CONVENTIONAL METHOD OF WASTEWATER TREATMENT

To this day, the majority of metal finishers are meeting, or attempting to meet,
effluent limitations by treating wastewater by conventional physical-chemical
treatment. The process basically involves the use of chemicals to react with soluble
pollutants to produce insoluble byproduct precipitants, which are removed
by physical separation via clarification and/or filtration.
Conventional treatment systems often include hexavalent chromium reduction,
cyanide oxidation, and chemical precipitation in a neutralization tank.
Typically, these steps are followed by clarification. As clarification is not a 100%
solids
separation device, additional polishing is often required using one of many filtration
devices. Increasingly, it is becoming common to eliminate the clarification stage
totally, and its polymer flocculation step, in favor of direct microfiltration. The
sludge from either separation stage is stored/thickened in a sludge tank, then
dewatered via a filter press.
Chromium Reduction
Chromium in metal finishing is normally used in the hexavalent ion form (Cr6+) in
plating or chromating. As it soluble at all pH values, the chemical reduction step
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to its trivalent (Cr3+) form is necessary to ensure removal by precipitation.
Commonly, trivalent chromium replacement processes are being employed for safety
considerations and the elimination of the reduction wastewater step. Exercise care
in selecting trichromium replacements that may contain ammonia and other
chemicals, which can cause complexing of other metals in waste treatment.
The reduction of hexavalent chromium is achieved by reaction with sulfur
dioxide gas (SO2), or more commonly sodium metabisulfite (MBS). The speed of the
reaction is pH dependent. At pH 2.5-3, the reaction is virtually instantaneous.
Above pH 4, the reaction slows to a point where it becomes impractical for use in
continuous flow systems.
The use of pH and oxidation-reduction potential (ORP) controllers is common.
Without automatic pH controllers, care must be exercised to ensure complete
reaction,
particularly in batch reactors where the pH is manually adjusted to pH 2.5
prior to MBS addition. MBS addition raises the pH of the solution, often to ranges
where reduction times are lengthy. As batch processes are usually controlled visually
by color change, a significant MBS overfeed often results.
Although MBS and SO2 are the most common chemical reducers used in hexavalent
chromium reduction, any strong reducing agent will suffice. Ferrous
iron in many forms, including ferrous sulfate, ferrous chloride, ferrous hydrosulfide,
or electrochemical ferrous production from iron electrodes, is used.
The primary benefit of ferrous reduction is that Fe2+ will reduce hexavalent
chromium at near neutral pH values. For low concentration applications (moderate
chromating use processes), ferrous addition can eliminate the complete
chromium reduction stage. The ferric ion formed in the process becomes an
excellent
coagulant in the precipitation stage.
The only drawback to ferrous reduction is the additional sludge generated by
its use, as three parts Fe2+ is required to reduce one part Cr6+.
Chromium Reduction Process Precautions
1. SO2 and MBS form noxious acidic vapors. Avoid excess formation and
inhalation of the vapors.
2. pH control is very important. Allowing pH to drift below 2 increases SO2
gassing vapors. Allowing pH drift upward to 4 increases reaction times to
impractical levels.
3. Underfeed of SO2/MBS causes chrome carryover. Overfeed of MBS/SO2
causes increased metal solubilities in neutralization, and reverses the particle
charge and, consequently, results in poor flocculation.

Cyanide Oxidation
Treatment of cyanide (CN) in metal finishing wastewaters is most commonly
performed
by oxidation in an alkaline chlorination process using sodium hypochlorite
(NaOCl) or chlorine gas (Cl2). Because of the toxic danger of Cl2 gas, NaOCl
processes are considerably more common.
The alkaline chlorination process either involves only first-stage CN oxidation,
whereby simple cyanides are converted to cyanates (OCN), or the addition of a
second-
stage reactor to convert cyanates to carbon dioxide (CO2) and nitrogen (N2).
First-stage CN oxidation is carried out at a pH of 10.5 or higher. The reaction
slows greatly at pH values below 10 and virtually ceases at pH values
below 9. The process only oxidizes simple cyanides, such as NaCN, KCN,
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Zn(CN)2, CdCN, CuCN, etc. Complexed cyanides, commonly found in metal
finishing wastewater as iron complexes, are not destroyed in alkaline
chlorination processes. In fact, complexed cyanides are not destroyed efficiently
by any common cyanide oxidation process, including ozone. The use
of high-pressure/high-temperature thermal processes will, however, destroy
complexes. Also, lengthy exposure to sunlight will convert complexed
cyanides to simple cyanides, to a small extent.
As federal and local regulations are generally written for total cyanide monitoring
and limiting, complex cyanides are often the species causing violations.
Complexed cyanides are most commonly formed by poor housekeeping, control,
and rinsing. Drag-out or drippage of CN from baths or bath rinses into acids
and chromates is very common. Steel electrode use in plating baths causes a
significant
amount of complexed cyanide input to the bath from constant decomposition.
Clean steel parts allowed to fall and accumulate in CN baths are another
major source of complexed CN formation.
Although complexed cyanide formation cannot be totally eliminated, reduced
formation through housekeeping and improved rinsing can reduce the concentration
to nonproblem levels.

Complexed cyanides are generated in both soluble and insoluble forms. The
insoluble form is removed via mass settling in the clarifier. Conversion of soluble
complexes to insoluble complexes can be achieved to some extent by the addition
of MBS to the neutralization tank. The efficiency is improved in the presence
of copper ion. Permanganate addition also has been reported to accomplish
improved precipitation of complexed cyanides.
The second-stage CN oxidation process is carried out at a pH of 8.0-8.5. An
amount of Cl2 comparable to that required in first-stage oxidation (3.5 lb Cl2:1
lb CN) is necessary to complete the conversion of OCN to CO2 and N2.
Most sewer use ordinances do not require cyanate oxidation or limit cyanate
in the discharge. Consequently, many treatment systems only employ first-stage
processes. A common problem associated with first-stage-only systems is the
propensity to gassing in the neutralization tank, with resultant clarifier floating
problems. This is caused by an uncontrollable cyanate breakdown, particularly
when excess residual Cl2 is present in the first-stage dischare.
Although reaction times for most simple cyanides and cyanates are 10-15
minutes, it is advisable to size reaction tanks at 1 hour and longer if affordable/
practical. Certain simple cyanides, including cadmium and copper,
only start breaking down after the sodium, potassium, and zinc cyanides are
destroyed, thus requiring longer contact periods. Furthermore, the longer the
reaction, the more efficient the gas venting becomes, reducing the incidence
of clarifier floating.
Because precise control of pH and Cl2 is important, pH and ORP controllers
are recommended in all continuous control reaction tanks.

Summary of Cyanide Process Precautions

1. First-stage oxidation must be controlled at pH 10.5 or higher. (The higher
the pH, the faster the reaction.)
2. Control the formation of complexed cyanides, as treatment processes do not
destroy them. Add MBS to the neutralization tank if soluble complexes cause
effluent violations.
3. Allow 1 hour or more reaction time to ensure completion of the reactions,
and for problem gas venting.
4. Underfeed of chemical allows CN pass through; overfeeds cause increased
gassing and reoxidation of trichrome.
Coagulation/Neutralization Process Considerations
Effluents from hexavalent chromium reduction and cyanide oxidation stages combine
with other alkaline and acid wastewater streams in a neutralization tank. The
express purpose of the neutralization tank is to create a suitable environment and
retention time for soluble pollutants to react and form insoluble precipitates for
eventual physical separation. The principal precipitation process employed in
conventional
wastewater treatment systems is that of hydroxide precipitation. Heavy
metals, the prime targets of neutralization-precipitation, have varying solubilities
depending on pH. In common mixed-metal wastewater streams, control of
the neutralization tank at pH 9.2-9.5 is generally suitable to lower metal solubilities,
as hydroxides, to concentration ranges where compliance is achievable.
In many cases, it is necessary to add chemical coagulants to the wastewater in
order to achieve minimum solubilities and superior flocculation/solids separation
in the clarifier. A proper coagulant will effectively tie up anionic surfactants,
wetters, and species such as phosphates, which interfere with polymer flocculation;
and also add bulk density for improved solids separation.

Where coagulants are required for good process performance, it is recommended

that two-stage neutralization reaction tanks be employed, as coagulants
perform better when reacted with the wastewater at pH values in the 5.5-6.5 range.
Common chemical coagulants include calcium chloride, ferrous salts, ferric
salts, and alum.
For improved coagulation, certain specialty coagulants are available from
chemical suppliers. These chemicals usually contain one of the above base salts,
which are sometimes blended with polymers, generally of a cationic nature.
Although these specialty products are expensive, with costs ranging from $400
to $1,000 per drum, their use is often necessary to achieve compliance.
Neutralization is generally achieved using caustic soda (NaOH) and sometimes
potassium hydroxide (KOH). Hydrated lime and magnesium hydroxide also
have wide utilization. Although these neutralization chemicals present certain
handling
and feeding problems associated with their solids content, lower metals solubilities
are achieved at maintenance of lower neutralization tank pH (8.0-8.5).
The introduction of strong chemical complexers used in production processes
commonly impedes the pollutant precipitation process. Common complexers/
chelators include ethylene diamine tetra acetic acid (EDTA), nitrilotriacetic
acid (NTA), quadrol, glucconates, glutamates, ammonia, and various amies.
Complexing agents are commonly used in electroless baths, electroplating bath
brighteners, alkaline cleaners, parts strippers, and numerous other applications.
Eliminating their use, where practicable, is the simplest means of mitigating their
adverse wastewater treatment effects. Where critical to the process, special means
and practices must be employed, which vary with the type and strength of the
complexer, as well as the metal(s) being complexed.
Often off-line pretreatment is necessary, as in the case of high volume electroless
bath use. In other cases, the use of specialty chemical precipitants, metered into
the complexed waste stream or into the neutralization tank, is suitable and
effective. Specialty chemical precipitants include dithiocarbamates, dithiocar-
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bonates, starch and cellulose xanthates, poly quaternary amines, and ozone
destruction/hydrosulfite reduction.

As complexing chemicals are primary reasons for noncompliance in conventional

systems, much care and time are necessary to solve the problems created
by them. Often significant trial testing in bench scale treatability tests and close
work with chemical suppliers are necessary to resolve complexing problems.
In some cases involving simple complexed wastewaters, conversion from
hydroxide precipitation to sulfide or carbonate precipitation in the neutralization
process will achieve necessary reductions in metal solubility. Most
metallic sulfides and metallic carbonates have lower solubilities than their
hydroxide counterparts.
Reaction times required for effective coagulation-neutralization-precipitation
vary among wastewater types and complexity. We recommend minimum
retention times of 30 minutes, 15 minutes in first-stage reactors. As metal
hydroxides tend to reduce in volume the longer they are mixed, the longest
practical reaction times are most desirable.
Common problems associated with neutralization/reaction tanks, which
impede clarifier separation of solids, include soluble complexes caused by
chelating agents; charge reversal caused by anionic surfactants, phosphates, and
MBS overfeed; solids buoyancy or flotation problems caused by excess oil and
grease or gas formation including chemical gassing caused by peroxides,
acetates, and carbonates or physical-induced gassing caused by suction leaks on
transfer pumps, or significant mixer vortex action; overfeed of dump solutions,
particularly alkaline cleaners; and high total dissolved solids (TDS), 7,000
ppm and higher, from overly zealous water conservation practices, or high
percentage
reuse of treated water.
FLOCCULATION/CLARIFICATION PROCESSES
The precipitates formed by the proper operation of the coagulation-neutralization
stage are commonly removed in conventional wastewater treatment systems
by clarification or sedimentation. This process involves solids removal by the efficient
settling of solids. Buoyancy caused by oils or floating caused by the entrainment
of gas bubbles will prevent efficient settling. Generally, floating problems
are controllable in the typical metal finishing wastewater installation. For certain
firms, which employ electrolytic/electrochemical pretreatment or ozone generation/
air diffusing treatment techniques, dissolved air flotation (DAF) is the preferred
unit for solids separation

Solids separation is improved in clarifiers, or DAF units, by polymer (polyelectrolyte)

flocculation. As the average charge of metal hydroxides is positive, a
negatively charged (anionic) polymer is used in the flocculation process. It is
imperative that the wastewater charge remain positive at all times. Coagulants
and/or cationic polymers may be necessary in certain wastewater types where
charge reversal is common, as in phosphating operations. Nominal flocculation
time of 1 minute is recommended for floc tank size. Variable speed mixers are
recommended
to allow some measure of control of floc size.
The size of the clarifier generally varies with the type and style. Basic, open/empty
sedimentation tanks commonly used in low-flow installations should be
sized for a maximum surface loading rate of 500 gal/day/ft2 of tank surface.
Most commonly employed clarifiers are of the lamella type or inclined plate
variety. These units are sized based on volumetric flow rate per square foot of plate
pack area projected on the plate incline, or cosine of the degree of plate angle;
typically
60O. Recommended loading rates are 0.2-0.4 gal/min/ft2 of projected plate
area, and a total suspended solids (TSS) concentration of 500 ppm or less.
Units are manufactured in basic hydraulic flow sizes, i.e., 30 gal/min or 75
gal/min, etc. In those cases of high TSS loads (500 ppm or higher), it is not advisable
to size a unit based solely on flow. In these high solids load applications, clarifier
selection should be based on 1 lb TSS per hour for each 20 ft2 of projected
clarifier settling area.
Manufacturers will supply design and operational information for their specific
unit. As a general rule, it is important to evacuate sludge as it accumulates
to prevent its buildup into the plate pack area. This creates blockages and
increases the upflow velocity in the open areas and carries TSS with the high flow.
Monthly draining is advisable to minimize ratholing and solids concretion.

EFFLUENT POLISHING
At times, clean water that overflows from a clarifier will require further removal
of suspended solids or polishing to meet more stringent discharge requirements.
This may be for water reuse or simply as insurance in case of a system malfunction.
Sand filters, devices consisting of one or more layers of various sizes and
types of granular media, are typically used. Gravel, sand, anthracite, garnet, and
activated carbon are common media.
The size and number of filters is, as with a clarifier, dependent on the volume
of wastewater to be filtered and the surface area of the filter media. Gravity-operated
sand filters usually are loaded at 0.25-0.5 gpm/ft2, whereas pressure sand filters
can operate in the 5.0-10.0 gpm/ft2 range, depending on the suspended
solids of the effluent.
Most sand filters need to be periodically cleaned or “backflushed” to remove
the solids that have built up. Clean water, process water, or dilute acid solutions
may be used for this back flushing. Backflush waters are generally returned to the
collection or equalization tank and returned to the treatment system. Pressure
sand filters require less backwash water than larger gravity types.
Operationally, care must be taken to ensure that pumps feeding or backflushing
the filters are operating at design capacity to ensure proper loading and
adequate cleaning of the media. Sand filter media are rarely replaced, except when
a severe system upset causes solids to block the water distribution headers.
SLUDGE THICKENING AND DEWATERING
Sludge (settled solids) produced from treatment of metal finishing wastes generally
contains between 1.0 and 2.0% total solids. Disposal of such a watery
sludge is very expensive. Most medium and large generators of wastewater
choose to thicken and dewater sludge, thus reducing the volume of waste to be
disposed.
A sludge thickener, although not always necessary prior to dewatering, serves
several
worthwhile functions. First, it creates storage volume for the sludge in the event
that the dewatering equipment is not in operation. Second, it allows for a consistent
sludge blanket level in the clarifier. Sludge can be intermittently removed from
the clarifier by means of a timer on the sludge pump. This reduces the possibility
of solids drafting over the clarifier weir(s) because of a high sludge blanket. Finally,
sludge stored in a thickener may increase in solids content to as much 3-4%.

Increased solids content does two things: it decreases cycle time required by the
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dewatering equipment (filter press, centrifuge, belt press) and, as a rule of
thumb, regardless of the type of dewatering equipment, the thicker the feed
sludge, the drier the sludge cake. The objective is to reduce the volume to be
disposed
of by removing as much water as possible.
The filter press is most often used in the dewatering of metal finishing
sludges because generally it is made to handle smaller volumes of sludge, is
simple to operate, and produces a dry, easily disposable filter cake. Sludge from
the thickener, or directly from the bottom of the clarifier, is usually pumped via
an air diaphragm pump to the filter press. The polypropylene filter media
retains the solids while the liquid portion or filtrate flows through the media and
discharges. Filtrate usually returns to the collection/equalization tank for retreatment.
After a certain length of time (2-4 hours), the chambers of the press are completely
full and a filter cake of 25-35% solids has formed. The hydraulic pressure
that had been holding the plates together is now released and the filter cake is
discharged.
Filter press operation requires little operator attention except at the beginning
and end of a press cycle. Presses without an automatic plate shifter often require
two people to separate the plates to discharge the cake, one on either side of the
press. Cake that has had enough time to sufficiently dewater will literally fall out
of the press upon opening.
The highest operational cost involved with a filter press is the replacement of
the filter cloths. Cloth life is directly dependent on the number of press cycles per
year. The metal hydroxide sludges produced from treatment of metal finishing
wastes are generally of moderate pH and nonabrasive. Cloth life of 1-2 years is
common. Replacement of cloths is labor intensive, especially the caulked, gasketed
variety, but all the cloths, even in a large press (10 ft3), can be changed in 3-4 hours.
Because plates and cloths are usually of polypropylene construction, they can be
routinely cleaned by immersion in an acid without damage.