES
Page
1 PRIMARY SEWAGE TREATMENT 7
2 TYPICAL TRICKLING FILTER SECONDARY TREATMENT PLANT 8
3 TYPICAL ACTIVATED SLUDGE SECONDARY TREATMENT PROCESS 9
4 ION EXCHANGE METHOD OF TREATING CHROMIUM RINSE WATERS OR
MIXED RINSE WATERS 30
5 EVAPORATIVE TREATMENT OF RINSE WATERS 122 31
6 CHEMICAL TREATMENT OF CYANIDE WASTE 33
7 CHEMICAL TREATMENT OF CHROMIUM WASTE 35
8 PROCESSES APPLICABLE TO MIXED CHROMIUM AND CYANIDE RINSE
WATERS 36
V
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TABLES
No. Page
1 EFFECTS OF COMPONENTS OF PLATING WASTES ON SEWAGE TREATMENT
PLANT 11
2 EFFECT OF PLATING WASTE COMPONENTS ON FISH LIFE 25 12
3 STATE REGULATIONS RE: WASTE WATER CRITERIA 15
4 SOME RESTRICTIONS ON PLATING AND METAL FINISHING WASTES
DISCHARGED TO SEWERS 17
5 VOLUMES OF CHROMIUM AND CYANIDE—BEARING WASTES FROM TYPICAL
PLATING OPERATIONS IN THE ELECTROPLATING INDUSTRY 20
6 CHEMICAL METHODS FOR DETOXIFYING WASTES 21
7 CHEMICAL CONSUMPTION IN WASTE TREATMENT 38
vii
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INTRODUCTION AND SUMMARY
There are between 15,000 and 20,000 metal—finishing facilities in the
United States. These include several thousand small—job shops, some
larger independent shops, and a larger number of captive facilities. The
captive shops are associated with manufacturing concerns producing speci-
fic end products, e.g., the automobile industry.
Electroplating and metal finishing waste streams are significant contri—
butants to stream pollution, either directly, owing to their content of
toxic and corrosive materials, such as cyanide, acids, and metals, or
indirectly, owing to the deleterious effect these components exert on
sewage treatment systems. Federal, state, and municipal regulations f ix—
ing the allowable concentrations of the harmful compon nts of these wastes
already have been established. The restrictions are fairly rigorous at
present. There is indication that they will, in many places, be made
more rigorous in the future. Enforcement of regulations may be expected
to become increasingly strict.
At the present time it appears that most of the smaller plating plants
are discharging rinse waters from chromium and cyanide operations
directly, with little or no in—plant treatment. Eventually, these
plants may be forced by Government agencies to trEat rinse waters.
There is an ample technology available for treating chromium and cyanide
rinse waters to any required degree of detoxification. The problem fac-
ing the smaller plater who may be forced to treat rinse waters before
disposal is not expressed by the question “Can the job be done?” but by
the question “What is the best and cheapest way for my particular plant
to do the job?”
A valid answer to this question must be based on a set of facts. These
are
(1) The volume and composition of the rinse waters to be treated
(2) The requirements set by Government agencies for an acceptable waste
effluent
(3) Capital costs for rinse water treatment facilities
(4) Operating costs for the treatment process
(5) Installation costs for the waste treatment facilities
(6) Credits from the recovery of metals, cyanide, or rinse water or the
decrease in sewage rental fees that might accrue to the selected
process.
One phase of this program is designed to provide such facts for the guid-
ance of the small plater. This state—of—the—art survey is an initial
effort to do so. It summarizes pertinent information appearing in the
open literature. The open literature, however, does iiot give ample
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coverage to the smaller plater. Additional information is being obtained
by such means as the circulation of questionnaires, by the sampling and
analyses of rinse water from many plating shops, and by the accumulation
of cost and some engineering data on the existing processes. Such inf or—
mation will be assembled and presented in a later report.
Another and possibly more important phase of the program is devoted to
the investigation and development of n w processes. This phase has just
begun.
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ELECTROPLATING AND METAL FINISHING
IN THE OVERALL WASTE PICTURE
The waste streams that are continuously, flowing into our natural waters
may be classified as natural, domestic, and industrial. Natural waste—
waters are those resulting from rain or melting snow. They carry silt,
sediment, soluble salts, small amounts of organic material and atmosphe-
ric gases, and floating pollution. Most of the natural wastewaters
discharge directly to natural water bodies without benefit of intermedi-
ate treatment. Some enter sanitary sewer systems as runoff after storms
through leaks, manholes, and seepage to dilute the normal waste burden of
the sewers. The polluting effects of natural wastewaters, as such, are
generally insignificant and transient. Natural waste streams can and do,
however, pick up and transport domestic and industrial wastes when they
are in the flow path, and these wastes may be deposited in streams or
sewer systems. For example, the runoff from farm lands may contain
unusually large amounts of soil and silt, and such materials as phosphate
and nitrate, residual insecticides, herbicides, etc. The runoff from the
vicinity of certain industrial plants may dissolve or physically trans-
port toxic materials from land or lagoon disposal sites. For this reason,
the land disposal of spent electroplating baths can be an undesirable and
possibly hazardous practice.( 1 -’ 2 )
Domestic waste streams are those generated in the kitchens, toilets,
bathrooms, noncommercial laundry rooms, and garages of the nation. Their
obnoxious characteristics and disease—producing potential have always
impelled mankind to do something about them, with the fortunate conse-
quence that adequate technologies have been developed to treat them.
The degree of treatment given domestic waste depei jds on a number of fac-
tors. These factors include the quantity of the sewage, the character-
istics of the natural water body that receives the treated effluent, and
population distribution along receiving streams, in most cases legally
set standards, and in a few regrettable cases mere expediency. Municipal
sewage treatment plants are primarily designed to treat domestic waste.
They are effective——sometimes with minor modifications——on many indus-
trial wastes as well, particularly those in which the pollutants are
organic. Some of the components of industrial wastes, however, are
incompatible with the processes used in domestic sewage treatment plants.
If their concentration exceeds certain low limits, they can seriously
impair or completely destroy the functioning of the plant.
Industrial waste streams are those arising from man’s commercial activi-
ties. Unlike domestic waste streams, which are reasonably constant in
composition and relatable to population in volume, industrial waste
streams cover the gamut of composition and volume. This variability
makes it necessary to consider each waste stream as a separate problem.
Solution of this problem requires basic data on the volume and composi-
tion of the waste and on the volume and composition of an effluent that
*References are listed on page 45.
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can be tolerated by a receiving stream, sewer, or treatment plant. This
is particularly true for the electroplating and metal finishing industry,
which emits highly toxic and sometimes corrosive wastewaters.
The Nature of Electroplating and Metal Finishing Wastes
Wastes from an electroplating and metal finishing plant may range from
virtually nontoxic to highly lethal and/or corrosive. Innocuous ef flu—
ents are achieved only by the use of thorough in—plant waste treatment
methods. Highly lethal or corrosive effluents are generally the result
of the accidental or intentional discharge of concentrated solutions.
The incidence of accidental or intentional discharge is minor in the
metal finishing field.
The wastewaters from the bulk of the plating plants in this country are
of low to medium toxicity, and they might be generally described in such
terms as noncatastrophic, presently tolerable, and borderline. Neverthe-
less, they are undesirably high in toxic and corrosive components, and
are not quite adequately controlled.
What is this typical, intermediate—grade waste that is emitted from the
majority of plants in the industry? Qualitatively, it is a dilute solu-
tion of toxic and corrosive chemicals such as hexavalent chromium, cya—
nides, metals, mineral acids, and alkalies. The dilution of the effluent
——as it leaves the plant——is almost never enough to render the solution
innocuous.
In a later section of this report, an attempt is made to characterize
this wastewater quantitatively.
Where Was tewaters j p
Wastewaters from plating and metal finishing plants always end up in some
natural body of water; most of these are surface bodies, but some are
possibly subterranean. However, the routes to these natural bodies of
water are different. A large majority of establishments run their wastes
to municipal sanitary sewers. Once In the sewage system, the industrial
wastes are diluted with domestic wastes, carried along with them to a
sewage treatment plant, and then to some natural body of water. In the
sewage system, the toxicity of the plating waste is decreased by such
mechanisms as dilution, mixing, neutralization, and precipitation, with
dilution exerting the greatest effect.
There are many metal finishing establishments situated in areas where
there is no municipal sewage system. The wastes from these plants must
take a more direct route to natural water bodies. These plants must
provide their own treatment before disposal; the extent of this treatment
will depend on the composition of the waste and on the levels of pollu-
tants permissible in the stream or lake.
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The Impact of Waste on Sewers
If sufficiently diluted and nearly neutral, plating wastes are only
mildly——if at all—--corrosive to sewer structures. But serious structural
damage from corrosion has occurred from concentratea and acidic wastes
not adequately diluted or neutralized before disposal. (3)
Plating wastes can create toxic conditions directly in sewers. Sewer
workers have been poisoned by cyanide gases generated from relatively
small accumulations of concentrated plating wastes in sewer systems.( 4
Even relatively dilute cyanide solutions in sewers can be dangerous.
Experimentation has shown that a solution containing as little as 50 ppm
of cyanide can generate lethal concentrations of cyanogen in sewer atmos-
pheres. A maximum of 20 ppm of cyanide in sewer waters is considered a
safe level by some, but other investigators state that 20 ppm of cyanide
in small sewers is dangerous and that as low as 10 pm can be harmful in
large sewers where men may work for long hoursJ 35 ’
Plating wastes may also exert indirect toxic effects in sewers by promo-
ting the anaerobic decomposition of domestic sewage in sewer lines.
Anaerobic decomposition gives rise to the formation of methane (sewer
gas) which has been known to suffocate sewer workers and which may cause
fires or explosions. Fortunately, there are few instances of these
phenomena.
Plating wastes also can cause the blockage of sewers by solids, although
this occurs rarely when wastes are sufficiently dilute.
The Impact of Waste on Sewage Treatment Plants
The general objective of sewage plants is to produce a treated effluent
that will meet specifications set by state regulatory bodies. Specific
objectives may be any one or combination of the following.
(1) To render the sewage inoffensive with respect to appearance, odor,
etc.
(2) To reduce the disease—producing potential of the sewage to a point
consistent with the subsequent usage of the water
(3) To avoid creating conditions that may kill the normal population of
aquatic life in the receiving stream or lake.
The size, nature, and subsequent usage of the receiving stream has a
great deal to do with the degree of sewage treatment required. Coimnuni—
ties on the seacoast, near large lakes, or on the banks of large streams
may simply screen their sewage and pump the untreated effluent into the
natural body of water. Federal and state regulations, mostly formulated
since about 1948, have done much to eliminate instances of serious and
growing pollution arising from this “no—treatment” practice. Prior to
1948, for example, less than 1 percent of the population in the Ohio
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River Basin was served by sewage treatment plants. By 1960 the percent-
age of the sewered population which operated or was constructing treat-
ment facilities had risen to 84 percent.( 6 )
Communities discharging their sewage effluents into reasonably large
streams or lakes may practice what is called “primary t ’ treatment. The
“primary” process is outlined in Figure 1. This amounts simply to screen—
ing to remove floating materials, grit and sand separation for the pro-
tection of plant equipment, and sedimentation (or settling) to remove
solid organic sewage. Primary treatment produces a more or less clear
effluent, but one that is still contaminated with oxygen—consuming com-
ponents and, possibly, disease—producing bacteria. Many municipalities
disinfect the final effluent from primary treatment plants by chlorina-
tion to eliminate any possible disease—producing organisms. In the
sedimentation or settling step of primary treatment processes, inorganic
chemicals such as iron or aluminum compounds and lime may be added to
improve settling characteristics and the clarity of the effluent. Plat-
ing wastes are seldom harmful to the primary treatment plants. Excess-
ively large volumes of plating waste could, however, overtax the capacity
of the sedimentation tanks with the result that the sewage would not
receive the intended or necessary degree of treatment. Large amounts of
acidic wastes can corrode equipment and pipes, and will increase the lime
consumption of the plant. The metal content of plating wastes adds to
the volume of sediment or sludge produced and may interfere with the sub-
sequent “digestion” of the sludge, if this is practiced by the primary
treatment plant.
Many communities, owing to the volume of their sewage effluent and the
nature and size of the receiving stream, are forced to practice what is
called “secondary” treatment. In this process, the sewage is screened,
freed of sand and grit, and subjected to sedimentation as in the “primary”
treatment method. The effluent from the primary sedimentation tank is
then given an additional or secondary treatment. This secondary treat-
ment amounts to aerating the solution in the presence of aerobic bacteria.
The aeration step provides oxygen for the bacteria and other forms of
microscopic life to feed upon and destroy most of the organic soluble or
colloidal pollutants that remain in the effluent from the primary treat-
ment. After these bacteria have done their job and the pollutants have
been ingested, the treated sewage again is subjected to sedimentation
where a secondary sludge settles out and the treated effluent is
discharged.
The aeration step can be accomplished in a number of ways with different
types of equipment. The two major processes of secondary treatment are
the trickling filter process and the activated sludge process. These
are outlined in Figures 2 and 3.
It is with plants using the secondary treatment that plating wastes can
wreak the most damage. This is because the chemicals and metals occur-
ring in these wastes may, if sufficiently concentrated, be toxic to the
bacterial colonies which make the process operate. There have been
numerous instances where the efficiency of secondary treatment plants
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Chlorine Gas
Bypochiorites
or Sand Separation >Sand, Fine Heavy ltinerals,
Stones, etc.
Sedimentation > Primary Sludge (Settled organic
matter; metal hydroxides of
iron, aluminum, trivalent
chromium, copper, zinc, cadmium,
adsorbed or coprecipitated
soluble or colloidal materials
calcium sulfate, etc.)
To Disposal or Digestion
—Disinfectioa
F
Effluent to Disposal in
Natural Waters
(Small amounts of suspended matter;
Oxygen consuming soluble and
colloidal materials;
Soluble inorganic sulfates, chlorides,
Variable percentages of the hexavalent
chromium, cyanides, and metals intro-
duced with the original sewage.)
Sewage (Domestic and industrial wastes)
‘if Products
Screening > (Large floating and suspended
matter: paper, sticks, plastics,
etc.)
Re agents
Grit
Iron and aluminum
salts, lime, etc.,
(May be added to.
promote settling.)
FIGURE 1. PRIMARY SEWAGE TREATMENT
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Effluent from Primary Treatment
______________ 1
Atmospheric Air- Trickling Filter
(Introduced by natural (A bed of crushed stone or gravel
convection.) onto which the sewage is sprayed
and through which it flows or
trickles. Aerobic bacterial
colonies build up on the surfaces
of the bed material and consume the
organic components still remaining
in the effuent from primary treat-
ment.)
Secondary Settling ) Sludge or Solids
Dislodged from the
Trickling Filter
(Composed of colonies
of aerobic bacteria
and other organisms,
adsorbed solids,
metal compounds, etc.)
Treated Effluent
(Contains relatively small amounts of
oxygen consuming organics; smaller
amounts of cyanide, chromium and
other metals than were present in the
effluent from the primary treatment.
Little or no disease producing bac-
teria. Soluble salts.)
To Anaerobic
Sludge Digestion
FIGURE 2. TYPICAL TRICKLING FILTER SECONDARY
TREATMENT PLANT
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Effluent from Primary Treatment
Air Aeration Tank
(Mechanically introduced (Aerobic bacteria present in the
by agitation, blowers primary effluent and introduced
etc.) in the process by circulation of
some of the secondary sludge which
has been activated, consume soluble
and colloidal organics, and may A portion is
ingest some metals and cyanides.) recirculated
to the aera-
tion tank to
fortify the
necessary
aerobic
conditions.
______ I
Secondary Sedimentation Tank ) Activated
Sludge
(Aerobic
bacterial
colonies,
adsorbed or
inges ted
metals, etc.)
Treated Effluent
(Contains relatively small amounts
of oxygen consuming organics.
Smaller amounts of cyanide, Excess Sludge
chromium, and other metals than to Anaerobic
were present in the primary Digestion
treatment. Little or no patho-
genic bacteria.)
FIGURE 3. TYPICAL ACTIVATED SLUDGE SECONDARY
TREATMENT PROCESS
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have been rossly or completely impaired by slugs of concentrated
wastes.( - Table 1 lists some of the important troublemaking com-
ponents of plating waste and shows their reported effects on primary and
secondary treatment plants.
There is another unit operation——practiced by both the primary and secon-
dary types of plants——in which the metals in plating wastes can be and
sometimes are harmful. This is in the so—called “sludge digestion” step
In which primary sludge, either alone or mixed with secondary sludge, is
subjected to treatment by anaerobic bacteria. In this process the con-
centrated sludge, still offensive and toxic, is converted to an innocuous,
readily disposable material. Digestion is carried out in the absence of
air in large, closed, heated tanks. The digestion process produces a
mixture of methane, hydrogen, and carbon dioxide which frequently is
burned to supply heat for the sewage plant.
The metal components of the plating wastes concentrate in the settled
sludge from primary and secondary treatment and become concentrated even
more in the sludge digestion tanks. Instances have been reported where
sludge digestion processes were completely halted due to the accumulation
of metals (such as copper) in the digestion tanks.(’ 6 ) It has been esti-
mated that when the total concentration of chromium, copper, nickel
zinc, and cadmium exceeds 400 ppm in digesters, failure can occur. ’ 7
Such concentrations could be produced by raw sewage containing 1.5 to 3
ppm of these metals.
Cyanide does not concentrate in sludges and, in fact, largely decomposes
in secondary treatment. However, if the cyanide content of the raw sew-
age exceeds certain levels, enough may be transferred to the digesters to
cause trouble .(l8) A steady feed of raw sewage containing 5 ppm of
cyanide is capable of disrupting digester operation.O- 9 )
The Impact of Waste on Streams, Lakes, Etc .
One of the benefits of plating wastes disposal via municipal sewers is
that the wastes become highly diluted and mixed with other wastes; the
toxic components are then removed in the sewage treatment process. This
is not true for plants that dispose of their wastes directly into natural
streams and lakes. Restrictions on the effluents from these plants are
significantly tighter than on effluents destined for municipal sewage
systems.
There always is some danger that the components of plating wastes in
streams can be harmful to man. Cases have been reported where latin
wastes were fed to a stream and caused fatalities to livestock.” 20 ’ 21
The major and most frequent danger, however, is the destruction of
aquatic life. This can occur with extremely low concentrations of cya—
nides and metal saits.( 2 2 24 ) The data in Table 2 provide some concept
of the lethal nature of these compounds to fish. These data show the
lowest concentrations which have been demonstrated to be lethal. The
lethal concentration will vary with the type of fish, the pH and hardness
of the water, temperature, etc.
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TABLE 1 • EffECTS OF CC 4PONENTS OF PLATING WiSTES C* SEWAGE TREAThENT PLMIT
Concentration Concentration
Partially with of “Slugs” Concentration
Precipitated Tolerable Appreciable Causing May Cause of Slug. Affects Partially
With or Corrosive to Concentration Effect at Temporary Increases Nigh causing Oxidizing or
Adsorbed by Equipment or at Steady Steady Flow, Impairment, Toxicity Sludge Considerable Ability Largely
Sludge Structure. Flow, ppm ppm ppm of Metals Volumes Impairment of Sludge Consumed
Hexava lent Chromium
Primary x
Trickling filter 1-4 10
Activated sludge x 2-8 5-10 10-50 100-500 x
Trivalent chromium
Primary x
Trickling filter x
Activated sludge x
Copper
Primary x
Trickling filter x 1-3
Activated sludge x 1 4(e) 50 x
I—’ Primary x
Trickling filter x 1-3
Activated sludge x 5-10 x
Cadmium
Primary x
Trickling filter x
Activated sludge x x
Nickel
Primary x
Trickling filter x
Activated sludge x 1-3
Cyanide
Primary
Trickling filter 2 ‘a’ 30 x X
Activated sludge 1-2 9’ / x x
Primary x
Trickling filter x
Activated sludge x
Solids
Primary x
Trickling filter x
Activated sludge X
(a) Combination of 9 ppm CN and 4 ppm Cu adversely affected sludge flocculation.
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TABLE 2. EFFECT OF PLATING WASTE COMPONENTS
ON FISH LIFE( 25 )
Component
Levels
Fatal
of Concentration
to Some Fish, ppm
Hexavalent chromium
5
Trivalent chromium
about 5
Cyanide
0.05
Ferrocyanide
1.45
Copper
0.02
Zinc
0.3
Cadmium
0.6
Nickel
5
Restrictions
Water pollution by domestic and industrial wastes has been recognized as
a threat to the health and welfare of the country for many years. Prior
to the 1940is many individuals, associations, Government agencies, and
communities fought isolated battles against pollution; many more did
substantially nothing. It was not until after World War II that public
officialdom became generally aware that water pollution had already
reached a serious level and that with the accelerating growth of popula-
tion and industry the problem could become catastrophic.
In 1948, the Congress of the United States passed the Water Pollution
Control Act which was to have the effect of unifying and implementing a
nationwide battle against water pollution. This act was extended in
scope and sanctioned by additional legislation in 1956, 1961, 1965, and
most recently the ‘Clean Water Restoration Act of 1966’.
Federal legislation is aimed primarily at maintaining the quality of
federally controlled interstate and other natural waters as they may
affect the public health and welfare. The laws allocate the authority
and responsibility for maintaining water quality to the individual states
and, in the case of interstate waters, to associations of states. Juris-
diction over intrastate waters is left to the individual association of
states with the provision that Federal intervention is possible upon the
request of a governor.
The role of the Federal Government is largely advisory and coordinating.
It provides guidelines for the states and interstate associations to
follow, reviews criteria and enforcement procedures set by the states,
determines their suitability for achieving the aims of the Federal water
quality laws, and adjudicates disputes or differences that may crop up
between states. The basic regulations for water quality are therefore
laid down by the individual states or by associations of states which
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either directly or indirectly determine the quality of all wastewater
generated within their jurisdictional area, industrial and domestic
alike.
Direct control by states or state associations applies when effluents
are sent directly to state or interstate waters. Such is the case for
municipal sewage treatment plants discharging into streams or lakes, or
rurally located industries discharging their waste directly to some body
of natural water. Indirect control by the states is exerted through
municipalities that operate the sewage treatment plants. These munici-
palities are answerable to the state for the quality of their sewage
plant effluents. It also is left to these municipalities to ascertain——
by proper regulation and enforcement——that industrial plants using their
sewers and sewage plants do not discharge wastes that would impair the
quality of the sewage treatment effluent.
The intent of various Federal and State agencies charge.d with the abate-
ment of stream pollution is to improve or maintain the quality of surface
waters at levels commensurate with the anticipated use for these waters.
A comprehensive guideline which sets forth the standards for the five
basic uses of water recently has been developed by the Federal Water
Pollution Control Administration. This guideline has been published as
a report entitled Water Quality Criteria. (135) The five basic uses of
water outlined in that publication are
(1) Recreation (including aesthetic uses)
(2) Fish, aquatic life, and wildlife
(3) Public water supply
(4) Agriculture
(5) Industry.
Since the majority of plating shops in the country are located in or near
highly urbanized areas, the restrictions placed upon their effluents are
influenced by the standards set for public water supply. These standards
are set by the U. S. Department of Health, Education, and Welfare and ate
to some extent tentative; periodically they are revised.( 27 ) The follow-
ing tabulation is an abridgement of specifications set up in 1962 (list-
ing only the specific components likely to be found in plating plant
effluents)
Recommended Maximum Levels for
Component Leve ppm Rejection, p p
Arsenic 0.01 0.05
Barium 1.0
Chlorine 250
Copper 1.00 ——
Cyanide 0.01 0.2
Iron 0.3
Cadmium 0.01
Nickel 2.0
Sulfate 250
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Recommended Maximum Levels for
Component Level, ppm Rejection, ppm
Tin 1.0
Zinc 5.0
Hexavalent chromium 0.05
Trivalent chromium 1.0
Lead 0.05
Silver 0.05
The “drinking water” specification is more or less a guideline based on
the toxic potential of the above components to humans. If the stream,
stream segment, or lake is used for fishing, restrictions on some com-
ponents (such as cyanide, barium, copper, and zinc) are much tighter; the
permissible levels are based on such conditions as the type of fish
involved, alkalinity, and hardness of the water.
Each state and association of states has adopted its own route to satis-
fying the objectives and intent of the overall Federal legislation. One
state, Pennsylvania, requires that all effluents meet the “Drinking
Water” standards except for chlorides, sulfates, and nitrates. It fur-
ther requires that hexav 9 le t chromium and cyanides in wastes be kept
below detectable levels.” 26
The majority of state agencies and interstate associations have adopted
a different approach. These agencies first determine the usage to which
the water in a stream, stream segment, pond, or lake is to be put and
then, employing various terminologies, classify the water according to
this usage. Each class is assigned maximum limits for the concentration
of pollutants by considering the dilution afforded by the stream itself
and by tributary streams, the naturally occurring “self” purification of
the stream, etc. Table 3 shows the regulations imposed by the states.
Municipalities also are obliged to produce sewage plant effluents that
meet the standards of the states or group agencies. They in turn apply
their own regulations to industries contributing to their sewerage
systems.
Municipal regulations are based on such factors as the volume of the
waste in relationship to the total volume of sewage waste; the type of
sewage treatment employed; limitations imposed on the sewage plant’s own
effluent; the number, size, and type of industry discharging to the
sewers; and, in some cases, the materials of construction and the engi-
neering details of the sewers or the treatment plants. Their specifica-
tions will require in—plant treatments ranging from “complete” to none.
Table 4 shows typical restrictions on flows to municipal sewers.
The disposal of concentrated wastes such as stripping or anodizing solu-
tions often is not specifically regulated, but these must be treated by
dilution, neutralization, and detoxification procedures to the point
where concentration of harmful components (acids, alkalies, cyanides,
metals) meets the requirements of the municipalities or states. In some
14
-------
I—S
TABLE 3. STATE REGULATIONS RE WASTE WATER CRITERIA
W M4M4
——_ -——
MOONS
.
. . , . ,, l . . .,Cl.lf.
! ‘
I444
— —
.I44
u4
A .ld9.v!Mll1
— — --—•
CHEMICAL CONSTITUENTS - DPM iou .o CONTSWO
C . 3 . Cd ss.s c .o .J ci 101 CN P.C94 .) 0 4,
-
— — — —- — - — — — -—- — ---- — — —
. I W*
- I_ i M
oil SoD 94. I Ts.W MENTS
I
— — -—
- I .,
—-—-—
-
j
4.941
-
—
___ -_
— — — —- — — — — - -—
— — — — — —
CONNICTICU9 K)j - -
DILAW4,I 43-31 I I - ‘ — ——
— - - - - --..- - -—— -- - -- -- —--- — ---—--—- —t---- --- — .-- - - - - — --- ——- -— - —— —— - - -
OSOSGIA 3-3935 J j
T
:
isiois ss .t,. ... (7) —.L .J o I .,
i iii lzi I liii rLll_LJLILJ Li_L ii iJ i i ii ;
54MM 43.44 — — ._. ( 1 )— - L L._J N ._ — -
IIN1OCCY 41534 — — — —
zi ii J±tH L t
‘— - -
- - - — -
TT T
NIOS TT - - -
N INWflO 9A . , . , - I I Li1 --
39104091771 171394! — -—-——------
- - —--- ;- - - 0 - - -‘ll!! - H
3940101*1 4.10.91 . . •. I 7 . _I. ..k.s ,n. h. .i.d ., 91.4, 11, 1*.. 0 - -
—— -—----4— M*Il0H;. AIh.ll. .MS .Js .I4S “-- r
) ) . 1 . , ..IIy.1u , 4 ,I, .. I Y .., s. 0 .Q, ——
— — — --————--- - —-—-—-- --- —- — ONW
I Is I--—- -——- —-——---- - I — 4 I
i E ’ft4
NOHS oI usss s.s.. P.bli . ll..l$4 Sl .S14 (I) MM.. ..l I.,i, 9’) Wd 1 14 7439 7 .11, 1 1* C.,t& C . _ .4l (I D) 7,.;. 1,4.0 . ... 7.. Cl)
)2PW39 .! 1*4 10 CASAC dC.llS..l . 0) h4.. ,II ,. 1*I..l.I. NIpS.. 4.39 9) C.&d . . 1* 1 , 3 9 . _I Cs ., 0.. , 139,17 (II) N•_ *39.4,7.41.. 5...,...
7 . 4 11.394. 3)1997) . 14 0* .. PWis.. . -I.IO M4,..C.,h. .*b r, . 4.I,.I NI
9) 739,. 4141,9 W.;p 4*114.. 1 .. Up.
(3) 5.39. 91394*1971 k.I , Ca 7) N 9,91.14 ... Wd P P.lI39IP 44439 * ID) 74*.. Alt., P*t. , ,bI. 011394,
C . _tNI C..... I, ! . ..1, ;, 9.4
-------
TABLE 3. STATE REGULATIONS RE: WASTE WATER CRITERIA (continued)
CHEMICAL CONSTITUENTS - PPM
H C C Cd
( Il .3 _ ; 4.) 0.
I 0 0.3 0.3 LL . T 0.4
t —
J .I 0.303 4
01 o’.4.a — — — I
- 0.d
‘?, . .: . -: - -
-!L_
-,
JJ iYi Hr_LiT
(04011 COMO’4T
. . ._ - - .. .
- -
“
—
c.io.
( II)
I — —
--
. .‘ ‘—
-. - V..4I.4A .
II I ) P.. ( I I
— - - - - ---
T
(I I ) (I I )
3p,4
.. II .
iiiiiiii ___
C I . . . ) ). I
_ —- -_-- - 1_’1
40. 0. 0
4
4442
4 __4 L
.. —
—
44 60.00
040400 CU013044 OH — e_a.ao
L A.. 104) . — —— .O.L (
‘
(400 )0 04000* r j
( I I )
.
.4 ,—
0
--
ii
( 0,
f .
( ‘ 0
i
T
iiii
iir
. .
( ,
). .
Ii
II
T
i
ii
-1*t ) 00 (0 )1 K MAIIOIAIS . ----- -- - - - -- - —-.
1TII1L . .LJ1LJ _L_L L, .. ,.
._ —. — —— (MA . 3 (, . 20p. 30
(0 —_ _. ._ OP.... 04.... °°
. — . — -— -—--
T r Tr I I 0 0 ). L0 p.
- -I - L1 - — —
s. , . .
HO) 0.3 0,0 0.0 0.4 -— —- --- - -—-(IO)-- 0.0 0.{ 1(O) 5- -————---- - -—(I2) —--- - — .-
I .
-tIMII I (0 00 ( (0 I V (TAO) lOUD OP ((MOM — — 0 3.P. ..
—= - -:-— -— -— . -- —.--_. . -- -— --.-. - ---
- —-- . — -- - -. - -- (IS) 2 ) 4 . .. I
_ - - :
t .± T.. HI : i H H 1 -H. H H) E.HI. H
.
._
P . ..
-
.
(I) ...p 1 .. 4 . * . A.
._
0.
004044004*
_
04(0004 H)
POPrNVIVANMA C . ..40
iii iiii
.. ‘ ). 4. I
1 - —.
( 0VNCUOUMA 44 44 ‘-
- t±j
( nAN _ 3 .o .
e.o_a, ,
‘ “
s_a.,
rl.4.
::;: .
-
0
—1 02)—-—--- Nk4.I.2,0 ., N4*0.IO ( ’ .
1 i
0 0 0
—----r— —
I ( 02)
f II
.EE
O0 0.4 4OMA . 4
0
0 , .4
‘1
E
‘000)04*
-
43334 J
—
——-—-——
.
- --
-
—-
I
—
—
--
—
—
----
—
—
—
—
— —
. . -—-.. - —-
( I) (2)
04* 1 010400004
W*3 )0I04000N .0,C.
—_____
W(HVIOGINI4
0404C004)M
N0
0*
12.1044
1-—---
4.1344
.H4dj
4
•
.i
—
LsO. (
. 1 . 0.)
—
s3i ’ 5 3 0
.-- —
— .— -—————— — —
(.. .---...._ - -. - -—-----.—-—— ---- - . .-...- — - -. . -.—-- ) ( ) —-—.-—.——-— —— - -— —— - —- -
** LJ I ... H 1”J
—
I
—- --.- - - - ...
-
—-(1
(— -
0 . P . . ..
- --‘ •
I )?)
—_ - - - .—,- ——— - - .————
0.0 )045
- - -- -- .---- II--- - - - ‘
((3
—_—
-—
-—
(04
: :r ’ 4
,- L --
- —
--—--—
liT iiilI TT l ir_ _L
. .:::‘
‘ ‘
—-
-
—
—-
I
HL
:H._
--L --
ii
—
A n _ I , . )
—
j#s_s.s
0.13 . s 1.04 230 220 C I
.
Taken from Finishers’ Management (June, 1968)
-------
TABLE 4 SOME RESTRICTIONS ON PLATING AND METAL FINISHING
WASTES DISCHARGED TO SEWERS
Other Total
6 Heavy Dissolved Suspended
pH CN Cu Cr Cd Zn Ni Ba Metals Solids Solids Ref .
Typical Limits 6—10 0 0.3 0.05 0.4 0.3 2.0 —— —— —— 28
Typical Range 5—10 0.2 0.4 0—10 0—5 0—5 2—10 0—50 2000—5000 200—1000 21
Examples of Limits:
New Jersey 6—10 1 1 3 3 3 10 Avg. 1500 Avg. 500 29
Conneaut, Ohio 5.5—9.5 3 5 2 30
(1951)
Canadian — — 2 1 350 31
New York (1963) —— 0.2 5.0 0.5 0.5 5.0 3.0 12
Kentucky City 5.5—9.0 < 2 (a)
-------
cases, associations of platers have adopted the policy that such wastes
should never be sent to municipal sewers or streams, but must be disposed
of by other means, such as sale to outside salvage orgatlizations. In
some cases municipalities permit the disposal of concentrated wastes to
sewers with ample dilution and/or neutralization, but only after notify-
ing municipal officials. The direct disposal of concentrated toxic or
highly acidic wastes to natural waters is practically never permitted.
18
-------
CHARACTERISTICS OF ELECTROPLATING AND
METAL FINISHING WASTES
Sources
Waterborne wastes generated in the electroplating and metal finishing
industry include the following.
(1) Rinse waters from plating, cleaning, and other surface finishing
operations.
(2) Concentrated plating and finishing baths that are intentionally or
accidentally discharged.
(3) Wastes from plant or equipment cleanup.
(4) Sludges, filter cakes, etc., produced by naturally occurring deposi-
tion in operating baths or by intentional precipitation in the purifica-
tion of operating baths, chemical rinsing circuits, etc., when flushed
down sewers.
(5) Regenerants from ion exchange units.
(6) Vent scrubber waters.
From the viewpoint of the smaller plater, by far the most important of
these wastes is the rinse water. It is the constantly flowing, production—
connected stream that is generally so large in volume that it cannot be
economically impounded for treatment before disposal; this stream is
usually concentrated enough to be toxic. Under present restrictions and
enforcement procedures, rinse water disposal may not present much of a
problem to many platers. With more stringent regulations and more rigor-
ous enforcement, it could become an acute problem.
It is a chief aim of this review to present to the smaller plater the
currently available conventional processes which can be applied to rinse
water wastes. It is an aim of the current research program (for which
this review is a preliminary phase) to investigate several possible new
approaches and, eventually, to present an evaluation of all the processes
available.
The other wastes (concentrated sludges, dleanup water, filter cakes,
regenerants, and scrubber waters) are not believed to be of great concern
to the smaller plater because they are not so vitally connected to pro-
duction and can be handled as isolated, more or less individual problems.
Quantities and Composition
Much of the information in the literature on the volumes and composition
of electroplating and metal finishing wastes refers to the large— or
intermediate—size plants that do routine plating. Table 5 presents a
cross section of this information. As will be seen from the data, there
19
-------
0
TABLE 5. VOLUMES OF CHROMIUM AND CYANIDE-BEARING WASTES
FROM TYPICAL PLATING OPERATIONS IN THE ELECTRO-
PLATING INDUSTRY
Type of Work Plated
Chromium—Bearing Waste
Volume,
gal.
Analyses,
ppm(a)
Volume,
gal.
Cyanide—Bearing Waste
Analyses, ppm(a)
Cr Ni Cu
CN Cu Zn
Cd
Ref.
Aircraft engines and parts
440,630/day
— —— —
293,760/day
— — —— — —
——
35
Automobile bumpers
480,000/day
—— —— — —
——
—— -— ——
—-
36
Automobile grills
100,000/day
700 —— —
——
—— —— ——
——
37
Missile parts
80,000/day
1 —— ——
32,000/day
80 —— ——
——
38
Office furniture
24,000/day
—— —— ——
——
— — —— ——
——
39
Typewriters and office machines
50,000/day
16 39 ——
——
39 —— ——
——
40
Instrumentation and control
——
— —— —
13,000/day
—— —— ——
——
41
equipment
Electronic hardware
828,000/day
— —— ——
259,200/day
200—1500 —— ——
——
42
Rome appliances
43,200/day
—— —— ——
108,000/day
—— —— ——
——
20
Television antennaes
——
— — — — ——
11,000/day
—— —— ——
——
43
Silverware
40,000/day
5 33 135
165,000/day
172 18 11
——
44
Instrument motors and electric
112,000/day
— — — —
——
—— —— — —
——
45
clocks
Automobile manufacture
620,000/day
30 80 70
410,000/day
204 —— 113
——
46
Unspecified
—— — —
250—400/hr
40—130 —— — —
——
47
Metal fastener plant
89,000/day
52 302 ——
——
—— —— ——
——
48
(a) Analyses not shown are not available.
-------
are wide variations in both the volume and composition from plant to
plant. This is because the waste streams from these plants are the
product of local plant conditions and practices such as dragout, rinsing
techniques, recovery methods employed, and the admixture of other waste
streams, such as those from machine shops.
There is little or no information on the volume and composition of wastes
that might be encountered in the smaller shops that do general plating.
It must be assumed, however, that the rinse waters from the smaller
establishments are extremely variable from shop to shop, and perhaps
from day to day or hour to hour within a specific shop. As an example
of the variability that may be expected, one article indicates that
“typical” rinse waters from general plating operations may contain from
2 to 76 ppm hexavalent chromiunT, 0.5 to 32 ppm copper, 0.1 to 2 ppm of
nickel, and 21 to 68 ppm
Methods for Treating Rinse Waters
The technology of plating and metal finishing waste treatment has been
thoroughly developed and has been the subject of numerous excellent
publications.(l 50—63) There are at most about a dozen unit processes
which are basic to the technology as a whole. Each does a specific job
with varying degrees of effectiveness, simplicity of application, and
cost. These unit operations are listed in Table 6 and are discussed in
the following sections.
TABLE 6 CHEMICAL METHODS FOR DETOXIFYING WASTES
Conventional Methods for Cyanide Rinses
Complete cyanide destruction by chlorine gas
Complete cyanide destruction by hypochlorites
Conversion of cyanide to cyanate by chlorine gas
Conversion of cyanide to cyanate by hypochiorites
Conversion of cyanide to ferrocyanide by ferrous sulfates
Conventional Methods for Chromium Rinses
Reduction of hexavalent chromium by sulfur dioxide
Reduction of hexavalent chromium by sulfites, etc.
Reduction of hexavalent chromium by ferrous sulfate
Precipitation of hexavalent chromium by barium compounds
Conventional Methods for Cyanide Rinses
Complete Cyanide Destruction by Chlorine Gas . Cyanide in rinse waters
can be completely destroyed by treatment with chlorine gas in an alkaline
solution at room temperature. The cyanide radical, CN, is disrupted with
21
-------
the carbon fragment being converted to carbonate and the nitrogen to
nitrogen gas. The reaction involved is
2NaCN + 5C1 2 1- 12NaOH - N 2 + 2Na 2 CO 3 1- lONaCl + 6H 2 0.
Sodium Chlorine Sodium Nitrogen Sodium Sodium Water
cyanide hydroxide carbonate chloride
The process is carried out by adding chlorine gas and an alkaline com-
pound, such as caustic soda or hydrated lime, to the solution. Special
equipment is required for the safe and efficient addition of chlorine.
Some form of agitation is also necessary to obtain adequate mixing and
reaction rates. The overall reaction is fairly slow, possibly requiring
hours for the complete destruction of cyanide——particularly if the solu-
tion contains heavy metals which may form cyanide complexes.
The process can be carried Out on a batch or continuous basis. If done
batchwise, it requires the installation of rather large tanks for storing
the rinse waters before treatment. It has been recommended that dupli-
cate tankage be provided——each capable of undergoing treatment while the
other is filling. Recommended tank sizes vary, ran in in capacities
corresponding to from 4 to 24 hours of operation.( 6 ’ 6 ” 66 ) If done con-
tinuously on a flow—through basis, this process requires some instrumen-
tation to control the reagent additions and the quality of the effluent.
In the chlorination step, which is conducted under highly alkaline condi-
tions, most of the heavy metals that accompany cyanide in the rinse
waters precipitate as hydroxides, or possibly as ferro or ferricyanides.
These latter respond slowly to the chlorine treatment and, if permitted
to settle out, probably receive little or no treatment. This is one of
the basic reasons for the vigorous agitation required in the process.
Sludge formation nearly always accompanies the chlorination process. The
sludge is composed of the precipitated metal hydroxides and, if lime is
used to provide the alkalinity, the sludge also contains calcium carbon-
ate and possibly calcium sulfate. In some cases the volume of sludge
produced may be too great for disposal to sewers. If so, provisions for
permitting the sludge to settle before disposal of the liquid phase must
be incorporated in the plant.
The suitability of this process for the smaller plater has been ques-
tioned by some authorities, primarily because of the potential hazards
and difficulty in handling, metering, and distributing the chlorine
gas( 67 ) and in maintaining the proper conditions of alkalinity in the
solution to prevent formation and evolution of poisonous cyanogen chlo-
ride. Commercial a lication of this process is described frequently in
the literature. (681D)
Complete Cyanide Destruction by Hypochlorites . Cyanide also may be com-
pletely destroyed by hypochiorites such as sodium hypochiorite (NaOC1),
calcium hypochiorite [ Ca(OC1)2}, or bleaching powder (CaOC1 2 ). The prob—
able reactions, analogous to the reactions with chlorine gas in an alka—
line medium, are shown below
22
-------
2NaCN + 5NaOC1 + 1120 N 2 + 2NaHCO 3 + 5NaC1
Sodium Sodium Water Nitrogen Sodium Sodium
cyanide hypochiorite bicarbonate chloride
4NaCN + 5Ca(OCl) 2 + 21120 - 2N 2 + 2Ca(HCO 3 ) 2 + 3CaC1 2 + 4NaC1
Calcium Calcium Calcium
hypochiorite bicarbonate chloride
2NaCN + 5CaOC1 2 + 1120 - - N 2 + Ca(HCO 3 ) 2 + 4CaC1 2 + 2NaC1.
Bleaching
powder
The process Is relatively simple and consists essentially of adding the
hypochiorite, either as a solution or as a solid to the rinse water. No
additional alkalinizing agent, such as sodium hydroxide or hydrated lime,
is required, as in the chlorine gas process.
Agitation also is required with hypochiorites to effect proper mixing.
The process with hypochiorites may be conducted batchwise or continuously.
This process probably is best suited to the needs of the smaller plater
who is faced with the necessity for complete destruction of cyanide.
Advantages of hypochiorite processes over the chlorination process are
(1) If sodium hypochiorite or calcium hypochiorite are used, the theo-
retical chlorine consumption is only half as great as that if chlorine
gas is used. If bleaching powder is used, the theoretical chlorine con-
sumption will be the same as for the chlorine gas process.
(2) Handling and metering of the hypochiorites is relatively simple and
nonhazardous.
(3) The reaction is more rapid than that with chlorine.
(4) If sodium hypochiorite is used, sludge production is minimized.
(14,76,77,78)
This process is also used commercially.
Conversion of Cyanide to Cyanate by Chlorine Gas . The cxanate radical
(CNO) is only about one—thousandth as toxic as cyanide( 4 ), and many
regulatory agencies will accept rather high cyanate concentrations in
effluents. The conversion of cyanide to cyanate by chlorine gas is a
rapid reaction, requiring only minutes. The reaction is, in fact, an
intermediate stage in the process for the complete destruction of cyanide
by chlorine. The chemical equation involved is
NaCN + Cl 2 + 2NaOH + NaCNO + 2NaC1 + 1120
Sodium Chlorine Sodium Sodium Sodium Water
cyanide hydroxide cyanate chloride
23
-------
It is carried out in the same fashion and type of equipment as the pro-
cess involving the complete destruction of cyanide by chlorine. It may
be conducted batchwise or continuously. Sludge formation also occurs in
this process and provisions for separating sludge from treated liquor may
be required.
Conversion of Cyanide to Cyanateb _ y Hypochlorites . The hypochlorites
also are capable of converting cyanides to the relatively nontoxic
cyanates by a similar reaction
NaCN + NaOC1 - NaCNO + NaC1
Sodium Sodium Sodium Sodium
cyanide hypochlorite cyanate chloride
Other hypochiorites, such as calcium hypochiorite or bleaching powder can
be used in place of sodium hypochiorite. The process is straightforward
and rapid.
For the smaller plater aiming at the partial destruction of cyanide, i.e.,
the conversion of cyanide to cyanate, the hypochlorite method is more
suitable than the chlorine method. This process has also been applied
practically using either chlorine or one of the hypochlorites.(60 7984 )
Conversion of Cyanide to Ferrocyanide by Ferrous Sulfate . The formation
of less toxic cyanide complexes such as ferro and ferricyanides also has
been used as a method for disposing of cyanide wastewaters. This process
involves the use of iron salts to form complex compounds with the free
cyanide in the wastes. Eventually these cyanide complexes are precipi-
tated and removed as a sludge. The use of ferrous sulfate, for example,
produces the characteristic dark blue sludge or Prussian blue.
The major advantage of this treatment method is that it is relatively
inexpensive where waste ferrous sulfate is available. However, consid-
erable quantities of sludge may be formed and the treated solutions are
strongly colored. There also is evidence that ferrocyanides may be de-
composed to free cyanide by sunlight. The regeneration of the cyanide
under these conditions would contaminate the receiving stream. (6I)
This method has received very little acceptance by the industry in this
country, but appears to be used in Europe.( 6474 ) The complexing pro-
cess apparently does not completely destroy cyanide under practical
operating conditions. Cyar4de levels in treated solutions may be as
great as 5 to 10 ppm. (85 ,86j
Conventional Methods for Chromium Rinses
Reduction of Hexavalent Chromium by Sulfur Dioxide, Sulfites, and Ferrous
Sulfate. . Chromium—bearing wastes often are disposed of by processes
involving the reduction of chromium to the trivalent form and the subse-
quent precipitation of the reduced chromium with alkali. This general
24
-------
process is employed extensively by int9rmegia e §qd large plating plants
for treatment of chromium wastewaters. ’ 37 ’ 5, l,oi—92)
Methods for reduction of hexavalent chromium vary with, each particular
plant. Common reducing agents are gaseous sulfur dioxide; sodium bisul—
fite, metabisulfite, or hydrosulfite; and ferrous sulfate.
Reduction with SO 2 is the method most commonly employed by many large
plating plants. Basic equipment for this method consists of sulfonators
for combining sulfur dioxide with water and agitated tanks for conducting
the reduction. During reduction sulfuric acid is normally added to main-
tain an acid solution with a pH range of 2.0 -3.0. Under these conditions,
the reactions which occur are
SO 2 + 1120 -* 11 2 S0 3 + 2CrO 3 + 3H 2 S0 3 - - Cr 2 (S0 4 ) 3 + 31120
Sulfur Water Sulfurous Chromic Sulfurous Chromic
dioxide acid acid acid sulfate
The approximate cheiñical usage is 1 pound of SO 2 per pound of chromic
acid (Cr0 3 ) in the waste solution.
A recent development in this treatment method is the utilization of the
sulfur dioxide contained in waste flue gases from boIler piants. ( 3 )
This novel technique involves the use of scrubbers for adsorption of the
sulfur dioxide in the waste chromium solutions. If complete reduction
is not obtained in the adsorption column, sodium bisulfite or some other
reducing agent is added for final treatment of the waste solution. One
such plant employing this technique reports that enough sulfur dioxide
is available from the boiler flue gases to completely treat the total
volume of waste chromium solution from the plating plant.
Other reducing agents, such as bisulfites or ferrous sulfate, also are
used by plating plants for treatment of chromium wastewaters. The reac—
tion with bisulfites is
4CrO 3 + 6NaIISO 3 + 3H 2 S0 4 - 2Cr 2 (S0 4 ) 3 + 3Na 2 SO 4 + 61120
Chromic Sodium Sulfuric Chromic Sodium Water
acid bisulfite acid sulfate sulfate
The bisulfite may be added as a solid or as a solution. As with sulfur
dioxide, the addition of sulfuric acid is required to maintain a pH of
about 2 to 3 to obtain rapid and complete reaction. The anhydrous form
of sodium bisulfite (Na 2 S 2 O 5 ) or sodium metabisulfite also may be used.
The reaction with ferrous sulfate is
2CrO 3 + 6FeSO 4 + 611 2 S0 4 3Fe 2 (S0 4 ) 3 + Cr 2 (S0 4 ) 3 ÷ 61120
Chromic Ferrous Sulfuric Ferric Chromic Water
acid sulfate acid sulfate sulfate
With ferrous sulfate, however, larger quantities of sludge are produced
than with sulfur dioxide or bisulfites. Some economic advantage for
25
-------
reduction with ferrous sulfate may be realized if quantities of waste
pickle liquor are readily available at the plating plant.
After reduction, the solution is acidic and contains the chromium and
other metals that may have accompanied the chromium rinse waters (copper,
nickel, etc.). If ferrous sulfate is used, the solution also will con-
tain relatively large amounts of iron. If this solution is discarded
directly to the sewer, it is sufficiently acid to be corrosive. Neu-
tralization, therefore, generally is required. This is done in various
ways. The acidic wastes may be combined with alkaline wastewaters, such
as treated cyanide wastes, or they may be treated with alkalies such as
sodium hydroxide or hydrated lime. The precipitates from the neutraliza-
tion step are composed of the hydroxides of the metals (chromium, nickel,
copper, etc.). If ferrous sulfate has been used for reduction, they also
will contain relatively large amounts of iron hydroxide. If neutraliza-
tion has been carried out with lime, the precipitates will contain excess
lime and calcium sulfate. It may therefore be necessary to provide a
settling tank to permit separation of the precipitates from the effluent
before their disposal.
After reduction it may be possible to dispose directly of the effluent.
The effluent may, however, require neutralization and precipitation of
the now trivalent chromium (and other metals) before disposal to reduce
its corrosiveness and whatever toxicity it may possess from such metals
as nickel, copper, etc. If the precipitated solids after neutralization
are too high or too potentially toxic to meet local regulations, the
neutralized effluent may have to be given some sort of solids—liquids
separation, such as sedimentation or filtration, prior to disposal.
Precipitation of Hexavalent Chromium by Barium Compounds . Removal of
toxic chromium from wastewaters also can be effected by precipitation as
hexavalent chromium.( 5 , 94 ) This method of treatment usually involves the
use bf barium salts for precipitation of insoluble barium chromate. With
barium chloride, f or example, the following reaction takes place
BaC1 2 + Na 2 CrO 4 BaCrO + 2NaC1
Barium Sodium Insoluble Sodium
chloride chromate barium chromate chloride
The major disadvantage of this method is that the additions of barium
chloride must be strictly controlled, as this chemical is highly toxic.
The sludges produced also are toxic and may result in an additional dis-
posal problem.
The process involving the precipitation of highly insoluble barium chro—
mate generally will require a solids—liquid separation step before the
effluent is disposed. Relatively few plants employ this process.
26
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Miscellaneous Methods for Treating Rinse Water
In addition to the previously outlined conventional processes for treat-
ing rinse waters, other methods described in the literature have been
used. These include the formation of cyanide complexes by the use of
polysuif ides to form relatively nontoxic sulfocyanates( 6 1 , 66 ), the des-
truction of cyanide by potassium permanganate(95), the conversion of
cyanide to cyanate by ozone( 58 , 96 ), the conversion of cyanide to cyanate
by hydrogen peroxide( 97 ), the complexation of cXanide by nickel salts to
form the highly stable nickel cyanide com iex( , the biological des-
truction of cyanide on trickling filters( ’ 9 ’ - 00 , the destruction of
cyanide by irradiation( - ), the use of techniques such as dialysis and
reverse osmosis to purify both chromium and cyanide rinse waters (102104),
the electrolytic reduction of hexavalent chromium, and the use of scrap
metal to reduce chromium( 105 ’ 06 ).
These processes are in various stages of development. Some, such as the
use of polysuif ides to complex cyanides, or the use of permanganate to
destroy cyanides, have been reduced to commercial practice. Some have
been merely suggested, i.e., the complexation of cyanide by nickel.
Reverse osmosis and dialysis as methods for treating electroplating
wastes are in early stages of development. Little is known about the
electrolytic reduction of hexavalent chromium -in rinse waters at this
time because the only reference to this process encountered was in
Japanese and a translation was not available.
The fact that these approaches have not been included in the discussion
of conventional methods should not be interpreted to mean that they are
being dismissed from consideration. Any one or several of them may prove
to have some merit as a means for treating rinse waters. They will be
evaluated during the course of the current research program.
Physical Methods for Treating Rinse Water
In addition to the chemical operations discussed in the foregoing sec-
tions, there are two commonly used physical methods that have been used
in the treatment of rinse waters. These are ion exchange and evaporation.
The technological and engineering aspects of ion exchange processes for
treating chromium solutions have been thoroughly developed. These pro—
cesses have been widely used in the treatment of chromium wastes and
mixed wastes not only for detoxification but also for the recovery of
chromium, water, and, in the case of hot rinses, of heat(43 ,56, 57 7 2 l).
Numerous applications of ion exchange to chromium wastes are reported in
the literature for the treatment of dilute rinse waters, more concentrated
rinse waters as might be produced in countercurrent rinsing, and for the
regeneration of plating baths.
Among the specific applications of ion exchange techniques in chromium
plating are
27
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(1) The purification of contaminated plating baths by using cationic
exchangers to remove iron, trivalent chromium, etc.
(2) The recovery of chromic acid from reclaim rinsing systems by the
use of cationic exchangers for the removal of impurities followed by the
concentration of the purified rinse solution by evaporative procedures.
(3) The detoxification of rinse waters containing chromium by using both
cationic and anionic exchangers to effect the removal of both trivalent
and hexavalent chromium as well as other impurities.
In the second of the applications cited above, it has been demonstrated
that a plant of size sufficient to produce about 1000 gallons of still
rinse solution containing about 7 oz/gal. of Cr0 3 every 48 hours of
operation was able to recover Cr0 3 at a total cost——including deprecia-
tion——of 8 cents per pound where Cr0 3 was selling for 28 cents per pound.
Recovery operations of this type are generally batch in nature.
Very little has been published on the applicability of anionic exchange
processes to the treatment of very dilute rinse waters containing 10 to
100 ppm of hexavalent chromium. The potentiality of such a process for
the smaller plater will be discussed in the final phase report on this
project.
Although laboratory and pilot—plant work have indicated the feasibility
of using ion exchange for straight cyanide rinse waters, the process has
found little use. The most frequently cited difficulties are ‘poisoning
of the resin’ by the irreversible adsorption of complex metal cyanides
such as those of nickel and iron, the production of hydrogen cyanide
within the equipment during adsorption, etc.
Ion exchange has been successfully applied, however, to mixed wastes
(chromium metals and cyanides) by a dual bed process in which the mixed
waste is first passed through a cationic exchanger to adsorb metals, help
break up complex metal cyanides and generate free hydrogen cyanide, and
then through an anionic exchanger to adsorb the liberated cyanide. The
published literature on the treatment of mixed wastes by the dual bed ion
exchange process cautions against the presence of too great a concentra-
tion of cyanide in the mixed waste, one reference stating that the cya-
nide should not exceed 4 to 5 percent (presumably of the total waste
components) and another stating that with increased cyanide some modifi-
cations of the exchanger would be required.
Regeneration, which amounts to removing the load of cyanide or metals
that the resins have absorbed, must be done periodically. This is accom-
plished by passing sulfuric acid and/or sodium hydroxide through the
resins to redissolve the metals or cyanides. The regenerated solutions
are greatly concentrated, but they are still toxic. If they are to be
discharged to waste, then they require the chemical treatments previously
discussed, but because they are concentrated and relatively low in volume
compared to the original rinse waters, treatment can be carried out
batchwise in small tanks. Recovery of cyanides, chromium, and other
metals from the regenerating solutions also is a possibility; however,
28
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its economic feasibility for the smaller plater would require study.
Water recovery for reuse in rinsing is a built—in feature of the ion
exchange process. A typical ion exchange application is shown in Figure
4.
Evaporative processes have found some use for both chromium and cyanide
rinse waters.( 43 ’ 5,] 22l24) Generally, evaporative processes are
economical only on concentrated rinses, such as those produced in still
tanks or multistage countercurrent rinsing. If the smaller plater
employs such rinsing techniques, evaporation processes may be worth con-
sideration not only for the recovery of plating chemicals but also of
rinse water. As with the ion exchange process the evaporative processes
have been thoroughly developed for both chromium and cyanide waste
streams. A typical evaporative process is shown in Figure 5.
Other Approaches
Other approaches to the detoxification of plating and metal finishing
effluents are described in the literature. The so—called “integrated”
approach is the most widely used of these. It is not strictly a method
for treating rinse waters so much as a method for eliminating toxic com-
ponents early in the rinsing operation. The theory, practice, applica-
tion, and cost factors associated wi 0 the integrated approach are pre-
sented in a number of articies.G’- 25 )
Other approaches which may be classified as rinse water treatments are
also described in the literature. In general, these are of the pre—
engineered “package type” and embody the known chemical or physical unit
operations discussed in this report. Typifying these is a recent for-
eign development said to be particularly suitable for the smaller
plater. (131)
Waste Reduction y In—Plant Control Measures
The cost of waste treatment for the plater is directly proportional to
the amounts of materials such as chromium and cyanide which have to be
treated and proportional through some coefficient to the volume of th
waste solution. In—plant control measure can reduce both the amounts of
toxic materials and the volume of flow.
These measures include
(a) The reduction of drag—in to the rinsing circuit by such means as
increasing draining time, the installation of drip boards or drip tanks,
air jetting, tumbling, or vibrating the pieces
(b) The curtailment in water usage by such expedients as countercurrent
rinsing, the use of sprays, better control of water flow, proper racking
and proper maintenance of racks, tanks, etc.
29
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Chromium Rinse Waters, Mixed Rinse Waters
(Chromium, nickel, copper, cyanide, etc.)
Periodic I Cation Exchanger Metal Recovery
Regeneration 1 - Selectively Adsorbs — —) if Feasible
with Sulfuric I Metals (Nickel, copper,
Acid I trivalent chromium,
L iron, aluminum, etc.) I
Chronic Acid
j /- Recovery if
Feasible
I I
____ ___ ___ 1 ’
Periodic Anion Exchanger Mixed Regeneraat
Regeneration Adsorbs Hexavalent Solution (All
with Sodium Chromium, Sulfate, metallic components
Rydroxide Chlorides, Phosphates of rinse water in
etc. concentrated form)
hatch eatment
by Chemical
To Reuse as Disposal Methods to Detoxify
Rinse Water ____________________
Disposal
FIGURE 4. ION EXC}1 GE METHOD OF TREATING CHROMIUM
RINSE WATERS OR MIXED RINSE WATERS
30
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Rinse Waters
(Relatively concentrated either
in still tanks or by counter-
current rinsing)
FIGURE 5. EVAPORATIVE TREATNENT OF RINSE WATERS 122
Returned Rinsing
Who,lly or Partly
Returned
Plating
31
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(c) The segregation of nontoxic wastewaters from the normal toxic waste
stream
(d) The prevention of leaks, overflows, and spills
(e) Provisions for impounding these if they should occur by standby
tanks, sumps, etc.
Space limitations and the cost of installing the equipment for many of
the techniques used for in—plant waste control preclude their use in the
majority of’sinall plating shops. It is certain, however, that many of
the waste disposal problems encountered in these shops could be elimi-
nated or diminished and made less costly by the adoption of such measures
where this is possible.
Selection of a Process
Conventional unit processes available for the treatment of rinse waters
have been described in the foregoing sections of this report. To deter—
mine which of the unit processes to use and their sequence in a complete
waste treatment facility requires a careful review of the technical,
practical, and economical factors. These factors are
(1) Rinse water volume and flow variations
(2) Physical and chemical characteristics of the rinse waters
(3) Regulations on effluent quality
(4) Plant facilities such as space, layout, etc.
(5) The feasibility of separating various waste streams within the
plant for separate treatment
(6) The feasibility of altering rinsing circuits to reduce the volume
of rinse water
(7) The feasibility of reducing dragout
(8) The feasibility of the recovery of metals, cyanide, or rinse water
(9) The suitability of existing equipment for waste treatment and the
cost of new equipment that may be required
(10) The cost of chemicals to carry out a given process
(11) Labor requirements
(12) Other operating expenses, such as power and maintenance and costs
incurred for solids disposal.
Various flowsheets that could be followed for the separate treatment of
cyanide rinse waters are outlined in Figure 6. Three of the commonly
used treatments are shown
(1) Complete destruction of cyanide by treating alkaline rinse waters
with chlorine gas, sodium hypochiorite, or calcium hypochiorite
(2) Partial destruction of cyanide, i.e., by converting it to the con-
siderably less toxic cyanate form, by milder treatment with the same
chlorine chemicals (these processes, requiring less time and fewer
chemicals, are frequently used)
32
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Direct
iisposal
Complexing of
Cyanide by:
Ferrous Sulfate
Sedimentation
Filtration, etc.
salof
Solid Waste
FIGURE 6.
CHEMICAL TREATMENT OF CYANIDE WASTE
Cyanide Rinse Waters 1
(Containing cyanide, copper, cadmium, zinc, alkali)
• 1
Destruction of
Cyanide by:
Chlorine Gas;
Sodium Hypochlorite;
Calcium Ilypochiorite
Partial Destruction
of Cyanide by: Chlorine
Gas; Sodium Hypochlorite;
Calcium Hypochiorite
I
I
‘I,
Disposal of
Liquid Waste
33
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(3) The complexing of cyanide by ferrous salts to convert it to a stable
ferrocyanide complex which is relatively nontoxic.
As is shown in Figure 6, after each of these primary treatments, various
paths may be taken before eventual disposal. The simplest path and one
that is frequently followed at the present time is to dispose directly
the treated effluent. All of these treatment processes result in the
formation of solids, including metal hydroxides, probably calcium sul-
fate, and precipitated complex cyanides. It is possible, therefore,
that restrictions on solids or potentially toxic metal hydroxides may
make additional treatment mandatory. This could involve separation of
the solids by sedimentation or settling, filtration, etc., before send-
ing the effluent to waste. It also would involve periodic separate
disposal of the solids.
Figure 7 is a diagram of the chemical methods for the separate acidic
chromium—bearing wastes. As with cyanide, direct disposal often is used
as depicted by the line at the left side of the diagram. Simple neutral-
ization of the generally acidic chromium wastes is practiced to some
extent but largely to reduce the corrosiveness of the usually acidic
solutions. Neutralization will precipitate any trivalent chromium,
copper, or nickel that may accompany the waste but will have little or
no effect on the hexavalent chromium. Neutralized chromium wastes may
be disposed of directly or, if precipitated solids are too high for
acceptance by authorities, some form of solids—liquids separation (sedi-
mentation, filtration, etc.) may be employed.
The sequential arrangements of unit operations in Figures 6 and 7 apply
to instances where chromium and cyanide rinse waters are treated sepa-
rately. In cases where chromium and cyanide rinses are mixed, the same
chemical treatments would be applicable as unit operations, but optimum
sequences for this operation would have to be decided and many factors
would enter into the decision. Sequential arrangements of unit opera-
tions which have been employed in the treatment of mixed rinse waters
are shown in Figure 8.
Costs
Published information on Waste treatment costs for the plating industry
falls into two categories
(1) That pertaining to large or intermediate size plants (mostly cap-
tive) doing what amounts to production line plating, with waste streams
reasonably constant in volume and composition and with carefully designed,
engineered, and operated treatment facilities
(2) That supplied by engineering or equipment companies in the business
of designing and installing waste treatment plants (This is usually
general in nature and is almost always——and quite justifiably——accom—
panied by statements or implications that specific plant surveys are
required for firm estimates of capital and operating costs. It is
34
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Direct
r jsposai -I-
Chromium-Bearing Rinse Waters
(Containing chromium, acid, nickel?, copper?)
I
V
I
Neutralization to
Precipitate Metals
FIGURE 7. CHEMICAL TREATMENT OF CHROMIUM WASTE
Neutralization by:
Sodium Hydroxide;
Hydrated Lime;
Limestone; Sodium
Carbonate; etc.
Reduction of Hexava lent
Chromium by: Sulfur
Dioxide; Sodium Bisulfite;
Sodium Metabisulfite;
Ferrous Sulfate; Scrap
Metal; Sulfuric Acid
Precipitation of
Hexava lent Chromium
by: Barium Chloride;
Witherite (bariu n
carbonate); Sodium
Hydroxide
Disposal of Liquid Waste
35
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Mixed Rinse Waters
(Containing chromium, cyanide, nickel, copper, zinc, etc.)
Neutralization Acidification Reduction
of Acid of Chromium
with SO 2
.1 1
Precipitation of Reduction of Neutralization
Chromium as Chromium with Precipitation
Barium Chromate PeSO 4 of Metals
with Lime or
Alkali
I
Complexation of Complexa ion of Partial
Cyanide with Cyanide with Destruction
PeSO 4 Additional PeSO 4 of Cyanide
if Necessary with
Sodium
_________ liypochlorite
Solids-Liquids
Separation
Separation
Dispo Die 1 sal Dispial Disposal
of Liquid of Solids of Liquid of Liquid
FIGURE 8. PROCESSES APPLICABLE TO MIXED CHROMIUM
AND CYANIDE RINSE WATERS
36
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probable that most of these firms can provide approximate estimates based
on their experience b üt whatever rule of thumb they employ is not
published.).
Capital costs of waste treatment plants for the small plater will depend
on a number of factors which include the type of waste; its volume and
composition; the degree to which it must be treated to produce an accept-
able effluent; the treatment process selected; whether the recovery of
metals, chemicals, or water is an objective; and the availability of
space, buildings, and utility services.
It is therefore impossible at this time to suggest any guidelines for
estimating capital costs to the smaller company contemplating waste
treatment on the basis of what has been learned from the open literature.
As this project continues, an effort will be made to gather more inf or—
mation. Hopefully, useful guidelines that will permit at least “ball-
park” estimates can be developed. Recently published examples of capital
costs for waste treatment are shown in the following tabulation.
Flow Capital
Rate, Concentration, Cost,
Waste Stream gpm ppm Treatment dollars
Chroinic acid rinse 100 40 Reduction 39,000
Chromic acid rinse 100 40 Ion exchange with 45,000
recovery
Chromic acid and 50 Chromium recovery 40,000
cyanide rinse Cyanide oxidation
Integrated treatment 15,000
The situation is almost as uncertain for operating costs. These will
depend on many of the factors listed above for capital costs. The corn—
ponents of operating costs are chemicals, labor, maintenance, utilities,
overhead, and amortization. Only the first, i.e., chemical costs, can
be predicted with any certainty from known conditions.
One engineering firm has published some broad guidelines which the job—
shop plater may find useful in attempting to predict the chemical costs
of treating rinse water wastes.(1 26 ) These are shown in the following
tabulation
Basis for Estimating Costs of Chemicals_to Detoxify
Chromium Wastes 3 to 4 cents/l00 square feet of chromium plated surface
2—1/2 to 5 cents/pound of chromic acid purchased
Cyanide Wastes 5 to 7 cents/100 square feet of surface plated
70 cents to $1/1000 pounds of barrel plated material
25 to 50 cents/pound of sodium cyanide purchased.
The author stresses that these costs are for the “average” plant which
probably does not exist. They are based primarily on average dragout
37
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rates* and on average oxidation of cyanide during plating. At best, they
may provide some basis for further investigation to the company inter-
ested in or faced with the requirement of waste treatment. Specific
costs of chemicals for waste treatment can only be predicted after a
careful plant survey and the selection of the best technical and economic
treatment method.
When these two steps have been taken, the amount of chromium to reduce,
the cyanide to destroy, and the acid or alkali to neutralize will be
known. From these data one can calculate the amount of chemicals that
theoretically will be required. Chemicals generally used in waste treat-
ment, the quantities required per pound of contaminant, and the approxi-
mate unit costs of these chemicals are listed in Table 7.
TABLE 7. CHEMICAL CONSUMPTION IN WASTE TREATMENT
Amount Required
per Pound of
Chemical Component, lb
Approximate
Unit Cost of
Chemical, $/lb
Chromium Wastes
Sulfur dioxide (SO 2 ) 1.9
0.11
Sodium bisulfite (NaIISO 3 ) 3.0
0.02
Sodium metabisulfite (Na 2 S 2 O 5 ) 2.8
0.06
Ferrous sulfate (FeSO 4 ) 8.8
0.01
Barium chloride (BaC1 2 ) 4.0
0.10
Cyanide Wastes
Chlorine gas (Cl 2 ) 2.7—6.8
Sodium hypochiorite (NaOC1) 2.9—7.2
0035 _ 018 (a)
0 37 .. 0 49 (b)
Calcium hypochiorite [ Ca(OC1) 2 } 2.8—6.9
0.425
Ozone (03) 1.8—4.6
0.20
Ferrous sulfate (FeSO 4 ) 2.3
0.01
Combined Wastes
Sulfuric acid ——
0.02
Type of Material
Vertical, well drained
Vertical, poor drainage
Vertical, very poor drainage
Horizontal, well drained
Horizontal, very poor drainage
Cup shaped work, very poor drainage
Barrel——angle
Barrel——horizontal
Dragout Rate
0.4—1.0 gal/bOO ft 2
2—3 gal/bOO ft 2
4—5 gal/bOO ft 2
0.8—2.0 gal/1000 ft 2
10 gal/bOO ft 2
24 gal/1000 ft 2
2—9 fluid ounces per load
5—30 fluid ounces per load
*Dragout rates may be estimated from “typical” data shown in the follow-
ing tabulation. (132—134)
38
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TABLE 7. (Coat.)
chemical
Amount Required
per Pound of
omponent lb
Approxima
Unit Cost
Chemical,
te
of
$/lb
SodIum
hydroxide
Combined
Wastes (Coat.)
——
0.03
Sodium
carbonate
——
0.25
Hydrated lime
——
0.01.
(a) Depending on quantity purchased, location, etc.
(b) Depending on form of sodium hypochlorite (granule, tablet) solution.
Cost shown is per pound of available chlorine.
Note: Costs shown in this table are approximate and may be expected to
vary, possibly within wide limits depending on quantities purchased,
freight costs, location, etc. Host of the costs shown have been taken
from a current issue of Oil, Paint, and Drug Reporter. In a few cases
cost information has been obtained from specific articles.
Sewer Rentals
Any discussion of costs should cover the topic of sewer rentals, and
other special charges made by municipalities for treating electroplating
and metal finishing wastes because these are definite cost items and must
be considered when evaluating the economics of waste treatment. There is
very little information in the open literature on these costs, and they
naturally vary from place to place and perhaps from one plant to another.
Those plating shops which incur such costs no doubt are aware of them
In some cases, these sewer rental fees or “penalty charges” for unusual
wastes, which amount to credits for waste treatment operations, may be
sufficiently great to justify some waste reduction or waste treatment
method.
Recovery
The recovery of chromium, cyanide, metals, and water might be important
factors in justifying the installation of waste treatment facilities for
a job—shop plater. Because of the variability of conditions existing in
individual plants, a decision on the merits of installing recovery sys—
téms can only be determined by a specific plant study in which such
factors as dragout rate, water costs, itility costs, sewer rental costs,
and the advantages of modifying rinsing techniques must be weighed.
39
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DISCUSSION
This state—of—the—art review has shown that there are many ways to treat
rinse waters. It has not shown that any given method or combination of
methods is clearly the most suitable for the requirements of the smaller
plater, or on the other hand, that any can be ruled out from considera-
tion. It is probable that any of the cited methods or combinations
thereof could, turn out to be the most feasible for a given metal finish-
ing plant.
As pointed out previously, the selection of an optimum method depends on
many factors, one of the most important of which is the volume and com-
position of the rinse waters.
One of the objectives of this study is to provide information on this
factor. This is being done by questionnaire and by the sampling and
analyses of rinse waters from many smaller establishments.
An additional objective of the study is to assemble as much information
as possible on the other factors that must be considered in the selection
of a process. These include present restrictions on effluent quality,
possible future restrictions, capital and operating costs, etc.
It is hoped that this information assembled in a final report will pro-
vide more positive guidance to the smaller plater than does this pre-
liminary review.
Some of the factors which might influence the selection of a process are
purely local. These include the space utilities and equipment available
for installation of a treatment facility. Probably the best that this
study can do to assist the smaller plater is to provide information on
the spatial equipment, labor, and utility requirements for the various
processes.
The foregoing discussion applies to existing processes which may well
turn out to be the most satisfactory for the smaller plater.
However, the program, as originally proposed to the Metal Finishers
Foundation and as is being carried out, involves an additional and
equally important objective. This is to investigate and, if indicated,
to develop new techniques and unit processes which might prove to be
simpler and more economic for smaller plants than the existing methods.
Work has already begun on three such approaches——solvent extraction, ion
flotation, and adsorption on relatively inexpensive materials. The
results obtained within the first few weeks of the experimental program
have been positive, but are still far from delineating technically and
economically feasible processes. As the experimental work continues,
these new approaches will be continuously appraised from the viewpoint
of their applicability to the problems of the smaller plater.
41
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ACKNOWLEDGNENT
This report was prepared by the Battefle Memorial Institute, Columbus
Laboratories, under contract to the Metal Finishers’ Foundation in partial
fulfillment of Federal Water Quality Administration Grant No. WPRD 2O1—O1—6 .
The advice and cooperation of Messrs. John Ciancia, Edward L. Dulaney, and
W. J. Lacy of F A are greatly appreciated. The study was directed by the
Poflution Abatement Committee of the Metal Finishers’ Foundation, Walter
V. Turner, Chairman; P. Peter Kovatis, Foundation Secretary.
The reveiw covered by this report was conducted by Battefle Memorial In—
stitute during the period of April though November, 196a. Battefle staff
participating in the program were: J. F. Shea, A. K. Reed, T L. Tewsbury,
and G. R. anithson, Jr.
43
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REFERENCE S
(1) Curnham, C. Fred, “Liquid Industrial Wastes, I Through VII”,
Industrial Wastes (September, 1959, through October, 1960).
(2) Gurnham, C. Fred, Principles _ of Industrial Waste Treatment , John
Wiley & Sons, Inc., New York (1955).
(3) Dobb, F. H., “Metal Wastes. Contribution and Effect”, Tech. Proc.
Amer. Electroplaters T Soc., pp 53—54 (1958).
(4) Anon., “Cost of Plating Waste Disposal is Reduced”, Steel, Vol 148,
No. 24, pp 160—161 (1961).
(5) Pettet, A.E.J., “The Disposal of Plating Shop Effluents”, J.
Electrodepon. Tech. Soc., Vol 25, pp 1—22 (1950).
(6) ilesler, J. C., “Recovery and Treatment of Metal Finishing Wastes by
Ion Exchange Processes”, Proc. 21st Ann. Water Conf. Eng. Soc. of
Western Pa., pp 89—98 (October 24, 1960).
(7) Moore, W., McDermott, G., Post, M., Mandia, J., and Ettinger, M.,
“Effects of Chromium on the Activated Sludge Process”, J. Water
Poll. Control Fed., Vol 33, p 54 (1961); Proc. 15th Ind. Wastes
Conf., Purdue Univ. Ext. Ser., Vol 106, p 158 (1961).
(8) Malany, G. W., Sheets, and Quillin, “Toxic Effects of Metallic Ions
on Sewage Microorganisms”, Sewage and Ind. Wastes, Vol 31, pp 1309—
1315 (1959).
(9) McDermott, G. N., Moore, W. Allen, Post, N. A., and Ettinger, M. B.,
“Effects of Copper on Aerobic Biological Sewage Treatment”, J. Water
Poll. Control Fed., Vol 35, pp 227, 238—241 (1963).
(10) Wisniewski, T. F., “Plating Room Waste and Stream Pollution”,
Plating, Vol 43, pp 494—496 (April, 1956).
(11) Stankey, S., “Effects of Chromium Wastes on Activated Sludge”,
Sewage & Ind. Wastes, Vol 31, pp 496—498 (1959).
(12) Marinaro, Alfred T., “Pollution Abatement. The Masters’ Electro-
plating Association and the National Association of Metal Finishers”,
Plating, Vol 53, pp 1230—1234 (October, 1966).
(13) Ingols, R. and Fetner, R., “Toxicity of Chromium Compounds Under
Aerobic Conditions”, J. Water Poll. Control Fed., Vol 33, pp 366,
369, 370 (1961).
(14) Serota, L., “Cyanide Waste Treatment——Hypochlorites”, Metal
Finishing, Vol 56, pp 61—64, 67 (January, 1958).
45
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(15) Serota, L., “Waste Dispo al”, Metal Finishing, Vol 55, No. 6,
pp 88-90; No. 7, pp 58-60; and No. 8, pp 69-71 (1957).
(16) McDermott, G. N., et al, “Effects of Copper on Aerobic Biological
Sewage Treatment”, J. Water Poll. Control Fed., Vol 35, No. 2,
pp 227-229, 238-241 (1963).
(17) Serota, L., “Science for Electroplaters 25. Waste Disposal I”,
Metal Finishing, pp 88-90 (June, 1957).
(18) Serota, L., “Waste Disposal”, Metal Finishing, Vol 55, pp 88-90
(June, 1957).
(19) Masselli, Joseph W., et al, “Effect of Industrial Wastes on
Sewage Treatment”, New England Interstate Water Pollution Control
Commission.
(20) Gasper, W. L., “Industrial Waste Treatment and Water Reclamation--
A Case Study”, Tech. Proc. Amer. Electroplaters’ Soc., pp 63-67
(1958).
(21) Hendel, F. J. and Stewart, V. T., “Flow-Through Treatment of
Metal Industry Wastes”, Sewage & md. Wastes, Vol 25, pp 1323-
1330 (1953).
(22) Dodge, B. F. and Zabban, W., “Disposal of Plating Room Wastes.
III. Cyanide Wastes; Treatment with 1-lypochiorites and Removal of
Cyanates”, Plating, Vol 38, pp 561-566, 571-586 (1951).
(23) Serota, L., “Waste Disposal”, Metal Finishing, Vol 55, pp 88-90
(1957).
(24) Cooper, J. E., “Treatment and Disposal of Plating Wastes”, Sewage
& md. Wastes, Vol 23, pp 295-308 (1951).
(25) Pickering, Quentin H. and Henderson, Croswell, “The Acute Toxicity
of Some Heavy Metals to Different Species of Warmwater Fishes”, Air
& Water Poll. mt. J., Vol 10, pp 453-463 (1966).
(26) Ceresa, Myron and Lancy, Dr. Leslie E., “Metal Finishing Waste
Disposal”, Metal Finishing, pp 56-62 (April, 1968); pp 60-65
(Nay, 1968); (June, 1968).
(27) Terry, L., “Public Health Service Drinking Water Standards”, Public
Health Service Publication No. 956 (1962).
(28) Day, R. V., “Disposal of Plating Room Wastes”, Plating, Vol 46,
pp 929-931 (1959).
(29) Hendel, Frank J. and Stewart, V. T., “Flow-Through Treatment of
Metal Industry Wastes”, Sewage & md. Wastes, p 1323 (November,
1953).
46
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(30) Nyquist, 0. and Carroll, H., “Design and Treatment of Metal
Processing Wastewaters”, Sewage & md. Wastes, Vol 31, pp 941-949
(1959).
(31) Kramer, A. E., et al, “Design of a Treatment Plant for Metal
Finishing”, Plating, Vol 54, pp 66-74 (January, 1967).
(32) Druschel, E. F., et al, “Continuous and Batch Treatment of
Industrial Wastes”, Metal Finishing, pp 58-63 (March, 1960).
(33) Newell, I. L., “Waste Disposal for Metal Finishing Industries”,
Plating, Vol 48, pp 373-378 (April, 1961).
(34) Corcoran, L. M., “Treatment of Anodizing Wastes by Ion Exchange”,
Sewage & md. Wastes, Vol 27, pp 1259-1261 (1955).
(35) Salvatorelli, J., “Aircraft Engine Wastes Treated in Continuous
‘Flow Through’ Plant”, Wastes Engineering, Vol 30, pp 310-314, 342
(1959).
(36) Cupps, C. C., “Treatment of Wastes for Auto Bumper Finishing”,
Industrial Water & Wastes, p lii (July-August, 1957).
(37) Fisco, R., “A Review of the Process of Hexavalent Chromium
Reduction Utilizing Waste Flue Gas”, Proc, 15th md, Waste Conf.,
Purdue Univ. Ext. Ser. 106, pp 15-18 (1961),
(38) Sweglar, C., “Plating Solutions”, Industrial Wastes, Vol 4, No. 3,
pp 40-42 (1959).
(39) Cram, Richard W., “Treatment of Nickel-Chromium Effluents”, Metal
Finishing, p 50 (April, 1964).
(40) Druschel, E. F., “Continuous and Batch Treatment of Industrial
Wastes”, Metal Finishing, p 58 (March, 1960).
(41) Anon., “Waste Treatment Controls Cut Chemical Costs Sharply”, Chem.
Processing, pp 83, 84 (October, 1959).
(42) Kempson, N. W., “Alkaline Chlorination of Metal Finishing Waste
Waters”, Wastes Engng., Vol 22, pp 646-648, 652 (1951).
(43) Weisberg, L. and Quinlan, E. J., “Recovery of Plating Wastes”,
Plating, Vol 42, pp 1006-1011 (August, 1955).
(44) Dodge, B. F. and Walker, C. A., “Disposal of Plating Wastes at a
Silverware Plant”, Plating, Vol 41, pp 1288-1294 (November, 1954).
(45) Lukas, V.D.P., “Treatment of Acid Wastes with Calcite”, Sewage &
md. Wastes, Vol 27, pp 1253—1258 (1955).
47
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(46) Besselievre, Edmund B., “Pontiac Motors Treats its Wastes”, Wastes
Engng., p 642 (November, 1958).
(47) Mulcahy, E. W., “Pollution by Metallurgical Trade Wastes”, Metal
Finishing Journal, p 289 (July, 1955).
(48) McElhaney, Harry W., “Metal Finishing Wastes Treatment at the
Meadville, Pa., Plant of Talon, Inc.”, Sewage & md. Wastes,
p 475 (April, 1953).
(49) Hesler, J. C., “Practical Methods for Treatment of Metal Finishing
Wastes”, Plating, Vol 42, pp 1019-1029 (August, 1955).
(50) “Methods for Treating Metal Finishing Wastes”, Ohio River Valley
Water Sanitation Commission, Cinncinnati, Ohio (1953).
(51) Eckenfelder, W. Wesley, Industrial Water Pollution Control , McGraw
Hill Book Company, New York (1966).
(52) Gurnham, C. Fred, Industrial Waste Water Control , Academic Press,
New York and London (1965).
(53) Nemerov, N. L., Theories and Practices of Industrial Waste
Treatment , Addison-Wesley Publishing Co. Inc., Reading, Massachusetts
(1963).
(54) Ross, R. D., Industrial Waste Disposal , Reinhold Publishing Co.,
New York (1968).
(55) Graham, A. K., Electroplating Engineering Handbook , Reinhold
Publishing Co., New York (1962).
(56) Serota, L., “Ion Exchange Properties”, Metal Finishing, Vol 56,
pp 68-70 (April, 1958).
(57) Serota, L.,, “Cyanide Removal by Ion Exchange”, Metal Finishing,
Vol 56, pp 72-75 (March, 1958).
(58) Serota, L., “Cyanide Waste Treatment Ozonation and Electrolysis”,
Metal Finishing, Vol 56, pp 71-74 (February, 1958).
(59) Serota, L., “Cyanide Waste Treatment--HypochioriteS”, Metal
Finishing, p 61 (January, 1958).
(60) Serota, L., “Science for Electroplaters. 30. Acidification of
Cyanide Waste”, Metal Finishing, V.1 55, pp 72-75 (November, 1957).
(61) Serota, L., “Cyanide Disposal Methods”, Metal Finishing, Vol 55,
pp 75-77 (October, 1957).
(62) Serota, L., “Treatment of Chromate Wastes”, Metal Finishing,
Vol 55, pp 65-67 (September, 1957).
48
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(63) Serota, L., “Waste Disposal III”, Metal Finishing, Vol 55, pp
69-71 (August, 1957).
(64) Lakin, J., “Effluent Treatment for the Small Plater”, Electroplating
and Metal Finishing, Vol 14, No. 3, pp 89 (1961).
(65) “Chromium Wastes--Recovery or Treatment?”, Sewage & md. Wastes,
Vol 25, pp 921-936 (1953).
(66) Corcoran, A. N., “Treatment of Cyanide Wastes from the Electro-
plating Industry”, Sewage & md. Wastes (Sewage Wks J.), Vol 22,
pp 228-238 (1950).
(67) Lancy, L. E., “Economic Study of Metal Finishing Waste Treatment”,
paper presented at 53rd Annual Convention, American Electroplaters
Society (June, 1966).
(68) Serota, L., “Cyanide Disposal Methods”, Metal Finishing, p 75
(October, 1957).
(69) Hanson, N. and Zabban, W., “Design and Operation Problems of a
Continuous Automatic Waste Treatment Plant at IBM, Rochester,
Minnesota”, Eng. Bull. Proc. 14th md. Wastes Conf., Purdue Univ.,
Vol 44, No. 5, pp 227-249 (1960).
(70) Garret, R. and Brennan, D., “Transworld Airlines Waste Treatment
Flexibility”, Proc. 16th Purdue md. Waste Conf., Eng. Ext. Series, Vol
109, pp 140-146 (March, 1962).
(71) Vought, “Approach to the Prevention of Water Pollution by Cyanide-
Bearing Solutions”, Plating, p 63 (January, 1967).
(72) Connard, John M., “Electrolytic Destruction of Cyanide Residues”,
Metal Finishing, Vol 59, p 54 (May, 1961).
(73) McElhaney, H. W., “Metal Finishing Wastes Treatment at the Meadville,
Pa., Plant of Talon, Inc.”, Sewage & md. Wastes, Vol 25, pp 475-483
(1953).
(74) Watson, K 0 S., “Treatment of Complex Metal Finishing Wastes”, Sewage
& md. Wastes, Vol 26, pp 182-196 (1954).
(75) Fair, C. M., “Economics in Metal-Finishing Wastes Management”, J.
Water Poll. Control Fed. (Sewage & Ind.Wastes), Vol 32, pp 632-
639 (1960).
(76) Stroh, J. and Allen, C., “Low-Cost Integrated Waste Treatment
at American Sterilizer”, Plating, Vol 44, pp 869-872 (1957).
(77) Lakin, J., “Effluent Treatment for the Small Plater”, Electroplating
& Metal Finishing, Vol 14, No. 3, p 89 (1961).
49
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(78) Balden, A., “Treatment of Industrial Process Wastes at Chrysler
Corp.”, Sewage & lad. Wastes, Vol 31, pp 934-940 (1959).
(79) Kohout, J., “Cyanide and Metal Waste Treatment at Western Electric,
Omaha Plant”, Eng. Bull. Proc. of 14th md. Wastes Conf., Purdue
Univ., Vol 44, No. 5, pp 723-731 (1960).
(80) Wickett, J., Jr., and Grant, L., “Compact Treatment Plant Gives
0 ppm CN”, Chem. Processing (November 19, 1962).
(81) Carrett, R. L., Garland, R. C., and Sawyer, T., “How Transworld
Airlines Treats Plating Shop Wastes”, Plating, Vol 45, pp 847-852
(August, 1958).
(82) Raymont, J.E.G. and Shields, 3., “Toxicity of Copper and Chromium
in the Marine Environment”, International 3. of Air and Water Poll.,
Vol 7, Nos. 4 & 5, p 435 (1963).
(83) Corcoran, Arthur N., “Treatment of Cyanide Wastes from the Electro-
plating Industry”, Sewage & lad. Wastes, Vol 22, pp 228-238 (1950).
(84) Salvatorelli, Joseph J., “Aircraft Engine Wastes Treated in
Continuous ‘Flow Through’ Plant”, Wastes Engineering, p 310
(June, 1959).
(85) Mulcahy, E. W., “Pollution by Metallurgical Trade Wastes. A Study
of Causes and Suggested Cures”, Metal Finishing, Vol 1, p 289
(July, 1955).
(86) Pinner, W. L., “Progress Report of American Electroplaters Society
Research Projects on Plating Room Waste”, Prot. 7th md. Waste Conf.,
Purdue Univ. Engag. Extn. Ser. No. 79, pp 518-540 (1952).
(87) Canan, J., “The Flue Gas Method of Treating Chrome Plating Wastes”,
Eng. Bull. Proc. of 14th lad. Wastes Conf., Purdue Univ., Vol 44,
No. 5, p 26 (1960).
(88) “Cost of Plating Waste Disposal is Reduced”, Steel, p 160 (June
12, 1961).
(89) Watson, Kenneth S., “Chromium Wastes--Recovery or Treatment”,
Sewage & md. Waste, p 172 (August, 1953).
(90) Kramer, A. E., et al, “Design of a Treatment Plant for Metal
Finishing”, Plating, Vol 54, p 66 (January, 1967).
(91) Gasper, Wayne L., “Industrial Waste Treatment and Water Reclamation,
A Case Study”, Tech. Proc. Amer. Electroplaters’ Soc., Vol 45,
pp 63-67 (1958).
(92) Wickett, 3. Allen, Jr., “Compact Treatment Plant Gives 0 ppm CN
for $130,000, Less”, Chemical Processing, p 19 (November 19, 1962).
50
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(93) Fisco, R., “Flue Gases Harnessed to Treat Tough Chromic Acid
Wastes”, Chemical Processing, Vol 26, pp 63, 64 (September, 1963).
(94) “Ion Exchange Processes in the Plating and Allied Industries, II.
Ion Exchange in Recovery Processes”, Electroplating, Vol 6, pp
121-130 (1953).
(95) “The Disposal of Toxic Effluents”, md. Chem. Mfr., Vol 31, pp
455-456 (1955).
(96) Sondak, W. and Dodge, F., “The Oxidation of Cyanide-Bearing Wastes
by Ozone”, Plating, Vol 48, pp 173, 280, 283, 284 (1961).
(97) Gurnham, C. Fred, Editor, “Liquid Industrial Wastes Part IV”,
Industrial Wastes, pp 75-80 (July, 1959).
(98) Cooper, J. E., “Treatment and Disposal of Plating Wastes”, Sewage
& md. Wastes, p 295 (March, 1951).
(99) Bucksteeg, Wilhelm, “Decomposition of Cyanide Wastes by Methods of
Catalytic Oxidation and Absorption”, 21st md. Waste Conf., Purdue
Univ. Engng. Ext. Series, pp 688-695 (May 3, 1966).
(100) Howe, R.HOL., “Biodestruction of Cyanide Wastes. Advantages and
Disadvantages”, mt. J. Air & Water Poll. Vol 9, p 463 (1965).
(101) Byron, R. F., et al, “Radiation Decomposition of Waste Cyanide
Solutions”, U.S. Patent 3,147,213 (July 11, 1961).
(102) Dvorin, R., “Dialysis for Solution Treatment in the Metal Finishing
Industry”, Metal Finishing, Vol 57, No. 4, pp 52-54 (1959).
(103) “Reverse Osmosis: An Old Concept in New Hardware”, md. Water Engng.,
Vol 4, No 0 7, pp 20-23 (July, 1967).
(104) Weiner, Robert F., “Acute Problems in Effluent Treatment”, Plating,
Vol 54, pp 1354-1356 (December, 1967).
(105) Serota, L., “Science for Electroplaters Waste Disposal”, Metal
Finishing, pp 58-60 (July, 1957).
(106) Barnes, G. E. and Weinberger, L. W., “Complex Metal Finishing
Wastes Licked by Effective Chemical Treatment”, Wastes Engng., Vol
28, pp 124-127 (1957).
(107) Trooper, E. B., “The Treatment of Certain Plating Solutions by Ion
Exchange”, Tech. Proc. Amer. Electroplaters’ Soc., pp 146-150
(1955).
(108) Bueltman, Charles and Mindler, A. B., “Rinse Water Reuse by Ion
Exchange”
51
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(109) “Waste Treatment at Douglas Aircraft”, Plating, Vol 42, pp 58-59
(January, 1955).
(110) Serfass, E. J., Muraca, R. F., and Gardner, D. G., “Treatment of
Cyanide Wastes by Ion Exchange”, Plating, Vol 40, pp 165, 168
(February, 1953); pp 268-278 (March, 1953).
(ill) White, J. M., et al, “Water and Plating Waste Treatment at Sperry”,
Plating, Vol 54, p 163 (February, 1967).
(112) Michaelson, A. and Burhans, C., “Chemical Waste Disposal by Ion
Exchange”, md. Water Wastes, Vol 7, pp 11-13 (1962).
(113) Fadgen, T. J., “Operation of Ion-Exchange Units for Treatment of
Electroplating Wastes”, Sewage & md. Wastes, Vol 27, pp 206-208 (1955).
(114) Smith, P. and Dykes, C., “Modern Methods of Waste Disposal”, Chem.
& Proc. Engr., Vol 40, No. 6, pp 200-203 (1959).
(115) Anon., “Effluent Treatment by Ion Exchange”, Electroplating and Metal
Finishing, Vol 16, pp 53, 54 (1963).
(116) Gurnham, C. Fred, “Liquid Industrial Wastes”, Sections I through VII,
Industrial Wastes (September, 1959, through October, 1960).
(117) Harris, E. P., “Recovery of Nickel,Chrornium,and Water”, Electroplating
& Metal Finishing, p 48 (February, 1961).
(118) Goldblatt, E., “Recovery of Cyanide from Waste Cyanide Solutions by
Ion-Exchange”, md. and Eng. them., Vol 51, pp 241-246 (1959).
(119) McGarvey, F. X., “The Application of Ion Exchange Resins to
Metallurgical Waste Problems”, Proc. 7th Industr. Waste Conf., Purdue
Univ., Engng.Extn. Ser. No. 79, pp 289-304 (1952).
(120) Bueltinan, C. G., “Ion-Exchange Treatment of Industrial Wastes”,
Sewage & md. Wastes, Vol 29, pp 1018-1023 (1957).
(121) Lakin, J.., “Effluent Treatment for the Small Plater”, Electroplating
and Metal Finishing, p 89 (March, 1961).
(122) Culotta, Joseph N., “Treatment of Cyanide and Chromic Acid Plating
Wastes”, Plating, Vol 52, No. 6, pp 545-548 (1965).
(123) Weisberg, Louis and Quinlan, E. F., “Recovery of Plating Wastes”,
Plating, p 100 (August, 1955).
(124) Neben, E. W., “Stop Chrome Waste, Pollution and Heat Loss”, Plating,
Vol 44, pp 52-55 (January, 1957).
(125) Lancy, L., “Plating Waste Treatment before Rinsing”, Products
Finishing, Vol 26, No. 10, pp 44-47, 50-52 (1962).
52
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(126) Lancy, Leslie, E., “An Economic Study of Metal Finishing Waste
Treatment”, Plating, Vol 54, pp 157-161 (February, 1967).
(127) Pinner, R., “Rinse Water Recirculation in Combination with the
Integrated Waste Treatment Method”, Electroplating and Metal
Finishing, p 208 (July, 1967).
(128) “Integrated Waste Treatment Facilitates 807 Rinse Water Recovery”,
Electroplating and Metal Finishing, p 213 (June, 1966).
(129) Lancy, L. E., “Integrated Treatment for Metal-Finishing Wastes”,
Sewage & md. Wastes, Vol 26, pp 1117-1125 (1954).
(130) Stroh, John and Allen, Clifford, “Low Cost Integrated Waste
Treatment at American Sterilizer”, Plating, p 869 (August, 1957).
(131) Anon., “New Packaged Plant Provides Standardized Control”, Electro-
plating and Metal Finishing, Vol 15, pp 446-447 (1962).
(132) Parker, H., “How to Determine Requirements for Rinse Waters in
Plating Processes”, Metal Progress, Vol 77, No. 2, pp 82, 83;
No. 6, p 146 (1960).
(133) Hanson, N. and Zabban, W., “Design and Operation Problems of a
Continuous Automatic Plating Waste Treatment Plant”, Plating,
Vol 46, pp 909-918 (1959).
(134) Spring, Samuel, “Water Supply, Rinsing and Drying”, Metal Finishing,
Vol 61, No. 4, pp 46-51 (1963).
(135) National Technical Advisory Committee, “Water Quality Criteria”,
Federal Water Pollution Control Administration, 13. S. Department
of the Interior Publication, Washington, D. C. (April 1, 1968).
53
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APPENDIX A
BIBLIOGRAPI-IY OF FOREIGN LITERATURE ON CYANIDE AND
REXAVALENT CHROMIUN WASTEWATER TREATMENT AND ANALYSIS
The bibliography which follows is supplemental to the references listed
previously in this report. This bibliography contains only foreign
references, some of which already have appeared in the aforementioned
list of references. The search was confined to papers concerned with
methods for treatment of analysis of wastewaters containing cyanides
and/or hexavalent chromium. The search was made using the indexes of
Chemical Abstracts because this is by far the most comprehensive abstract
journal available.
The search included the 1969 abstracts and went back through the year
1957. As the search continued backwards through the cumulative indexes,
it was apparent that the foreign references became less in number and
the number of American references increased.
The references in the bibliography below are grouped into several classi-
fications to make it easier for the user to locate the desired references.
The latest references appear first. In most cases the Chemical Abstracts
(C.A.) reference is given. Where the C.A. reference is omitted, the
reference originated in the previous bibliography.
An explanation is appropriate here as to what is included under the
various headings. In the treatment section, the term “chemical means”
refers to oxidation by chlorine, hypochiorites, permanganates, etc., and
to reduction by sulfur dioxide, ferrous sulfate, etc. The groupings
under electrolysis and ion exchange are self explanatory. The “miscel-
laneous” treatment section contains references to biological degradation,
adsorptive processes, water reuse, etc. There is a section listing
review articles. These would be useful for a relative newcomer to the
field for obtaining a quick study of the methods for treating cyanide or
hexavalent chromium wastewaters.
The search included analytical titles because in wastewater problems
analysis plays such an important role. These references also were divided
up and placed under appropriate headings. Again the term “chemical” is
used and here it refers to methods in which a quantitative determination
is made by titration. The other headings are easily interpreted. In
some cases the abstracts described analyses in which a combination of
methods are used and these are grouped separately.
Finally a section on patents is included. For an appreciable number of
these, the abstracts gave little or no.detail.
A-i
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TREATMENT OF CYANIDE WASTEWATER BY CHEMICAL MEANS
(1) Thielemann, Horst, “Analytical and Hygienic Studies on the Occur-
rence of Toxic Cyanide Compounds in the Electroplating Waste Water
of the VEB Television Factory”, (includes section on Treatment),
Stassfurt Werk, bile, Wiss. Z. Martin—Luther—Univ., Haile Witten—
berg, Math.—Naturwiss. Reihe, 18 (1), 71—80 (1969) (Ger.); C.A. 71,
128442d (1969).
(2) Kandzus, P. F. and Mokina, A. A., “Use of Ozone for Purifying Indus-
trial Waste Waters”, Tr., Vses. Nauch.—Issled. Inst. Vodosnabzh.,
Kanaliz., Gidrotekh. S—oruzhenii Imzh. Gidrogeol., (20), 40—5 (1967)
(Russ.); C.A. 71, 332l2q (1969).
(3) Kollau, K. N. and Reidt, M. J., “Investigations on a Pilot Plant
for the Continuous Treatment of Effluent Containing Cyanide”, TNO
Nieuws, 24 (2), 48—62 (1969) (Neth.); C.A. 71, 6388v (1969).
(4) Smirnov, D. N. and Monastyrenko, E. S., “Automatic Apparatus for the
Continuous Detoxification of Cyanide—Containing Waste Waters”,
Vodosnabzh., Kanaliz., Gedrotekh. Sooruzheniya, (5), 29—36 (1967)
(Russ.); C. A. 70, 90595v (1969).
(5) Kieszkowski, Marek and Krajewski, Stanislas, “Purification of
Cyanide—Containing Water with Permanganate”, Tech. Eaux (259—260),
21—7 (1968) (Fr.); C.A. 70, 6439s (1969).
(6) Saito, Toshihide and Ozasa, Yoshio, “Aeration of Cyanide Waste.
Capture of Gasified Hydrogen Cyanide”, Osaka Kogyo G utsu Shikenjo
Kiho, 19 (3), 191—4 (1968) (Jap.); C.A. 70, 31502q (1969).
(7) Bisehoff, Ch., “Fine Purification of Waste Water by Ozone with Low
Pollution Load”, Fortschr. Wassercheni. Ihrer Grenzgeb., (9), 121—30
(1968) (Ger.); C.A. 70, 14237q (1969).
(8) Shabunin, I. I., “Purification of Cyanide—Containing Waste Waters
by Air”, Tsvet. Metal, (7), 7—8 (1968) (Russ.); C.A. 69, 69571d
(1968).
(9) Lancy, L. E. and Fischer, G., “Determination of Cyanides Which can
be Decomposed by an Alkali and Chlorine Treatment”, Galvanotechnik,
59 (3), 192—3 (1968) (Ger.); C.A. 69, l2779y (1968).
(10) Rejka, Bohumul, “The Effect of Copper in Plating Wastes Treatment”,
Koroze Ochr. Mater., 11 (5), 104—6 (1967) (Czech.); C.A. 68,
117040h (1968).
(11) Ceamis, Mihail, “The Chemistry of the Treatment of Waste Waters From
Plating Shops. Purification of Cyanide—Containing Waters”, md.
Usoara, 14 (12), 730—4 (1967) (Rom.); C.A. 68 ll7038p (1968).
A-2
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(12) Rejha, B., “Why is the Permanganate Oxidation of Cyanide Wastes
Used”, Koroze Ochr. Mater., 11 (2), 39—42 (1967) (Czech); C.A. 68,
107721s (1968). —
(13) Kieszkowski, N., “Treating of Cyanide Effluents with Sodium Hypo—
chlorite”, Koroze Ochr. Mater., 11 (4), 77—80 (1967) (Czech.); C.A.
68, 98458g (1968).
(14) Kieszkowski, N., “Oxidation of Cyanides in Waste by Means of Sodium
Hypochiorite”, Pr, Inst. Mech. Precyz., 15 (1), 62—71 (1967) (Pol.);
C.A. 68, 24435a (1968).
(15) Jaickle, Heiner, “Degradation of Cyanides by Acids”, Galvanotechnik,
58 (7), 470—4 (1967) (Gee.); C.A. 68, 15925h (1968).
(16) Zwicky, H. P., “New Possibilities of Detoxication of Cyanide Con-
centrates by the Berliner—Weiss (white lead) Process”, Ber. mt.
Vortragstag. PRO Aqua, Basel 1965, 331—6 (Pub. 1966) (Ger.); C.A.
68, 6O15j (1968).
(17) Kollau, K. N., “Purification of Cyanide—Containing Waste Water”,
Constructiematerialen, 1 (6), 27—31 (1967) (Neth.); C.A. 67,
93800g (1967).
(18) Imai, Yuichi, “Effects of Various Metallic Ions on the Treatment
of Waste Liquor from Electroplating Baths. The Treatment of
Cyanides”, Kinzoku Hyonien Gijutsu, 16 (7), 288—92 (1965) (Jap.);
C.A. 67, 9379 9p (1967).
(19) Hartinger, Ludwig, “Removal of Heavy Metals From Waste Water Under
Difficult Conditions”, Wasser, Luft Betr., II (6), 353—9 (1967)
(Ger.); C.A. 67, 84678w (1967).
(20) Monastyrenko, E. S., “Electrode Systems for Control of Cyanides in
Waste Waters”, Mater. Soveshch. Molodykh. Spets. Vses. Nauch. Issled.
Vodosnabzh. Kanaliz. Gidrotekh. Sooruzhenii Imzh. Gidrogeol., 57—68
(1966) (Russ.); C.A. 67, 36191k (1967).
(21) Kieszkowski, Marek and Krajewski, Stanislaw, “Detoxication of
Cyanide—Containing Effluents with Potassium Permanganate”, Pr.
Inst. Mech. Precyz., 14 (3), 68—73 (1966) (Pol.); C.A. &7, 14684w
(1967).
(22) Krajewski, Stanislaw, “Iron Compounds in Electroplating Cyanide
Effluents”, Pr. Inst. Mech. Precyz., 14 (2), 59—64 (1966) (Pol.);
C.A. 66, 68726j (1967).
(23) Gandhi, P. G. and Varde, R. S., “Cyanide Waste Disposal”, Environ.
Health, 7 (4), 226—34 (1965) (Eng.); C.A. 66, 49O82e (1967).
(24) Oehme, F., “Comparison of Conventional Systems for the Removal of
Cyanides”, Tech. Eau (Brussels), (237), 39—41 (1966) (Fr.); C.A.
66, 40577n (1967).
A-3
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(25) Dembeck, H., “Methods of Treating Chemically and Biologically Con-
taminated Effluents from Laboratories”, Glas—Instr.—Tech., 10 (1),
2—10 (1966) (Ger.); C.A. 65, 855g (1966).
(26) Asendorf, Erich, “Errors in Cyanide Decontamination”, Galvanotech—
nik, 57 (4), 258—9, Discussion 260—2 (1966) (Ger.); C.A. 65, 8554c
(1966).
(27) Bahenski, V. and Zika, Z., “Treating Cyanide Wastes by Oxidation
With Ozone”, Koroze Ochrana Mater., 10 (1), 19—21 (1966); C.A. 65,
6907c (1966).
(28) Oehme, F., Laube, K. H., and Syden, H., “Comparison of the Most
Important Conventional Processes for the Chemical Removal of Cya—
nides”, Galvanotech. Oberflaechenschutz, 7 (3), 74—84 (1966) (Ger/
Fr.); C.A. 65, 356a (1966).
(29) Oehme, F. and Wyden, H., “New Method for the Determination and
Elimination of Cyanide”, Metalloberflache, 19 (9), 273—8 (1965)
(Ger.); C.A. 64, 435a (1966).
(30) Pavlovskii, A. P., “Removal of Cyanide Compounds from Waste Water”,
Vodosnabzh. i Sanit. Tekhn., (8), 36 (1965) (Russ.).
(31) Coleman, A. K., “Utilization of Waste Chrome Liquors for the Treat-
ment of Waste Cyanide”, Effluent Water Treat. 3., 4 (8), 365—7,
369—79 (1964) (Eng.); C.A. 61, l5825b (1964).
(32) Komendova, V. and Jadrny, 3., “Direct Purification of Cyanide—
Containing Sewage”, Vodni Hospodarstvi, 250—4 (1961); C.A. 61,
5352e (1964).
(33) Sundberg, Anders, “Purification of Waste Water From Surface Treat-
ment”, Ted. Tidskr, 93 (46), 1259—60 (1963); C.A. 61, 28l5f (1964).
(34) Gotzelmann, W. and Spanier, C., “The BW Process. A New Method for
Treating Cyanide Effluents with Ferrous Sulphate”, Galvanotechnik,
54 (5), 265 (1963); C.A. 59, 6123f (1963).
(35) Lancy, Leslie E. and Zabban, Walter, “The Relation Between Analysis
and Treatment of Cyanide Wastes”, Metalloberflaeche, 17 (3), 65—70
(1963); C.A. 59, 2503b (1963).
(36) Milovanov, L. V., Belevtsev. A. N., and Shchukina, G. A., “Purif i—
cation of Cyanide Effluents From Plating Shops”, Stochnykh Vod,
Vses. Nauchn.—Issled. Inst. Vodosnabzh., Kanaliz., Gidrotekhn.
Sooruzhenii I Inzh. Gidrogeol., (3) 4—16 (1962); C.A. 59, 1371g
(1963).
(37) Broucek, Jiri, “Oxidation of Cyanide Water With Peroxide”, Korose
Ochrana Mater., 95—6 (1962); C.A. 58, 13597g (1963).
A .-4
-------
(38) Asendorf, Erich, “Automatic Decontamination of Wastes Containing
Cyanide from Galvanizing Techniques and Salt Bath Hardening”,
Metall’-Reinig. Vorbehandi., 8 (3), 33—5 (1959); C.A. 58, 11093c
(1963).
(39) Ch’un-’Lin. Wang, “Oxidation of Cyanides in Industrial Waste Water
by the Action of Chlorine”, Hua Hsuch Tung Pao, (7), 37—8 (1960);
C.A. 58, 9951g (1963).
(40) Palaty, Jiri and Stanek, Miloslav, “Chlorination of Cyanide Waste
Waters by Injection into a Chlorinator”, Sb. Vysoke Skoly Chem.—
Technol. Praze, Oddil Fak. Technol. Paliv. Vody, 3 (1), 115—127
(1959); C.A. 57, 16343i (1962).
(41) Palaty, Jiri and liorakova—Jakubu, Marta, “The Course and Rate of
Removal of Cyanides From Water Under Natural Conditions”, Sb.
Vysoke Skoly Chem.—Technol. Praze, Oddil Fak. Technol. Paliv Vody,
3 (1), 83—114 (1959); C.A. 57, l4896f (1962).
(42) Bahensky, V., “New Method of Oxidation of Cyanide—Bearing Waste
Water From Electroplating”, Korose Ochrana. Mater., 67 (1961); C.A.
57, l3560h (1962).
(43) Petrov, V. I., “Effectiveness of the Purification of Waste Waters
Containing Cyanides”, Gigiena I Sanit., 27 (4), 61 (1962); C.A. 57,
448le (1962).
(44) Lurie, Yu Yu and Panova, V. A., “Method of Controlling the Extent
of Purification of Cyanide Waste Waters with Active Chlorine”,
Gigiena i Sanit., 25 (8), 44—6 (1960); C.A. 54, 25419b (1960).
(45) Müller, Werner, “In—Situ Detoxification o Cyanidic Sewage”,
Wasserwirtsch.—Wassertech., 10, 71—4 (1960); C.A. 54, 2635f (1960).
(46) Jadrny, J. and Koinendova, V., “Disposal of Metal Finishing Waste
Waters”, Vodni hospodarstvi, 9, 428—31 (1951); C.A. 54, 2635f (1960).
(47) B 1a Balla and Tibor Bene, “Removal of Cyanide From Industrial
Waste Waters by Chlorination. I. Technological Inve tigations”,
(Nehézvegyipari Kutatô Intézet, Veszprém, Hung.), Nehdzvegyipari
Kutató Intézet lCOzleményei, 1, 191—7 (1959); “II. Analytical
Methods”, Ibid., 199—206; C.A. 54, 70l9g (1960).
(48) Robinson, K., “The Treatment of Trade Effluents at Wilmot—Breeden,
Ltd., Brigwater”, Metalurgia, 61, 3—5 (1960).
(49) Sencha, I. Yu, “Installation for Removing Cyanides From Industrial
Waste Waters”, Gigiena I Sanit. 23 (9), 64—6 (1958); C.A. 53,
10607h (1959).
(50) Wild, F., “Effluent Problems. Chemical Treatment”, Metal Industry,
92, 111—13 (1958); C.A. 53, 915d (1959).
A-5
-------
(51) Pine, H., “Chlorination in the Treatment of Trade Wastes—Cyanide
Effluents, Treatment of Trade Waste Waters and Prevention of River
Pollution”, Isaac, Peter C. G., Editor, Univ. Durham—King’s Coil.
Dept. Civil Eng. Bu],l., No. 10, 312 pp, 185—94 (1957); C.A. 52,
8909g (1958).
(52) Kalinin, A. T., “Factors Affecting the Activity of High—Temperature
Cyanid.ing Baths, and a New Rapid Method for Disposal of Wastes From
Cyanide Baths”, Novye Metody Termichesk. Obrabotki V Rasplavien.
Solyakh i Shchelochakh Sbornik, 133—8 (1955); C.A. 52, 8909g (1958).
(53) Lancy, L. E., “Plant for Continuous Alkaline Chlorination of Waste
Waters Containing Cyanide”, Wass. Luft u. Betnieb, 2, 144—147 (1958).
(54) “Trade Effluent Treatment at Vauxhall Motor Plants”, Surveyor,
Lond., 117, 467—468 (1958).
TREATMENT OF HEXAVALENT CHROMIUM WASTEWATER BY CHEMICAL MEANS
(55) Avrutskii, P. 1., “Control of the Chromium (VI) Concentration in
Waste Waters”, Vodosnabzh.,, Kanaliz., Gidrotekh. Sooruzheniya, (5),
23—8 (1967) (Russ.); C.A. 70, 108995n (1969).
(56) Kollau, K. N. and Reidt, M. J., “Pilot Plant for the Continuous
Purification of Chromic—Acid Containing Effluent”, T.N.0. Nieuws,
23 (9), 367—74 (1968) (Neth.); C.A. 70, 22742r (1969).
(57) Koide, Syogo, “Waste Water From Plating Works. VII. Treatment of
Waste Water Containing Chromic Acid by Sulfite Reduction”, Kogyo
Yosui, (99), 40—54 (1966) (Jap.); C.A. 69, 45878h (1968).
(58) Barnoky, L., “An Apparatus for Controlling Chromium Removal From
Wastes of Chromium Plating Plants”, Fortschr. Wasserchem. Ihre
Grenz geb., (3), 127—36 (1965) (Ger.); C.A. 68, 53l07a (1968).
(59) Boose, C. A., “Chromic Acid—Containing Industrial Waste Water in
the Metal Industry”, Constructiemateriales, 1 (3), 22—5 (1967)
(Neth.); C.A. 68, l5923f (1968).
(60) Takamatsu, Hideo, “Treatment of Chromic Acid Wastes with Nitrites”,
Kiazoku Hyomen Gizutsu, 16 (10), 449—53 (1965) (Jap.); C.A. 66,
98293h (1967).
(61) Cram, R. W., “A Realistic Approach to Waste Treatment”, Proc.
Ontario md. Waste Conf. 9th, 54—64 (1962) (Eng.); C.A. 64, 1807h
(1966).
(62) Oehme, Friedrich, “Removal of Cr(VI) Compounds in Alkaline Medium
in Waste Waters Containing Cyanides”, Galvanotechnik, 56 (9),
545—8 (1965) (Ger.); C.A. 64, 431c (1966).
A-6
-------
(63) Jenkins, S. H., Keight, D. B., Ewins, Avril, “Solubility of Heavy
Metals Hydroxides in Water, Sewage and Sewage Sludge. II. Precipi—
tation of Metals by Sewage”, Air Water Pollution, 8 (11—12), 679—
93 (1964) (Eng.); C.A. 62, 10210e (1965).
(64) Shcherbakov, A. A., Pinaevskaya, E. N., and Antoshkina, N. A.,
“Decontamination of Sewage From Bichromate Production”, Ochistka
Stochnykh Vod Urala, Akad. Nauk SSR, Ural ’sk Filial, Otd. Vodn.
Resursov, 85—90 (1963); C.A. 61, 10436b (1964).
(65) Hantge, E., “Precipitation Agents for Neutralized Electroplating
Effluents”, Galvanotechnik, 54, 282 (1963).
(66) Kapitaficzyk, Kazimierz and Kurzawa, Zbigniew, “Recovery of Cr From
Industrial Wastes” (Politech. Poznai i, Poland), Poznai5. Towarz.
Przyjaci6l Nauk, Prace Komisji Nauk Podstawowych Stosowanych, 1
(2), 9 pp (1960) (Eng. Summary); C.A. 55, 3020a (1961).
(67) Weiner, Robert, “The Application of Flocculents in Sewage Treat-
ment”, Metallwaren—Ind. und Galvano—Tech., 51 (5), 221—7 (1960);
C.A. 54, 2 5417c (1960).
(68) Jadrny, J. and Komendova, V., “Direct Treatment of Effluents Con-
taining Chrome”, Vodn. hospod., 10, 67—70 (1960) (Eng. summary).
(69) Beck, N. T. and Bardi, I., “Reduction of Chromium (VI) by Different
Reducing Agents”, Acta Univ. Szegediensis. Acta Phys. et Chem.
(N.S.), 4, 54—8 (1958) (in Eng.); C.A. 53, 594lb (1959).
(70) Bandrowska, C. and Buntner, E., “Recovery of Chromium and Copper
From Pickle Liquors”, Przemysl. Chem., 13, 602—3 (1957); C.A. 52,
7087e (1958).
(71) Weiner, R., “Waste Waters in the Metal Industry”, Eugen G. Leuze
Verlag, Saulgau/W irtt., 152 pp (1958); Gas—u. Wasserfach, 100,
395—396 (1959).
(72) Meinck, F., “Method for Reducing Toxicity of Waste Waters Contain-
ing Chromic Acid”, Metalloberflaeche, 1, 105 (1947).
(73) Grindley, J., “Treatment and Disposal of Waste Waters Containing
Chromate”, J. Soc. Chem. Inc., Lond., 64, 339 (1945).
(74) Meinck, F., “The Treatment and Disposal of Waste Waters From
Chromium—Plating Plants”, Metallwarenind., 42, 37 (1944).
TREATMENT OF CYANIDE AND HEXAVALENT CHROMIUM
WASTEWATERS BY CHEMICAL MEANS
(75) Kogan, B. I., “Chemical Purification of Waste Waters of Galvanizing
Shops”, Sovren. Sposoby Ochistki Stochnykh Vod. Tsekhov Gal’ranopok—
rytii Mashinostroit Predpr., 11—23 (l968)(Russ.); C.A. 71, l28440b
(1969).
A-7
-------
(76) Shchitova, 0. N., “Performance of Working Neutralizing Stations”,
Sovrem. Sposoby Ochistki Stochnykh Vod. Tsekhov Gal’vanopolkrytii
Nashinostroit Predpr., 98—108 (1969) (Russ.); C.A. 71, 128428d
(1969).
(77) Dobrov, G. P., “Planning of Automated Stations for Neutralization
and Purification of Waste Waters”, Sovrem. Sposoby Ochistki
Stochnykh Vod. Tsekhov Gal’vanopokrytii Mashinostroit Predpr.,
109—16 (1968) (Russ.); C.A. 71, 128396s (1969).
(78) Plecity, V., “Efficiency of Automatic Industrial Water Purifica-
tion”, Koroze Ochr. Mater., 12 (5), 111—12 (1969)(Czech.); C.A. 71,
24569j (1969).
(79) Krajewski, Stanislaw and Kieszkowski, Marek, “Treatment of Water
Containing Cyanurate, Hexavalent Chromium, and Large Quantities of
Iron”, Tech Eau (261), 23—32 (1968) (Fr.); C.A. 70, 40516z (1969).
(80) Koniecka, Krystyna, “Treatment of Chromium and Cyanide Waste
Waters”, Gaz, Woda Tech. Sanit., 42 (8), 280—1 (1968) (Pol.); C.A.
70, 31504s (1969).
(81) Leisegang, L., “Purification Methods for Industrial Waste Water”,
Wasser. Luft Betr., 12 (3), 136—40 (1968); C.A. 69, 29964c (1968).
(82) Jaron, Stanislaw, “Automatic Regulation of pH in CN and Cr+ 6 Waste
Water Treatment”, Pomiary, Automat. Kontr., 14 (4), 172—3 (1968)
(Fol.); C.A. 69, 28812q (1968).
(83) Kollau, K. N. and Reidt, N. J., “Purification of Rinse Water Con-
taining Chromic Acid and Cyanide Obtained From Electrolytic and
Chemical Processes”, T.N.O. Nieuws, 23 (3), 186—93 (1968) (Neth.);
C.A. 69, 21773u (1968).
(84) Smirnov, D. N. and Karpunin, N. Ya., “Modern Methods for Automation
of Units for Purification of Waste Waters of Galvanizing Shops”,
Sovrem. Sposoby Ochistki Stochnykh Vod Tsekhov Gal’vanopokrytii
Mashinostroit Predpr., 73—7 (1968) (Russ.).
(85) Arnold, Kurt, “Residence Times for Decontamination and Neutraliza-
tion of Waste Waters of the Metal Industry”, Galvanotechnik, 59
(1), 22—31 (1968) (Ger.); C.A. 68, 98470e (1968).
(86) Coleman, A. K., “Utilization of Waste Chrome Liquors for the Treat-
ment of Waste Cyanide”, Effluent Water Treat. J., 8 (1), 29—33
(1968) (Eng.); C.A. 68, 98459h (1968).
(87) Hatch, R. and Taybor, R. W., “Chemical Treatment of Waste Water,
Especially in Standardized Installations”, Tijdschr. Oppervlakte
Tech. Metal, II (12), 378—85 (1968) (Neth.); C.A. 68, 800l8z (1968).
(88) Meucci, Fulvio, “Conservation of Water by Reuse in Italy”, Chem.
Eng. Progr., Symp. Ser., 63 (78), 54—65 (1967)(Eng.); C.A. 68,
62552u (1968).
A- 8
-------
(89) Bouchard, J., “Purification of Waste Water From Electroplating Ing.
Quim (Mex.), 12 (129), 40—2 (1967) (Span.); C.A. 67, 84683u (1967).
(90) Robbins, K., “The Treatment of Industrial Effluents”, Tetracol, 5,
32—7 (1966) (Eng.); C.A. 67, 36214v (1967).
(91) Krajewski, Stanislaw and Kieszkowski, Marek, “The Treatment of
Effluents Containing Cyanides, Chromium (VI) and High Amount of
Iron Compounds”, Pr. Inst. Mech. Precyz., 14 (3), 59—67 (1966)
(Pol.); CA. 67, l4681t (1967).
(92) Meyer, Gianni, “Modern Electrical Apparatus for the Measurement of
Physical and Chemicophysical Characteristics of Water and for Their
Automatic Control”, Acqua md., 8 (44), 11—22 (1966) (Ital.); C.A.
66, R21980x (1967).
(93) Kuntz, A., “Decontamination and Neutralization of Waste Waters in
the Metal Industry”, Galvanotechnik, 57 (8), 505—13 (1966) (Ger.);
C.A. 65, 18318b (1966).
(94) Elcock, C. R., “Inorganic Effluents——A Case History”, Effluent
Water Treat. J., 5 (6), 314—18 (l965)(Eng.); C.A. 65, lO32lc (1966).
(95) Monastyrenko, E. S. and Zin’kova, E. N., “Automatic Neutralization
of Waste Waters Containing Cyanides”, Vodosnabzh. i Sanit. Tekhn.,
(3), 23—7 (1966) (Russ.); C.A. 65, 3550c (1966).
(96) Drakhlin, E. E., “Clarification of Sewage From Metal—Plating Plants
and Printing Plate Production”, Sb. Tr., Leningr. Inst. Inzh.
Zheleznodor. Transp., (220), 108—23 (1964) (Russ.); C.A. 65, 3548a
(1966).
(97) Simon, Michel, “Purification of Waste Water From Industrial Chemi-
cal Surface Treatments”, Tech. Eau (Brussels),(229), 17—27 (1966)
(Fr.); C.A. 64, l5563c (1966).
(98) Hettwer, E. W., “Plating Waste Treatment”, Proc. Ontario Ind. Waste
Conf. 9th, 87—102 (1962) (Eng.); C.A. 64, 1808c (1966).
(99) Simon, M., “International Meeting on Effluent Treatment”, Galvano,
35 (352), 367—9 (1966) (Fr.).
(100) Suess, R., “Measurements and Control Problems in the Neutralization
and Treatment of Waste Water”, Industrieabwasser, 56—61 (1962)
(Ger.); CA. 62, 8823e (1965).
(101) Hefele, H. (Robert Bosch G.m.b H., Stuttgart, Ger.), “Rinse and
Recovery Methods that Lower the Costs and Simplify Waste Treatment
Problems”, Galvanotechnik, 55 (10), 589—611 (1964) (Ger.); C.A.
62, 3795c (1965).
A-9
-------
(102) Preston, W. C., “The Control of Effluent Treatment Processes”,
Electroplating & Metal Fin., 156 (May, 1965), 193 (June, 1965).
(103) Nohse, W., “New Experiences with the Lancy Process”, Galvanotech—
nik, 56 (2), 92—95 (1965).
(104) Rothkegel, Josef, “The Treatment of Effluents From Nonelectrolytic
Wet Chemical Metal Finishing Processes”, Metalloberflaeche, 18
(4), 97—101; (5), 133—6 (1964); C.A. 61, 13034h (1964).
(105) Stone, E.H.F., MacKenzie, K.C.E.., and Robinson, J.B.C., “The
Kynoch Effluent Treatment Plant”, J. Inst. Metals, 92, 33—40
(1963); C.A. 60, 661ld (1964).
(106) Hartinger, L., “Experiences with Waste Water Purification Instal-
lations in Galvano—Technical Industries”, Industrieabwasser, 20—6
(1963); C.A. 61, 431b (1964).
(107) Rhyn, H. (Polymetron A.--G. Zuerich, Switz.), “Instrumentation for
Treatment of Industrial Wastes”, Ber. Intern. Vortragstag. PRO
AQUA, Basel, 396—404 (1961) (Pub. 1963); C.A. 59, 6123c (1963).
(108) Lancy, Leslie E., “pH and Solubility of Heavy Metal Hydroxides”,
Galvanotechnik, 54, 139—141 (1963).
(109) Dufournet, M., “Purification of Waste Waters From Surface Treat-
ment of Metals”, Chim. et md. (Paris), 84, 85—105 (1960); C.A.
55, 7721h (1961).
(110) Kirchoff, F., “New Attitudes with Respect to the Effluent Problem”,
Galvanotechnik, 52, 115 (1961).
(111) Lutter, E., “Detoxication of Plating Waste Water”, Metaliwaren
md. u. Galvano—Tech., 48 (7), 296—300 (1957); C.A. 54, 25419d
(1960).
(112) Zejda, Ed, “Directions on the Processing of Waste Water From Cya-
nide Production and Plating Shops”, Vodni hospodarstvi, 5 (4),
128—30 (1955); C.A. 54, 25417i (1960).
(113) Dufournet, N., “Purification of Waste Waters From Superficial
Treatment of Metals”, Chim. et Industr., 84, 85—105 (1960).
(114) Wittmann, J., “Electroforming Effluents Including Chromate, Metals
and Cyanide”, Corrosion et Anticorrosion, 7 (7), 288—293 (1959).
(115) Smith, P. and Dykes, C., “Modern Methods of Waste Disposal”, Chem.
& Proc. Engr., 40 (6), 200 (1959).
(116) Justh, R.,, “Treatment of Effluents in the Metal Finishing Industry”,
Electroplating & Metal Fin., 12, 11—14, 47—50 (January, 1959).
A-lO
-------
(117) Douwenga, P., “Plant for the Treatment of Waste Waters From Plat-
ing Baths”, Metalloberflaeche, 12 (1), 22—26 (1958); Chim. et
Industr., 80, 450 (1958); C.A. 52, 19597a (1958).
(118) Wedekind, B., “Waste Water Purification in the Metal Industry”,
Metall., 12, 515—19 (1958); C.A. 52, 15377c (1958).
(119) “Effluents Treatment”, Chem. Tr. J., 143, 1362 (1958).
(120) Lancy, L. E., “Integrated (Plating) Waste Disposal Method”, Elec-
troplating & Metal Fin., 10, 251—253 (1957); J. Appi. Chein.,
Lond., Abstr., 8, 1—13 (1958).
(121) Hartung, K. H., “Treatment and Neutralization of Waste Waters”,
Metalloberflaeche, 12 (1), 17—21 (1958); Chiin..-et Industr., 80,
449 (1958).
(122) Raub, E. and Wiegand, H., “Waste Waters From Used Plating Baths”,
Metalloberflaeche, 12 (1), 1—4 (1958); Chim. et Industr., 80, 450
(1958).
(123) Wild, F., “Effluent Problems. II. Chemical Treatment”, Metal md.,
Lond., 92, 111—113 (1958); J. Appi. Chem., Lond., Abstr., 8, ii—
235.
(124) Rohde, H., “Present Condition of Treatment of Waste Waters From
the Iron and Metal Industry”, Gas—u. Wasserfach, 97, 778—782
(1956).
(125) “The Disposal of Toxic Effluents”, Industr. Chem. Mfr., 31, 455—
456 (1955).
(126) Eissner, G., “Detoxification and Neutralization of Waste Waters
From Galvanizing Plants”, Metaliwarenind, 46, 452—461 (1955);
Chem. Zbl., 128, 7780 (1957).
(127) Rupprecht, G., “The Treatment of Waste Waters From Galvanizing
Works”, Metalloberflaeche, 9, B, 70—73 (1955).
(128) Mulcahy, E. W., “Pollution by Metallurgical Trade Wastes. A Study
of Causes and Suggested Cures”, Metal Finishing J., 1, 289 (July,
1955).
(129) “The Disposal of Toxic Effluents”, Industr. Chem., 31, 455—456
(1955).
(130) Evans, V., “Effluents in the Metal—Finishing Industries”, Metal
md., Lond., 211—214 (1954).
(131) Nosek, J., “Waste Waters From Galvanizing Processes”, Voda, 31,
168-476 (1951); Chem. Zbl., 123, 4672 (1952).
A-il
-------
(132) Petru, A.., “Treatment Plants for Waste Waters From the Treatment
of Metal Surfaces”, Wasserwirtsch .aft—Wassertech., 2, 210 (1952);
Gas—u. Wasserfach., 94, 163—164 (1953).
(133) Pettet, A.E.J., “The Disposal of Plating Shop Effluents”, J. Elec—
trodepos. Tech. Soc., 25, 1—22 (1950).
(134) Mulcahy, E. W., “The Treatment of Plating and Pickling Shop
Wastes”, J. Electrodepos. Tech. Soc., 22, 227 (1947).
TREATMENT OF CYANIDE WASTEWATER BY ELECTROLYSIS
(135) Pungor, Erno and Toth, Kiara, “Recent Developments in the Theory
and Application of Some Ion—Selective Membrane Electrodes”, Hung.
Sd. Instrum., (14), 15—20 (October, 1968) (Eng.); C.A. 71,
131040h (1969).
(136) Rumi, Vladimir and Topinka, M., “Detoxication of Cyanide—Containing
Electroplating Waste Waters by Continuous Electrolytic Chlorina-
tion”, Metalloberflaeche, 23 (8), 225—31 (1969) (Ger.); C.A. 71,
94581f (1969).
(137) Okuda, Hideo, “Electrolytic Treatment of Concentrated Cyanide
Waste. I. Optimum Condition for Electrolysing Solution”, Kagaku To
Kogyo (Osaka), 43 (1), 23—9 (1969) (Jap.); C.A. 70, 83510k (1969).
(138) Ruml, V. and Topinka, M., “Disposal of Cyanide Waste Water From
Electroplating Plants by Continuous Electrolytic Chlorination”
Voc. Hospod., 18 (15), 205—10 (1968)(Czech); C.A. 69, 80008w (1968).
(139) Koniecka, Drystyna, “Electrolytic Decomposition of Waste Cyanides”,
Gaz, Woda Tech. Sanit., 41 (6), 201—2 (1967) (Pol.); C.A. 68,
l5888y (1968).
(140) Drabek, B. and Komendova, V., “Electrochemical Purification of
Cyanide Effluents”, Fortschr. Wasserchem. Ihre Grenzgebe, 3, 103—
12 (1965) (Ger.); C.A. 67, 49881k (1967).
(141) Fioshin, N. Ya. and Tomilov, A. P., “Industrial Electrosynthesis
of Organic Compounds” (Including a section on Electrolytic Des-
truction of Cyanides in Waste Waters), lJsp. Elektrophim. Org.
Soedin., Akad. Nauk SSSR, Inst. Elektrokhim, 256—77 (1966) (Russ.);
C.A. 67, l4681t (1967).
(142) Drogon, Jerzy and Pasek, Ludwik (Transport Equipment Works,
Rzeszow, Poland), “Continuous Electrolytic Destruction of Cyanide
Wastes”, Electroplating Metal Finishing, 18 (9), 310—13 (1965)
(Eng.); C.A. 63, 17677e (1965).
(143) Komendova, V. and Drabek, B., “Electrochemical Purification of
Cyanide Waste Water”, Vodni Hospodarstvi, 14 (11), 411—14 (1964);
C.A. 62, 8824c (1965).
A-l2
-------
(144) Stemparski, Stefan and Drogon, Jerzy, “Electrolytic Purification
of Spent Cyanide Electrolytic Baths”, Gaz., Woda Tech. Sanit., 36
(4), 158—9 (1962); C.A. 60, 8893d (1964).
(145) Lurte, Yu. Yu. and Genkin, V. E., “Electrochemical Purification of
Plating Shop Wastes”, Ochistka Stochnykh Vod, Vses. Nauchn.—lsslecl.
Inst. Vodosnabzh., Kanaliz., Gidrotekhn. Sooruzhenii i Inzh.
Gidrogeol., (3), 50—63 (1962); C.A. 59, 2504c (1963).
(146) Dart, H. C., Gentles, J. D., and Renton, D. G., “Electrolytic Oxi-
dation of Strong Cyanide Wastes”, J. Appi. Chem. (London), 13,
55—64 (1963); C.A. 58, 1l093e (1963).
(147) Genkin, V. E., “Electrochemical Purification of Cyanide—Containing
Waste Waters in an Experimental Apparatus”, Vestn. Tekhn. i Ekon.
Inform. Nauchn.—Issled. Inst. Tekhn.—Ekon Issled Gos. Kom. Soy.
Mm. SSR p0 Khim. (6—7), 51—4 (1961); C.A. 58, 3 195a (1963).
(148) Anon., “Electrolytic Oxidation of Cyanide”, The Water Waste Treat-
ment J,, 8 (8), 412 (1961); C.A. 57, 7044d (1962).
(149) Sztafrowski, Pavel and Kotulski, Baleslaw, “Electrochemical Oxida-
tion of Cyanides in Sewage”, Przemysl. Chem., 40, 339—41 (1961);
C.A. 56, 4540d (1962).
(150) Kurz, H. and Weber, W., “Electrolytic Cyanide Detoxication by the
Cynox Process”, Galvanotech. Oberflaechenschutz, 3, 92—7 (1962)
(Ger. Fr.).
(151) Lur’e, Yu. Yu. and Genkin, V. E., “Electrochemical Purification
of Waste Water Containing Cyanide Compounds”, Zhur. Priklad. Khim.,
33, 384—9 (1960); C.A. 54, 10192h (1960).
(152) Schmidt, Hans and Meinert, Hasso, “Electrolysis of Cyanides. I.
Electrolysis of Cyanides in Aqueous Solutions”, Z. Anorg. u.
Allgem. Chem., 293, 214—27 (1957); C.A. 52, 8789f (1958).
(153) Lakin, J., “Treatment of Plating Shop Effluent”, Electroplating
and Metal Finishing, 9, 221—4 (1956); C.A. 51, .5594ç (1957).
(154) Allais, G. and Noisette, H. G., “Problems Arising From the Purifi-
cation of Waste Waters From Metal Treatment Works”, Eau, 44, 131-
140 (1957).
TREATMENT OF HEXAVALENT CHROMIUM WASTEWATER BY ELECTROLYSIS
(155) Uneri, Saadet, “Cathodic Reduction Mechanism of Chromates”, Kim.
Muhendisligi, 3 (27), 10—15 (1968) (Turkish); C.A. 69, R64016s
(1968).
A-13
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(156) Schuize, Guenter, “Electrochemical Reduction of Chromic Acid—
Containing Waste Water”, Galvanotechnik, 58 (7), 475—80 (1967)
(Ger.); C.A. 68, 15876t (1968).
(157) Matulix, Yu. Yu. and Nitskene, A. Yu., “Mechanism of the Electro—
reduction of Chromic Acid on Various Cathodes”, Lietuvos TSR
Mokslu Akad. Darbai, Ser. B. (1), 45—70 (1959); C.A. 53, 12882h
(1959). —
TREATMENT OF CYANIDE WASTEWATER BY ION EXCHANGE
(158) Rueb, Friedmund, “Conditioning Metal Industry Waste Waters by
Ionic Exchange”, Wasser, Luft Betr., 13 (8), 292—6 (1969) (Ger.);
C.A. 71, 128432a (1969).
(159) Marquardt, Kurt, “Waste Water Detoxication and Neutralization
Installations Combined with a Final Treatment by Selective Ion
Exchange”, Metalloberflaeche, 23 (8), 231—6 (1969) (Ger.); C.A.
71, 94573e (1969).
(160) Bahensky, V., “Technical and Economical Importance of Plating
Wastes Treatment With Ion Exchangers”, Korose Ochr. Mater., 11
(5), 97—100 (1967) (Czech); C.A. 68, ll7037n (1968).
(161) Inczedy, J. and Frankow, T., “Ion Exchange Treatment of Waste
Waters Containing Cyanide”, Period. Polytech. Chem. Eng. (Buda-
pest), II (1), 53—9 (1967) (Eng.); C.A. 68, 15867r (1968).
(162) Olivero, Leonardo, “The Problem of Effluents of Plating Shops”,
Galvanotechnica, 17 (4), 75—85 (1966) (Ital.); C.A. 65, 10322b
(1966).
(163) Hissel, J. and Mrs. M. Cadot—Dethier, “The Determination of Cya—
nides in Water”, Tribune Cebedeau (Centre Belge Etude Doc. Eaux),
18, 272—96 (1965) (Fre.); C.A. 63, 16028h (1965).
(164) Meleshko, V. P. and Kochkina, I. T., “Clarification of Cyanide
Waste Waters with Ion Exchange Resins”, Okhrana Vodn. Resursov i
Ochistka Stochn. Vod (Voronezh: Voronezhsk. Univ.) Sb., 144—50
(1964) (Russ.); C.A. 62, 10211d (1965).
(165) Fridinan, I. D., “Use of Ion—Exchange Resins for the Purification
From Cyanides of Waste Waters in the Gold—Extracting Plants”,
Teoriya I Prakt. lonnogo Obmena, Akad. Nauk Kaz. SSR, Tr. Resp.
Soveshch, 140—3 (1962); C.A. 61, ll74Ob (1964).
(166) Guenther, H., “Detoxification of Cyanide Waste Water”, Elektrie,
16, 88—92 (1962); C.A. 57, 8373a (1962).
(167) Goldblatt, E., “Recovery of Cyanide From Waste Cyanide Solutions
by Ion Exchange”, md. & Eng. Chem., 51, 241—246 (1959).
A—14
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TREATMENT OF HEXAV ALENT CHROMIUM WASTEWATER BY ION EXCRM GE
(168) Shko batova, T, L. and Ryzhova, L. I., “Ion Exchange Extraction
of Nickel, Zinc, and Chromium From Waste Waters of Electroplating
Shops”, Vodosnabzh. Kanaliz. Gidrotekh. Sooruzh. Nezhved. Rasp.
Nauch. Sb. (1), 57-70 (1966) (Russ.); C.A. 66, 117992d (1967).
(169) Zdybiewska, Maria and Sznura, Anna (Silesian Tech. Univ., Giliwice,
Poland), “Trials on the Application of Ion Exchangers for Recovery
and Disposal of Some Substances From Industrial Wastes. I. Recovery
of Chromium”, Zesz. Nauk. Politech. Slaska, Inz. Sanit., (9), 167—
83 (1966) (Pol.).
(170) L’vovich, B. I. and Vol’Khin, V. V., “Ion Exchafige Extraction of
Chromium From Spent Electrolytes and Wash Waters From Electroplat-
ing Shops”, Sb. Nauchn. Tr. Permsk. Politekhn. Inst., (14), 112—18
(1963) (Russ.); C.A. 63, 343f (1965).
(171) Meleshko, V. P. and Evsikova, L. P., “Purification of Chromium—
Containing Sewage”, Okhrana Vodn. Resursov i Ochistka Stochn. Vod
(Voronezh: Voronezhsk. Univ.) Sb., 151—6 (1964) (Russ.); C.A. 62,
11521 (1965).
(172) Lurte, Yu. Yu. and Antipova, P. S., “Removal of Chromium From
Plating Wastes Through Ion Exchange”, Ochistka Stochnykh Vod,
Vses. Nauchn.—Issled. Inst. Vodosnabzh., Kanaliz., Gidrotekhn.
Sooruzhenii I Inzh. Gidrogeol., (3), 39—49 (1962); C.A. 59, 2504a
(1963).
(173) Korshunov, I. A., Subbotina, A. I., and Shirokova, E. I ., “Extrac-
tion of Metals and Their Compounds From Dilute Solutions. I. Ion—
Exchange Extraction of Chromium”, Trudy po Khimii i Khim. Tekhnol.,
4, 270—7 (1961).
(174) Kaeding, Joachim and Trieglaff, Kurt, “Purification of Chromium—
Containing Sewage by Means of Ion Exchangers”, Wasserwirtsch.—
Wassertech., 10, 66—71 (1960); C.A. 54, 16702b (1960).
(175) Gabrielson, G., “Purification of Chromic Acid Solutions by Cation
Exchange”, Metal Finishing J., 5, 19—21 (1959).
TREATMENT OF CYANIDE AND HEXAVALENT CHROMIUM
WASTEWATERS BY ION EXCHANGE
(176) Tanner, M., “Design and Operation of a Plating Waste Treatment
Plant”, Water Pollut. Contr. (London), 67 (4), 401—6 (1968) (Eng.);
CA. 70, 315l8z (1969).
(177) Glaytnan, J., “Treatment of Plating—Shop Waste”, Galvano, 37 (378—
379), 489—93 (1968) (Fr.); C.A. 69, 82825j (1968).
A-15
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(178) Deinbeck, Hermann, “Recirculation of Industrial Rinse Waters for
the Reduction of Waste Waters”, Wasser, Luft Betrieb, 10 (2), 93—
7 (1966) (Cer.); C.A. 65, 1951b (1966).
(179) Krug, 3., “Ion Exchange in Electroplating”, Galvanotechnik, 15,
423 (1963).
(180) Goekel, H., “Effluent Treatment Plant for Industrial Wastes and
the Resulting Sludge Problems”, Galvanotechnik, 54 (5), 259—264
(1963).
(181) Furrer, F., “Ion Exchange Plant for Purifying and Treating Electro-
plating Effluents”, Galvanotechnik, 54 (5), 272—277 (1963).
(182) “Effluent Treatment by Ion Exchange”, Electroplating and Metal
Finishing, 16, 53 (1963).
(183) Pearson, A.A.L. and Parker, G. G., “Ion Exchange Process for the
Recovery of Water Polluted in Metal Finishing Operations”, Trans.
Inst. Metal Finish., 38, 159—165 (1961); J. Appi. Chem., Lond.,
Abstr., 12, 117 (1962).
(184) Pearson, A. A. and Parker, G. G., “Treatment of Works Effluent”,
Electroplating & Metal Fin., 14, 200 (1961).
(185) Krusenstjern, A. V., “Ion Exchange in the Treatment of Waste
Waters”, Metalloberflaeche, 12 (1), 4—5 (1958).
TREATMENT OF CYANIDE AND/OR HEXAVALENT CHROMIUM WASTEWATER
BY MISCELLANEOUS MEANS OR BY MEANS NOT STATED IN ABSTRACT
(186) Thiele, H., “Detoxification of Cyanide—Containing Waste Water by
Catalytic Oxidation and Adsorption Process”, Fortschr. Wasserchem.
Ihrer Grenzgeb., (9), 109—20 (1968) (Ger.); C.A. 70, 4O511u (1969).
(187) Shimuzu, Tatsuo, Taguchi, Hisaharu, and Teramoto, Shiro, “Micro —
bial Treatment of Cyanide—Containing Industrial Wastes. III. Con-
tinuous Treatment of Cyanide—Containing Industrial Wastes by
Fusarium Solani”, Hakko Kogaku Zasshi, 46 (10), 807—13 (1968)
(Jap.); C.A. 70, 31515w (1969).
(188) Brebion, C., “Removal of Certain Toxic Pollutants of Chemical
Origin From Liquid Industrial Wastes”, Terres Eaux, 21 (55), 9—17
(1968) (Fr.); CA. 69, 99199f (1968).
(189) Blumenthal, S. C., et al., “Cyanide Metabolism in Higher Plants.
III. Biosynthesis of —cyanoalamine”, J. Biol. Chem., 243 (20),
5302—7 (1968) (Eng.); C.A. 69, 84l89d (1968).
(190) Weiner, Robert, “Temporary Electroplating Waste Water Detoxifica-
tion”, Galvanotechriik, 59 (7), 605—9 (1968) (Ger.); C.A. 69,
800l9a (1968).
A-16
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(19],) Misono, Terunobo, “Biological Treatment of Industrial Waste Water:
Biological Treatment of Factory Waste Water”, Kagaku Kogaku, 32
(6), 523-7 (1968) (Jap.); C,A. 69, 54152u (1968).
(192) Honda, Shigeru and Kondo, Goro, “Activated—Charcoal Treatment of
Waste Water Containing Cyanide”, Osaka Kogyo Gijutsu Shikensho
Kiho, 18 (4), 367—71 (1967) (Jap.); C.A. 69, 4587Oz (1968).
(193) Taguchi, Hisaharu, et al., Shimizu, Tatsuo, Teramoto, Shiro,
“Microbial Treatment of Industrial Wastes Containing Cyanide. I.
The Effect of Some Environmental Conditions on the Growth Rate and
the Cyanide Degradation Activity of Fusarium Solani”, Hakko Kogaku
Zasshi, 45 (7), 630—6 (1967) (Jap.); C.A. 69, 5065j (1968).
(194) Mokry, Jan, “Possible Biochemical Purification of Waste Water Con-
taining Cyanide Compounds”, Przem. Chem., 46 (10), 572—5 (1967)
(Pol.); C.A. 68, 62487b (1968).
(195) Lueck, Winfried, “Electrical Cyanide Control of Galvanic Waste
Waters”, Ber. mt. Vortragstag. PRO AQUA, Basel, 343—8 (1965) (Pub.
1966) (Ger.); C.A. 67, 120028v (1967).
(196) Rueb, Freidmund, “Treating Waste Water of Metal—Working Plants”,
Wasser, Luft, Betr., 11 (6), 339—45 (1967) (Ger.); C.A. 67,
84686x (1967).
(197) Brebion, C., Cabridene, R., and Huriet, B., “Biology of Cyanide.
Treatment Possibilities of Residual Water Containing Cyanide.
Analytical Techniques”, Eau, 53 (10), 463—70 (1966) (Fr.); C.A.
66, 49081d (1967).
(198) Bogers, P.F.G., “Neutralization of Waste Water in the Surface
Treatment of Metals”, Tijdschr. Oppewlakte Tech. Metal., 10 (11),
370—6 (1967) (Dutch).
(199) Pinner, P., “Rinse Water Recirculation in Combination with the
Integrated Waste Treatment Method”, Electroplating & Metal Finish-
ing, 209—222 (July, 1967).
(200) Barta, H.E.P., “Plating Wastes—Automatic Recovery Saves Materials,
Money, and Manpower”, Effluent Water Treat. 3., 5 (7), 374—6
(1965) (Eng.); C.A. 65, l0322a (1966).
(201) Palaty, J., “Purification of Cyanide Wastes on Black Coal Slag”,
Sb. Vysoke Skoly Chem. Technol. Praze, Technol. Vody, 5 (1), 7—15
(1962) (Czech); C.A. 63, l579d (1965).
(202) Lurte, Yu. Yu., Kandzas, P. F., and Mokina, A. A., “Possible Utili-
zation of the Chemical Action of Ultrasound in Clarifying Industrial
Waste”, Nauchn. Soobshch. Vses. Nauchn.—Issled Inst. Vodosnabzh.
Kanaliz., Gidrotekhn. Sooruzh. I Inzh. Gidrogeol., Ochistka Prom.
Stochn. Vod, Moscow, 7—9 (1963) (Russ.); C.A. 62, 3793g (1965).
A .-17
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(203) ]3atista, Renato G. and Hard, Robert A. (Massachusetts Inst. of
Technol., Cambridge), “Solvent Extraction of Transition Metals
From Th iocyanate Solutions”, Trans. AIME, 227, 124—30 (1963).
(204) Randall, 3. A., “Notes on Plating Shop Drainage”, Electroplating
and Metal Finishing, 16 (9), 311—312 (1963).
(205) Asendorf, E., “Continuous Detoxification of Waste Waters by the
Degussa Process”, Wasser. Luft Betrieb, 2, 200—2 (1958); C.A. 57,
13560g (1962); also Water Poll. Abstr. 33, Abstr. #157 (1960).
(206) Pijck, 3,, Hoste, 3., and Gillis, 3. (Univ. Ghent, Belg.), “Radio—
metric Control of Analytical Separation Procedures”, Mikrochim.
Acta, 76—86 (in English) (1962).
(207) Dinsti, G. and Hecht, F. (Univ. Vienna), “Radiochemical Testing of
the Extractive Separation of Chromium and Manganese”, Mikrochim.
Acta, 321—6 (1962) (Ger.).
(208) Silman, H., “The Re—Use of Water in the Electroplating Industry”,
Chemistry and md., 2046—2051 (1962).
(209) Blanke, Nohse, and Woliman, “Not Removal——But Regeneration”,
Galvanotechnik, 53, 220—228 (1962).
(210) “A New Fully Automatic Effluent Neutralization and Treatment
Installation”, Galvanotechnik, 53, 194—196 (1962).
(211) Hendrickx, Y., “Adsorption of Anions on Bentonites”, Proc. U.N..
Intern. Conf. on Peaceful Uses At. Energy, 2nd, Geneva, 27, 178—81
(1958) (Pub. 1959); C.A. 55, 17159g (1961).
(212) Bucksteeg, W., “Microbial Decomposition of Cyanides in Waste
Water”, Schweiz. Z. Hydrol., 22, 407—19 (1960) (Ger.); C.A. 5 ,
10760g (1961).
(213) Kalauch, Carl, “Sewage Disposal of Electrodeposition Shops”,
Wasserwirtsch. Wassertech., 10, 343—6 (1960); C.A. 55, 6743i (1961).
(214) “Recovery of Nickel, Chromium, and Water”, Electroplating and Metal
Finishing, 14 (2), 48 (1961).
(215) “Disposal of Wastes From Metal Treatment Plants”, Metal Finishing
U., 7, 24—25 (1961).
(216) Rutgers, A. 3. and Rendrickx, Y., “Negative Adsorption of Anions
by Suspensions of Bentonites”, Experientia, 14, 316—18 (1958) (in
English); C.A. 8769i (1959).
(217) Pettet, A.E.J. and Mills, E. V., “Biological Treatment of Cyanides
With and Without Sewage”, 3. Appl. Chem. (Lond.), 4, 434—44 (1954);
C.A. 52, 9494h (1958).
A—18
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REVIEWS O METHODS FOR TREATMENT OF CYANIDE
AND URXAVALENT CHROMIUM WAST WATERS
(218) Oehme, F,, “Development Trends of Waste Water Detoxification in
the Metals Industry. I. Cyanide Detoxification”, Oberflaeche—
Surfaces 9 (6), 142—5; (7), 159—62 (1968) (Ger.); C.A. 69,
R99203c (1968).
(219) Antoine, Louis, “Water Pollution. Treatment of Industrial Wastes”,
Tech. Eau (257), 37—51 (1968) (Fr.); C.A. 69, R69545y (1968).
(220) Chakrabarty, R. N. and Bhaskaran, T. R., “Some Practical Approaches
to Treatment of Wastes From Small Electroplating Industries”,
Technology (Sindri), Spec. Issue, 3 (4), 26—8 ç1966) (Eng.); C.A.
68, R1O7737b (1968).
(221) Belevtsev, A. N. and Genkin, V. E., “Purification of Waste Waters
From Galvanic Coating Plants”, Zh. Vses. Khim. Obshchest., 12
(6), 644—51 (1967) (Russ.); C.A. 68, Rl077l6u (1968).
(222) Rueb, Friedmund, “Waste Water Processing in the Treatment of Metal
Surfaces”, Metalloberflaeche, 22 (3), 65—9 (1968) (Ger.); C.A. 68,
R107712q (1968).
(223) Heynemann, W. and Bradke, H. J., “Waste Water Treatment in the Iron
and Metal Treatment Industries”, Oesterr.—Abwasser—Ruridsch., 12
(5), 72—4; (6) 81—8 (1967) (Ger.); C.A. 68, R897l7p (1968).
(224) Mirsch, E., “The Determination of Cyanides in Wastes and Surface
Waters”, Fortschr. Wasserchem. Ihrer Grenzygeb., 2,120—7 (1965)
(Ger.); C.A. 68, l59l7g (1968).
(225) Nagendran, R. and Parthasaradhy, N. V., “Present Trends in the
Treatment of Cyanide Effluent in Electroplating”, Trans. Soc.
Advan. Electrochem. Sci. Technol., 1 (3), 6—9 (1966); C.A. 68,
R15856m (1968).
(226) Mattock, G., “Modern Trends in Effluent Control”, Metal Finishing
J., 168—175 (May, 1968).
(227) Doslçar, 3. and Gabriel, 3., “Removal of Cyanide Wastes in the
Machinery Industry ”, Werkstattstechnik, 57 (4), 197—9 (1967)
(Ger.); C.A. 67, R57l20b (1967).
(228) Bouchard, 3., “International Meeting About Effluents Treatment”,
Galvano, 35 (350), 197—200 (1966) (Fr.); C.A. 67, 5557e (1967).
(229) Weiner, Robert, “fletoxication of Cyanide Concentrates”, Galvano—
technik, 56, 459—62 (1965) (Ger.); C.A. 66, R88472b (1967).
(230) Weiner, Robert, “The Development and Current Status of Ion Exchan-
gers in Electroplating Water Treatment”, Galvanotechnik, 57 (8),
518—27 (1966) (Ger.); C.A. 66, R5591r (1967).
A-l9
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(231) Oehrne, Friedrich, “Methodical Fundamentals of Waste Water Purif i—
cation”, Galvanotech. Oberflaechenschutz, 6, 139—41 (1965); C.A.
65, R19832e (1966).
(232) Hugenneyer, Cello, “Treatment of Waste Waters From Metal Finishing
Industries”, Met. ABM (Assoc. Brash, Matais),22 (100), 199—211
(1966) (Port.); C.A. 65, R1951c (1966).
(233) “Outworkers Bring Plating and Effluent Disposal Right Up—to—Date”,
Industrial Finishing (London), 18, 27 (January, 1966).
(234) Gilmore, A. J. and Gow, W. A., “Cyanide Recovery From Gold—Barren
Waste Solutions: A Literature Review”, Can., Dept. Mines Tech.
Surv., Mines Branch, Inform. Circ. IC 145, 10 pp (1953); C.A. 59,
4895g (1963).
(235) Bahensky, V. and Chalupa, J., “Recent Progress in Electroplating
Effluents”, Galvanotechnik, 54, 10—11 (1963).
(236) Bon, J. J., “Waste Water From Metal Surface Treatment”, Tech. Eau
(Brussels), 184, 61—4 (1962); C.A. 57, 5730c (1962); C.A. 66,
R3l8939x (1967).
(237) Pettet, A.E.J., “Treatment of Plating Wastes and Cyanides”, Inst.
Sewage Purif., Symp. Trade Wastes, 79—94 (1957); C.A. 55, 3890d
(1961).
(238) Volz, K., “Electroplating Waste Water”, Metalloberflaeche, 12, 1—4
(1958); C.A. 52, 195961 (1958).
(239) Pa ztó P ter, “Removal of Cyanides From Waste Waters”, Besthmol6
Vizgazdálkodási Tudomanyos Kutato Intezet, 110—24 (1955); C.A. 52,
l49lOc (1958).
(240) Allen, Robert, “Disposal of Waste Materials in the Electroplating
Industry”, Disposal md. Waste Materials Conf., Sheffield Univ.,
81—7 (1956); C.A. 51, 8549d (1957).
ANALYSIS FOR CYANIDE BY CONVENTIONAL CHEMICAL MEANS
(241) Rejha, Bohumil, “Reliability of Permanganate as an Indicator of
the Detoxification of Cyanides”, Korose Ochr. Mater., 13 (2), 45—6
(1969) (Czech.); C.A. 71, l28 1 *23y (1969).
(242) Dolzhartskaya, Yu. B. and Edel’man, 1. I., “Determination of Cya—
nides in Some Industrial and Waste Waters”, Koks. Khim., (8), 37—8
(1969) (Russ.); C.A. 71, 104994j (1969).
(243) Wantschura, Rainer, “Determination of Total Cyanide in Waste Waters
of the Electroplating Industry and in Municipal Sewage”, Gas—
Wasserfach, 110 (26), 711—12 (l969)(Cer.); C.A. 71, 73826z (1969).
A-20
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(244) Leschber, Reimar and Schlichting, Hilde, “Decomposability of Com-
plex Metal Cyanides During the Determination of Cyanide in Waste
Water”, Fresenium’ z. Anal. Chem., 245 (5), 300—3 (1969) (Ger.);
C.A. 71, 42021d (1969).
(245) Schuster, H and Winkel, P., “Cyanide Detoxication. Estimation of
Cyanide DetoxicatIon by the Lancy Method”, Galvanotechnik, 59 (3),
189—92 (1968) (Ger.); C.A. 68, 107720r (1968). —
(246) Pociecha, Zygmunt, “Complexometric Determination of Cyanides in
Water and Sewage”, Chem. Anal. (Warsaw), 12 (2), 243—51 (1967)
(Pol.); C.A. 67, 9 3 782c (1967).
(247) Khie, Karl, “Occurrence and Study of Cyanogen”, Oesterr.—Abwasser—
Rundsch., 11 (4), 58—61 (1966) (Ger.); C.A. 67, 25230w (1967).
(248) Fleps, Walter, “Determination of Free and Bound Cyanide in Indus-
trial Waste Water”, Gesundh.—Ingr., 84 (7), 209—12 (1963); C.A.
60, 14247h (1964).
(249) Bahensky, V. and Zika, Z., “The Quantitative Determination of Cya—
nides in Effluents”, Galvanotechnik, 53, 122 (1962); C.A. 57,
3222e (1962).
(250) Lur’e, Yu. Yu. and Panova, V. A., “Determination of Cyanides and
of Active Chlorine in Purified Waste Water”, Tsvetnye Metally, 33
(8), 14—15 (1960); C.A. 55, ll7l2h (1961).
(251) Schlechting, Hilde, “Determination of Cyanide in Waste Water”,
Gesundh.—Ing., 81, 248—9 (1960); C.A. 54, 254l2g (1960).
ANALYSIS FOR CYANIDE AND HEXAVALENT CHROMIUM
BY CONVENTIONAL CHEMICAL MEANS
(252) Machu, Willi, “The Analytical Investigation of Sewage”, Galvano—
technik, 51, 161—7 (1960); C.A. 61, l597b (1964).
ANALYSIS FOR CYANIDE BY ELECTROCHEMICAL MEANS
(253) Berndt, Tilo, “Amperometric Cyanide Determination in Waste Water”,
Acta IMEKO, 3, 289—96 (1967) (Ger.); C.A. 71, 42025h (1969).
(254) Gerchinan, Lois L. and Rechnitz, Garry A., “Potentiometric Titration
of Cyanide Using the Cation—Sensitive Glass Electrode as Indicator”,
Fresanius’ Z. Anal. Chain., 230 (4), 265—71 (1967) (Eng.); C.A. 68,
26691e (1968).
(255) Sinirnov, D. N. and Monstyrenko, E. S., “Automatic Control of Cya—
nides in Waste Waters”, Vodosnabzh. Kanaliz. Gidrotekh. Sooruzh.
Mezhved. Resp. Nauch. Sb., (1), 95—108 (1966) (Russ.); C.A. 66,
98310m (1967).
A—2l
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(256) Oehme, F. and Disam, J., “Cyanide Detoxication. Amperometric
Measurement of Small Concentrations of Activated Chlorine in Cya-
nide Detoxication”, Galvanotechnik, 58 (4), 236—44 (1967); C.A.
67, 46982h (1967).
(257) Oehine, F., “Application of Laboratory Recorder POLY—RECORDER to
Direct Potentiometric Determination of Sodium and Cyanide”, Glas—
Instrum.—Tech., U, (1), 16—21 (1967) (Ger.).
(258) Musha, Soichior and Ikeda, Sariae, “Successive Amperometric Titra-
tion of Cyanide, Chloride, and Cyanate Using Rotating Platinum
Electrode”, Bunseki Kagaku, 14 (9), 795—803 (1965) (Jap.); C.A.
63, 1553la (1965).
(259) Roennefahrt, K. W., “Electrochemical Methods of Analysis for Water
and Effluents”, Wasser Luft Betrieb., 9 (6), 365—70 (1965) (Ger.);
C.A. 63, l2874a (1965).
(260) Gauchat, Charles, “Industrial Application of Potentiometry”, Dec—
hema Monograph, 35 (528—555), 125—31 (1959); C.A. 57, 4000h (1962).
ANALYSIS FOR CYANIDE AND HEXAVALENT
CHROMIUM BY ELECTROCHEMICAL MEANS
(261) Helbig, Herbert, “Amperometry and Related Electrochemical Methods
in Process Technology”, Chem. Tech. (Leipzig), 21 (9), 553—7
(1969); C.A. 71, 108646v (1969).
ANALYSIS FOR CYANIDE BY COLORIMETRY
(262) Zika, Z., “Determination of Cyanides by Modified Colorimetric
Method Using Picric Acid”, Koroze Ochr. Mater., 13 (1), 20—3 (1969)
(Czech.); C.A. 71, 533hz (1969).
(263) Blaha, Jan., “Toxicity and Determination of Free and Complex Cya—
nides in Water”, Vom Wasser, 34, 175—95 (1967) (Ger.); C.A. 69,
45940x (1968).
(264) Dietz, F., “New Results on Cyanide Determination”, Vom Wasser, 34,
202—8 (1968) (Ger.); C.A. 69, 38561w (1968).
(265) Hamamura, Norikatsu, “Rapid Determination of Cyanide Ion in Indus-
trial Wastes”, Eisei Kagaku, 13 (4), 183—6 (1967) (Jap.); C.A. 68,
42954h (1968).
(266) Leschber, Reimar, “Determination of Cyanides in Waste Waters by
Known Analytical Methods”, Galvanotechnik, 58 (7), 462—70 (1967)
(Cer.); C.A. 68, 15900w (1968).
A-22
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(267) Gafitanu, Mioara and Marculescu, Victoria, “Analytical Methods for
Determining Cyanides in Surface and Waste Waters”, Hidroteh.
Gospodarirea. Apelor Meteorol, 12 (1), 38—42 (1967) (Rom.); C.A.
67, 67409s (1967).
(268) Mirsch, H., “Determination of Cyanides in Waste Waters and Surface
Waters”, Fortschr. Wasserchem. Ihre Grenzgeb., 1, 120—7 (1964)
(Ger.); C.A. 67, 36190j (1967). —
(269) Jenkins, S. H., Hey, A. E., and Cooper, J. S., “Determination of
Cyanide in Low Concentration”, Air WaterPollution, 10 (8), 495—
519 (1966) (Eng.); C.A. 65, 15062f (1966). —
(270) Gahensky, V., “A Rapid Method of Estimating Cyanides in Waste
Waters”, Korose Ochrana Mater., 1 (5), 106—7 (1963) (Czech.); C.A.
64, 19179d (1966).
(271) Mrkva, M., “The Effect of Ferro— and Ferricyanides on the Deter-
mination of the Free Cyanides in Water”, Vodni Hospodarstvi, 15
(1), 22—5 (1965); C.A. 63, 5371h (1965).
(272) Lur’e, Yu. Yu. and Panova, V. A., “Determination of Cyanides and
Thibcyanates in Waste”, Zavodsk. Lab., 31 (4), 420—1 (1965)
(Russ.); C.A. 63, 343h (1965).
(273) Lur’e, Yu. Yu. and Panova, V. A., “Determination of Cyanates in
Waste”, Zavodsk. Lab., 31 (4), 421 (1965) (Russ.); C.A. 63, 343g
(1965).
(274) Palaty, J., “Colorimetric Determination of Cyanides for Waste
Treatment Plants”, Sb. Vysoke—Skoly Chem.—Technol. Praze, Oddil
Fak. Technol. Palev Vody, 4 (1), 259—67 (1960) (Czech); C.A. 62,
l4317g (1965).
(275) Lur’e, Yu. Yu. and Panova, V. A., “Determination of Cyanides in
Waste Waters with Sulfanilic and Barbituric Acids”, Nauchn.
Soobshch. Vses. Nauchn.—Issled. Inst. Vadosnabzh., Kanaliz.,
Gidrotekhn. Sooruzh. i Inzh. Gidrogeol., Ochistka Prom. Stochn.
Vod, Moscow, 31—4 (1963); C.A. 61, 14342f (1964).
(276) Dyatlovitskaya, F. G., “Determination of Cyanides in Industrial
Sewage by Using Barbituric Acid”, Vopr. Gigieny Naselen. Mest.
(Kiev. Gos. Izd. Med. Lit Ukr. SSR) Sb.,, 4, 208—13 (1963); C.A.
61, 14342d (1964).
(277) Bark, L. S. and Higson, H. G., “Investigation of Reagents for the
Colorimetric Determination of Small Amounts of Cyanide. II. A
Proposed Method for Trace Cyanide in Waters”, Talanta, 11 (3),
621—31 (1964) (Eng.); C.A. 60, 10390d (1964).
(278) Ferrari, Andres, “Quantitative Continuous Analysis ofWaste Water”,
Tech,. Eau (Brussels), 184, 55 -69 (1962); C.A. 57, 5729e (1962).
A-23
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(279) Russell, F. R. and Wilkinson, N. T., “The Determination of Cyanides
in Effluents”, Analyst, 84, 751—4 (1959); C.A. 54, 25411a (1960).
(280) Zdenek, Kubista, “The Determination of Cyanides in Industrial Waste
Waters”, Korose a Ochrana materialu, 1 (2), 26—8 (1957); C.A. 52,
977g (1958).
(281) Knie, K. and Gams, H., “Determination of Cyanides in Waste Water”,
Osterr, Wasserwirtsch, 8, 282—4 (1956); C.A. 51, 14173c (1957).
ANALYSIS FOR HEXAVALENT CHROMIUM BY COLORIMETRY
(282) Poniinov, I. S., et al., “Apparatus for the Automatic Control of
Chromium in Industrial Waste Waters From Electroplating Shops”,
Sb. Dokl. Sib. Soveshch. Spektrosk., 3rd Krasnoyarsk, USSR, 121—3
(1964) (Pub. 1966) (Russ.); C.A. 68, 33011m (1968).
ANALYSIS FOR CYANIDE AND HEXAVALENT
CHROMIUM BY COLORIMETRY
(283) Zuse, Manf red, “Spectrophotometric Determination of Cyanide, Hypo—
chlorite, Chromate, and Nitrite in Waste Water”, Galvanotechnik,
57 (8), 500—4 (1966) (Ger.); C.A. 65, 19827c (1966).
(284) Bahensky, Vl. and Chalupa, J., “Rapid Control Method for Effluent
Composition”, Galvanotechnik. 55 (12), 709—11 (1964) (Ger.); C.A.
62, 143l8g (1965).
(285) Krusenstjern, A. V. and Harst, H., “Analysis of Galvanic Waste
Water”, Metalloberflaeche, 13, 315—16 (1959); C.A. 60, 2631d (1964).
ANALYSES FOR CYANIDE AND/OR HEXAVALENT CHROMIUM
BY VARIOUS COMBINATIONS OF METHODS
(286) Kollau, K. N. and Reidt, N. 3., “Estimation of the Cyanide Content
in Waste Water and the Estimation of the Cyanide and Cyanogen
Chloride in Treated Waste Water”, TNO Nienws, 24 (8), 465—71 (1969)
(Neth.); C.A. 71, 1l635q (1969).
(287) Mertens, Hans, “Determination of Free Cyanide in Waste Water”, Gas—
Wasserfach, 110 (13), 349—54 (1969) (Ger.); C.A. 70, l08977h (1969).
(288) Namiki, Hiroshi, “Methods of Testing Polluted Water”, Bunseki
Kagaku, 17 (2), 244—52 (1968) (Jap.); C.A. 68, R98447c (1968).
(289) Dembeck, Hermnann, “Suitability of Various Procedures for Determin-
ing Cyanogen in Waste Water”, Wasser, Luft Betr., 10 (2), 822—3
(1966) (Ger.); C.A. 66, 68712b (1967).
A-24
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(290) Simon, Michel, “Determination of Cyanide in Industrial Waste Water”,
Tech. Eau (Brussels),(239), 17—22 (1966) (Fr.); C.A. 66, 5 8 699p
(1967).
(291) Borchert, 0.., “The Analysis of Waste Water”, Netalloberflaeche, 19
(10), 31,0—12 (1965) (Ger.); C.A, 65, 3550b (1966).
(292) Bilobran, Stanislawa, “Determination of Cyanides in Industrial
Galvanic Waste Liquors”, Prace Inst. Mech. Precyzyjnej, 11, 55—61
(1963) (Pol.); C.A. 63, 6710g (1965).
(293) Weber, W., “Methods for the Determination of Small Quantities of
Cyanide in Plating Wastes”, Galvanotechnik, 51, 287—93 (1960);
C.A. 56, 7044g (1962).
(294) Dozanska, Wiera, “Occurrence and Estimation of Cyanides in Sewage
Water”, Roczniki P&nstwowego Zakladu Rig., 8, 517—28 (1957); C.A.
52, 7584f (1958).
(295) Linford, A., “Instrumentation in the Disposal of Finishing Wastes”,
Electroplating & Metal Fin., 8, 384—388 (November, 1955).
PATENT S
(296) Grahmann, Herbert, et al., “Decontamination of Alkali Cyanide,
Acid, and Chromium—Containing Waste Waters”, German (East) 66,396
(April 5, 1969); C.A. 71, Pll6373u (1969).
(297) Abend., Rudolf, “Safe Control for Chlorination of Waste ater Con-
taining Cyanides”, German 1,301,280 (August 14, 1969); C.A. 71,
Pl05023d (1969).
(298) Nakamura, Takakatsu, et al., “Purification of Cyanide Waste Liquor”,
British 1,150,096 (April 30, 1969); C.A. 71, 24613u (1969).
(299) Sven—Nilsson, I ., “Elimination of Hexavalent Chromium Coming From
Electroplating Baths”, Swedish 218,495 (January 23, 1968); C.A.
71, 18299e (1969).
(300) Goetzmann, Karl, “Detoxification of Wastes Containing Cyanides”,
German 1,290,495 (March 6, 1969); C.A. 71, 15888k (1969).
(301) Zievers, James F., et al., “Metal Finishing Waste Treatment”,
British 1,143,473 (February 19, 1969); C.A. 70, P 80722v (1969).
(302) Schuster, Hans and Bartsch, Harry, “Decontamination and Neutrali-
zation of Dilute and Concentrated Waste Water”, German 1,280,164
(October 10, 1968); C.A. 70, 22760v (1969).
A-2 5
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(303) Goetzelmann, Willi, “Selective Removal of heavy Metal Complexes
From Industrial Waste Water by Ion Exchange tt , German 1,270,504
(June 12, 1968); C.A. 69, 80027b (1968).
(304) Kato, Hajime, “Purification of Spent Solution Containing Chromic
Acid”, Japan 68,08,922 (April 11, 1968); C.A. 69, P60387r (1968).
(305) “Lowering the Toxicity of Waste Waters Containing Cyanide”, French
1,494,619 (September 8, 1967); C.A. 69, P29992r (1968).
(306) Schuize, Guenter, “Treatment of Cyanides and Chroinates in Waste
Water”, German (East) 58,070 (September 20, 1967); C.A. 69,
P21782w (1968).
(307) Abend, Rudolf, “Detoxification and Neutralization of Waste Water
of the Metal Industry”, German 1,264,353 (March 21, 1968); C.A.
68, P1l7056t (1968).
(308) Rumi, Viadimer, et al, “Apparatus for Electrolytic Chlorination of
Waste Cyanide Waters”, Czech. 124,107 (August 15, 1967); C.A. 68,
Pl17053x (1968).
(309) Abend, Rudolf, “Detoxication of Sewage Containing Cyanide and Nit-
rite”, German 1,257,693 (December 28, 1967); C.A. 68, P89753x
(1968).
(310) Miroshnichenko, V. F., “Purification of Cyanide—Containing Dis-
charge Waters”, USSR 194,012 (March 13, 1967); C.A. 68, 89749a
(1968).
(311) Schwabe, Kurt and Berndt, Tilo, “Method for Ampermetric Measure-
ment of Cyanide Content in Waste Waters”, German (East) 56,655
(June 20, 1967); C.A. 67, P111265t (1967).
(312) “Decontamination of Aqueous Cyanide Waste Solutions”, French
1,471,715 (March 3, 1967); C.A. 67, P93818u (1967).
(313) Borchert, Otto, “Process for Purifying and Demetallizing of
Cyanide—Containing Electrolytes”, German (East) 55,619 (April 20,
1967); C.A. 67, P93815r (1967).
(314) “Treatment of Chromate Waters”, French 1,462,447 (December 16,
1966); C.A. 67, P67439b (1967).
(315) Nightingale, Joseph, “Treatment of Electroplating Wastes”, British
1,066,213 (April 26, 1967); C.A. 67, P36250d (1967).
(316) Pollard, Robert E., “Apparatus for Mixing and Metering Fluids”,
Canadian 751,612 (January 31, 1967); C.A. 67, P23404g (1967).
(317) Schuize, Guenter, “Gas Purifier for Galvanic Waste Water”, German
(East) 57,057 (July 20, 1967).
A-26
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(318) Siemens and Raiske, A. G., “Automatic Measurement of Cyanide Con-
tent and of pH of Industrial Wastes”, Neth. Appi. 6,510,886 (April
12, 1966); German Appi. (October 8, 1964); C.A. 65, P6910d (1966).
(319) Siemens and Haiske, A. G., “Automatic Measurement of the Cyanide
Content in Industrial Waste Water”, Neth. Appi. 6,511,035 (March
4, 1966); German Appi. (September 3, 1964), 13 pp; C.A. 65, P1954c
(1966). —
(320) Dart, Michael C., “Electrolytic Treatment of Cyanide Wastes”,
British 1,025,282 (April 6, 1966); C.A. 65, P480c (1966).
(321) Buczylo, Edward, “Continuous Neutralization of a1vanic Waste
Waters”, Przedsiebiorstovo Projektowania i Budowy Zakiadow
Przemyslu Metalowego I Elektrotechnicznego, Polish 49,679 (Decem-
ber 29, 1961); C.A. 64, Pl7246f (1966).
(322) Coleman, Arthur K., (assigned to British Aircraft Corp., Ltd.),
“Oxidation of Cyanide to Oxamide in Metal Finishing Waste Solutions
Containing Hexavalent Chromium and Cyanide”, British 1,021,876
(March 9, 1966) 6 pp; C.A. 64, 15566b (1966).
(323) Bonnivard, G., “Recovery of Chromium From Alkaline Solutions”,
assigned to Institut de Recherches de la Siderugie Francaise
(IRSID) and Bureau de Recherches Geologiques et Minieres (BRGM),
French 1,461,411 (December 9, 1966).
(324) Nohse, Walter, Dohmann, Harold, and Weidner, Siegfried, “Removal
of Cyanides From Electrolytes”, German 1,193,920 (June 3. 1965),
1 p; C.A. 63, P7908h (1965).
(325) Kurz, Hans, “Decomposition of Toxic Cyano Compounds”, German
1,188,568 (March 11, 1965); C.A. 62, P12795 (1965).
(326) Bures, Jiri, “Removal of Cyanide From Waste”, Czech. 111,840
(August 15, 1964); C.A. 62, P6252d (1965).
(327) Sutnieks, R., “Treatment of Cyanide Wastes”, Swedish 186,438
(November 26, 1963); C.A. 62, 5058g (1965).
(328) Kampschulte, W. and Cie., “Removal of Toxic Cyanides From Solu—
tions”, Belgian 613,851 (February 28, 1962); Ger. Appi. (February
13, 1961); C.A. 57, P10939a (1962).
(329) “Apparatus for the Treatment of Aqueous Cyanide Solutions”, British
895,741 (May 9, 1962); C.A. 57, P12272e (1962).
(330) “Apparatus for Continuously Detoxifying Waste Liquors Containing
Soluble Cyanide or Free 1-lydrocyanic Acid”, British 895,742 (May 9,
1962); C.A. 57, P8403 (1962).
A-27
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(331) “Continuously Detoxicating Waste Liquors”, British 895,740 (May 9,
1962); C.A. 57, P7908h (1962).
(332) Shcherbakov, A. A., Bogachev, G. N., ntoshkina, N. L., Makarova,
L. F. , Pinaevskaya, E. N., and Panachev, B. I., “Purification of
Waste Waters”, USSR 141,411 (October 6, 1961); C.A. 56, 9898h
(1962).
(333) Horak, Vaclav, etal., “Decreasing the Cyanide Content of Wastes
From Tempering and Other Processes”, Czech. 96,653 (September 15,
1960); C.A. 55, P25115f (1961).
(334) Bengtsson, Anders Eric, “Recovery of Chromium Compounds from Waste
Liquors”, German 1,067,795 (October 29, 1959); C.A. 55, P15856b
(1961).
(335) “Potentiometrically Measuring and Reducing Chromate Ions in Aqueous
Solution”, British 853,326 (November 2, 1960); C.A. 55, P12159d
(1961).
(336) Raynaud, Marcel and Bizzini, Bernard, “Removal of Cyanides From
Industrial Waste Water”, French 1,193,911 (November 5, 1959); C.A.
55, P1978d (1961).
(337) Ainsworth, F. G., et al., “Automat. Treatment of Plating Plant
Effluent”, British 824,081 (November 25, 1959); C.A. 54, P9l76g
(1960).
(338) Pfohe, Hugo and Hausner, Hans, “Electrolytic Purification of Water
and Recovery of Metals From Waste Waters”, German 905,360 (March
16, 1954); C.A. 52, P88O4h (1958).
(339) Wallace & Tiernan, Incorporated, “Treatment of Cyanide Solutions”,
British 759,109.
(340) Gullemann, A., “Treatment of Waste Waters Containing Cyanide Com—
Pounds”, German (East) 7,432 (1957).
A-28
* U. S. GOVERNMENT PRINTING OFFICE 1970 0 - 400-817
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