Removing Metal In Waste Water

The metals removal process is often divided into four steps: (1) pretreatment; (2) precipitation;
(3) flocculation; and (4) settling. Each of these steps will be discussed in this subsection, with
reference to the methods and chemicals employed by survey respondents.
6.2.4.1 Pretreatment
Prior to metals precipitation, many shops use "pretreatment" processes to affect substances that
require special treatment or interfere with subsequent treatments.Chemicals used during metals
precipitation include ferrous sulfate, sodium hydrosulfite, aluminum sulfate, soda ash and sodium
dithiocarbamate (DTC). Ferrous sulfate is sometimes added to function as a reducing
agent, but more often to provide co-precipitation for the removal of metals from chelated
wastewaters.
6.2.4.2 Precipitation
Precipitation is the process by which dissolved metals are made insoluble, usually as
metal hydroxides. With metal finishing wastewaters this is brought about by the addition of
alkali treatment reagents. Two alkalis are most commonly used for hydroxide precipitation:
sodium hydroxide (i.e., NaOH, or, as it is commonly referred to, caustic soda or simply caustic) and
lime (i.e., calcium hydroxide or hydrated lime, Ca(OH)
The metals precipitation process begins with pH adjustment, as previously shown in Exhibit 6-1.
The pH is usually adjusted to between 8.5 and 10.0, with 9.2 being the most frequent target. The
optimal pH for precipitating metals from a wastestream will depend mostly on the species of
regulated metals present. Each metal hydroxide has a characteristic solubility that is dependent on
pH. Exhibit 6-10 shows the solubility curves for the hydroxides of commonly regulated metals
(metal sulfides have different curves with minimum solubilities at much lower concentrations than
hydroxides, ref. 348). The lowest point of each curve corresponds to the pH at which that metal
species will be removed to its minimum solubility point. For example, copper will be removed to its
minimum concentration if the pH of the precipitation step is held at 9.0. Since the low points of the
curves occur at different pHs, it is necessary to make a compromise when selecting a target pH
(pH control set-point). Often, the pH control set-point selection process is based on the need to
reach a low concentration for a particular metal species (e.g., cadmium) that is regulated to a
lower concentration than other species.
Exhibit 6-11 shows the process schematic of a single-stage neutralizer with provisions for adding
both acid and base. Since most combined waste streams are acidic when entering the metals
removal step, many facilities do not provide for the addition of acid. However, it is useful in
instances when caustic has been inadvertently added in excess and therefore is present in most
system designs. With a single-stage system, proportional control for reagent addition is required to
maintain a reasonably constant effluent pH. The elevation of the reagent storage and gravity
feeding through a proportioning valve is one mode of control. Use of variable speed pumps will
achieve the same level of control. If incoming wastes are subjected to wide swings in reagent
demand, a two-stage neutralization system should be used. The first stage would control at a pH
of approximately 6 to 7 (ref. 39).
Required residence volume in the neutralizer depends on the reagent used. Assuming good mixing,
a minimum of 15 minutes residence volume is required for sodium hydroxide; with lime as the
alkali, a minimum of 30 minutes is required (ref. 39).
The level of residual dissolved metals after pH adjustment depends on the pH control set-point,
the mixture of metals in the wastewater, and whether any compounds are present that interfere
with metal hydroxide precipitation.
6.2.4.3 Flocculation

Nearly every metals removal system uses chemical aids to foster particle growth before
the wastewater enters the clarifier. By adding coagulating/flocculating agents in slowmix reactors, the solids in a wastewater can be agglomerated into sturdy, fast-settling
particles easily separated in the clarifier. Coagulants/flocculants in broad commercial use
include inorganic chemicals such as alum and ferrous sulfate (previously discussed as
pretreatments and co-precipitants) and a highly diverse range of organic polyelectrolytes with
varying characteristics suitable for different wastewaters. Organic polyelectrolytes are superior to
inorganic compounds because both the charge density and valence have been synthetically
introduced to the large polymer molecule. The length of the polymer also allows the particles to
"knit" together. Normally the appropriate polyelectrolyte is selected by testing a range of different
polymers and observing settling behavior after mixing.
6.2.4.4 Clarification
Removal of solids by gravity settling (clarification) is the most common method of separating
insoluble particles from a waste stream before discharge. Clarification is a relatively simple process
that relies on a density difference between the particles and water and the presence of gravity.
However, it is often the unit operation of the waste treatment process most subject to upsets. With
effluent limits placing strict control on the level of suspended solids in the wastewater, many
modifications to the original circular clarifier have resulted from research and development
activities. The two most successful approaches include the sludge blanket clarifier and the plate
settler. In the sludge blanket unit, the clarifer inlet first passes through a sludge blanket of
agglomerated particles. The mixing tends to promote particle growth and reduce the concentration
of slow-settling particle fines. The plate settler (Exhibit 6-12) relies on a series of inclined plates
between which the wastewater flows in an upward direction. In essence, the particles must only
settle a few inches before impinging on the plate surface. The particles then slide down the plate
surface to the base of the separator. In a chamber of equal size, plate settlers can provide
considerably greater effective settling volume than a conventional clarifier.
Performance of clarifiers varies significantly depending on the type of waste, the design of
upstream components, and the design of the clarifier itself. According to EPA, a "properly operating
system" has a total suspended solids (TSS) concentration of 50 mg/l or less and the mean
concentration of such systems is 16.8 mg/l TSS (ref. 386). A well-operated clarifier will have, at
best, 5 to 10 mg/l of suspended solids in the overflow (ref. 477). Frequently, turbidity in the
overflow contributes to the metals content of the discharge and makes strict pollutant guidelines
difficult to meet. Consequently, many advanced waste treatment systems employ a polishing filter
that uses a sand bed or mixed media filter to remove suspended solids not effectively removed by
clarification (ref. 39). Another option is the use of membrane filtration, which either supplements
or replaces the clarification step (see Section 6.4.4).
Granular media polishing filters are used for the removal of suspended solids in the 5 to 50 mg/l
range where an effluent of less than 1 Jackson Turbidity Unit2 (JTU) is desired (ref. 362). These
units typically contain graded sand or multimedia such as garnet, ground anthracite and silica
sand. The principal solids removal mechanism of these units is straining. When a single medium
such as sand is employed, it will classify in the filtration tank according to size, with the smallest
grains at the top. When water flows downward through the sand, which was common with older
designs, the solids would form a mat on the surface and filtration only occurred in the top few
inches. The sand bed was then cleaned by an upward washing of the bed with water or with water
and air (ref. 362). A patented alternative design permits upward feed flow and a continuous
backwash of the sand bed as described in Exhibit 6-13.
Multimedia filters employ two or more filter media with different grain size and densities. The
media are selected such that the smaller particles are the most dense (e.g., garnet with a specific
gravity of 4.5 and particle size of 0.2 to 0.4 mm), the medium-sized particles have an average
density (e.g., sand grains with a specific gravity of 2.65 and a grain size of 0.5 mm) and the
largest particles are the least dense (e.g., anthracite grains with a specific gravity of 1.6 and a
grain size of 1.0 mm). When mixed and permitted to settle, the multimedia bed will grade itself
according to the density of the material. Therefore, the smallest particles will locate at the bottom
and the largest particles at the top. When the feed stream flows from top to bottom, the courser

suspended solids will be removed in the upper layers of the filter and the smaller suspended solids
near the bottom. Backwashing is performed in the opposite direction.
The results of the Users Survey indicate that 58 respondents (or 19.3%) employ polishing filters.
Some respondents to the Users Survey use alternative methods of removing metal hydroxides
rather than using standard clarification. PS 036 and PS 168 pump the entire volume of treated
wastewater containing precipitated metals through a filter press (use of the filter press is normally
reserved for settled sludge). Both of these shops have wastewater flow rates below 3,000 gpd,
which is the reason they are able to use this method of separation. As indicated by Roy (ref. 38),
when direct filtration is used, the gelatinous character and the shear bulk of solids results in
premature blinding or blockage of the filter, causing minimal hydraulic throughput. One respondent
to the survey uses dissolved air flotation (DAF) rather than settling (PS 240). A DAF unit generates
fine air bubbles that attach to the hydroxide particles and cause them to rise to the surface of a
tank, where they are removed by skimming. It is a treatment technology commonly used by
industries with oily wastestreams (e.g., petroleum refining and industrial laundries). Several shops
use membrane filtration to separate precipitated metals. This method of treatment is a viable
alternative to conventional clarification for plating shops, but currently is more common to the
printed circuit board industry. Microfiltration is discussed in Section 6.5.3.