Chemical Technology 87

It must be remembered, however, that these materials are extremely corrosive and must
be handled with care.
Acid hydrolysis usually proceeds more rapidly in solution. Thus, stirring in an open
container with excess acid is feasible though potentially dangerous. Another method is to
mix the waste with sand or other adsorbent in a pit or trench and then add the acid.
Disposal of wastes by this method cannot be performed in an area where groundwater
contamination is possible. Treated waste streams will generally require pH adjustment
before they can be discharged.
One final word of caution: Do not treat cyanides or phosphides with strong acids as
hydrogen cyanide gas and phosphine gas, both highly toxic, will be given off as reaction
products.
Alkaline Hydrolysis: Alkaline hydrolysis mostly utilizes sodium hydroxide, but alkali
carbonates (limestone), alkaline hypochlorite, calcium compounds lime, slaked lime), and
magnesium and aluminum compounds are also used.
As with acid hydrolysis, alkaline hydrolysis can be performed in batch processes in
open tanks with stirring, although this may be dangerous. Treatment in a trench filled with
adsorbent material is recommended for treatment of small quantities of wastes, especially
pesticide wastes. This should be done only in areas where groundwater contamination will
not occur.
If a large volume of waste is to be discharged after treatment, it will probably be
necessary to adjust the pH.

2.5 ION EXCHANGE

Ion exchange is a treatment technology applicable to (a) metals in wastewaters where
the metals are present as soluble ionic species (e.g., Cr 3 and Cr04 - z); (b) nonmetallic
anions such as halides, sulfates, nitrates, and cyanides; and (c) water-soluble, ionic
organic compounds including (1) acids such as carboxylics, sulfonics, and some phenols,
at a pH sufficiently alkaline to yield ionic species, (2) amines, when the solution acidity
is sufficiently acid to form the corresponding acid salt, and (3) quaternary amines and
alkysulfates.
Ion exchange, when used in hazardous waste treatment, is a reversible process in
which hazardous cations and/or anions are removed from an aqueous solution and are
replaced by nonhazardous cations and/or anions such as sodium, hydrogen, chloride, or
hydroxyl ions. Ion exchange resins are cationic if they exchange positive ions (cations)
and anionic if they exchange negative ions (anions). When the waste stream to be treated
is brought into contact with a bed of resin beads (usually in a packed column), an
exchange of hazardous ions for nonhazardous ions occurs on the surface of the resin
beads. Initially, a nonhazardous ion is loosely bound to the surface of the resin. When
a hazardous ion is near the resin, it is preferentially adsorbed to the surface of the resin
(based on the differences in ionic potential), releasing the nonhazardous ion.
Cation exchange resins contain mobile positive ions, such as hydrogen (H') or sodium
(Na'), which are attached to immobile functional acid groups, such as sulfonic (S03-) and
carboxylic (COO-) groups. Anion exchange resins have immobile basic ions, such as
amine (NHz-), to which the mobile anions, such as hydroxyl (OW) or chloride Cr), are
attached.
88 Unit Operations in Environmental Engineering

Ion exchange material is contacted with the solution containing the ion to be removed
until the active sites in the exchange material are partially or completely used up
("exhausted") by that ion.
After exhaustion, the resin is then contacted with a relatively low volume of a very
concentrated solution of the exchange ion to convert ("regenerate") it back to its original
form.
For instance, in the case of a sodium-based resin, a strong solution of sodium
chloride is typically the regenerant solution. The regenerant solution forces the previously
removed ions back into solution. This relatively low volume solution, now highly
concentrated with the contaminant ions, must then be treated prior to disposal for recovery
or removal of the hazardous cation or anion contaminants. There will continue to be a
high concentration of the regenerant ion (sodium in the above example) in the used
regenerant solution because excess regenerant ion is necessary to force the contaminant
ions back into solution. The direction and extent of the completion of the exchange
reaction depend upon the equilibrium that is established between the ions in the solution
(M+X-) and those in the exchange material (R-W).

2.5.1 Ion Exchange Process

Most ion exchange operations are conducted in packed columns. The aqueous solution
to be treated is continuously fed to either the top or the bottom of the column. A typical
fixed-bed ion exchange column consists of a vertical cylindrical pressure vessel with
corrosion-resistant linings. If appropriate, a filter is installed at the inlet of the column to
remove suspended particles because they may plug the exchange resin. Spargers are
provided at the top and bottom of the column to distribute waste flow. Frequently, a
separate distributor is used for the regenerant solution to ensure an even flow. The resin
bed, usually consisting of several feet of ion exchange resin beads, is supported by a
screen near the bottom distributor or by a support bed of inert granular material.
Externally, the unit has a valve manifold to permit downflow operation, upflow
backwashing (to remove any suspended material), injection of the regenerant solution, and
rinsing of any excess regenerant.
A typical process for a basic two-step cation/anion ion exchange system includes a
series treatment with separate cation and anion exchange systems. Some systems contain
both anion and cation exchange resins in the same vessel. The pressure vessels used for
ion exchange generally range in size from 2 to 6 feet in diameter for prepackaged modular
systems, which typically handle 25 to 300 gpm flow rates, to a maximum custom size of
12 feet in diameter, which can handle flow rates up to 1,150 gpm. The height of these
vessels varies between 6 and 10 feet to provide adequate resin storage, distribution nozzle
layout, and freeboard capacity for bed expansion during backwashing. The nominal
surface loading area of the ion exchange vessels ranges from 8 to 10 gpm/ft 2.
Ion exchange is used to remove a broad range of ionic species from water including:
1. All metallic elements when present as soluble species, either anionic or
cationic.
2. Inorganic anions such as halides, sulfates, nitrates, cyanides, etc.
3. Organic acids such as carboxylics, sulfonics, and some phenols, at a pH
sufficiently alkaline to give the ions.
 Chemical Technology 89

4. Organic amines when the solution acidity is sufficiently acid to form the
corresponding acid salt.
Sorptive resins can remove a wide range of polar and non-polar organics.
A practical upper concentration limit for ion exchange is about 2,500 to 4,000 mg/R..
A higher concentration results in rapid exhaustion of the resin and inordinately high
regeneration costs. Suspended solids in the feed stream should be less than 50 mg/R. to
prevent plugging the resins, and waste streams must be free of oxidants.
This technology is used to treat metal wastes including cations (e.g., Ni, Cd, Hg) and
anions (e.g., Cr04 , Se04 , HAs04). Limitations are selectivity/competition, pH and
suspended solids. Highly concentrated waste streams (greater than about 25,000 mg/R.
contaminants) can usually be separated more cost effectively by other means. High solid
concentrations (greater than about 50 mg/R.) should be avoided to prevent resin binding.
Ion exchange is used to extract specific metals from solution. To date, some 30
synthetic "metal loving" compositions of resins that attract specific metals have been
developed. The method of attraction employed by the synthetic compositions is similar
to that of living cells. Natural cells have a built-in survival mechanism that is highly
selective for the capture and transport of certain metals necessary for cellular nutrition,
specifically iron, cobalt, zinc, copper, sodium, nickel, potassium, magnesium, and
manganese. The synthetic compounds are patterned after the high efficiency and natural
metal extraction capability of living cells.
Specific ion exchange and sorptive resins systems must be designed on a case-by-
case basis. It is useful to note that although there are three major operating models (fixed
bed cocurrent, fixed bed countercurrent, and continuous countercurrent), fixed bed
countercurrent systems are most widely used. The continuous countercurrent system is
suitable for high flows. Complete removal of cations and anions ("demineralization") can
be accomplished by using the hydrogen form of a cation exchange resin and the hydroxide
form of an anion exchange resin. For removal of organics as well as inorganics, a
combination adsorptive/demineralization system, can be used. In this system, lead beds
would carry sorptive resins which would act as organic scavengers, and the end beds
would contain anion and cation exchange resins. By carrying different types of adsorptive
resins (e.g., polar and non-polar), a broad spectrum of organics could be removed.
Capacities of resins vary greatly with the manufacturer of the resin. The amount of
resin needed must be determined by chemical tests using the wastewater to be treated. A
resin manufacturer should also be contacted to ensure the correct choice of resins. In order
to facilitate the proper selection, the following items of information should be available:
(1) name of hazardous material to be removed, (2) concentration (approximate) of
hazardous substance, (3) amount of wastewater to be treated, and (4) chemical analysis
of ions.
In a new development, Rohm and Haas has developed a family of six carbonaceous
adsorbents produced by the pyrolysis of fully activated IERs. After pyrolysis, the beads
acquire a carbon shell that combines the high adsorbent activity of activated carbon with
the physical strength and controlled pore size of the polymeric bead. A major application
for this carbonaceous resin is groundwater remediation, where both high reactivity and
selectivity are required to capture selected contaminants to the ppm and ppb concentration
range.
Applicability: The list of pollutants for which the ion exchange system has proved
90 Unit Operations in Environmental Engineering

effective includes aluminum, arsenic, cadmium, chromium (hexavalent and trivalent),

copper, cyanide, gold, iron, lead, manganese, nickel, palladium, platinum, selenium, silver,
tin, zinc, and more. Thus, it can be applied to a wide variety of industrial concerns.
Because of the heavy concentrations of metals in their wastewater, the metal finishing
industries utilize ion exchange in several ways. As an end-of-pipe treatment, ion
exchange is certainly feasible, but its greatest value is in recovery applications. It is
commonly used as an integrated treatment to recover rinse water and process chemicals.
Some electroplating facilities use ion exchange to concentrate and purify plating baths.
Also, many industrial concerns, including a number of nonferrous metals manufacturing
plants, use ion exchange to reduce salt concentrations in incoming water sources.
The ion exchange process may be used to remove cyanide in a ferrocyanide complex
from wastewater. The process generates a concentrated stream of the complex, which may
be treated using cyanide precipitation. Ion exchange is applicable to cyanide removal
when the cyanide is complexed with iron. Experimental data have shown that a specific
resin is very selective to the removal of iron cyanide complexes.
Ion exchange has been used in hydrometallurgical processing for recovery of valuable
metals. Uranium processing and extraction is an active field for both liquid and solid ion
exchange. It has also been used for removal and isolation of radioactive wastes. Ion
exchange can also be used to remove certain organic compounds, however, in general
there are other more competitive processes available for this use.
With the exception of occasional clogging or fouling of the resins, ion exchange has
proved to be a highly dependable technology. Only the normal maintenance of pumps,
valves, piping and other hardware used in the regeneration process is required. Few, of
any, solids accumulate within the ion exchangers, and those which do appear are removed
by the regeneration process. Proper prior treatment and planning can eliminate solid
build-up problems altogether. The brine resulting from regeneration of the ion exchange
resin must usually be treated to remove metals before discharge. This can generate solid
waste.
Advantages and Limitations: Ion exchange is a versatile technology applicable to
a great many situations. This flexibility, along with its compact nature and performance,
makes ion exchange a very effective method of wastewater treatment. However, the resins
in these systems can prove to be a limiting factor. The thermal limits of the anion resins,
generally in the vicinity of 6O o e, could prevent its use in certain situations. Similarly,
nitric acid, chromic acid, and hydrogen peroxide can all damage the resins, as will iron,
manganese, and copper when present with sufficient concentrations of dissolved oxygen.
Removal of a particular trace contaminant may be uneconomical because of the presence
of other ionic species that are preferentially removed. The regeneration of the resins
presents its own problems. The cost of the regenerative chemicals can be high. In
addition, the waste streams originating from the regeneration process are extremely high
in pollutant concentrations, although low in volume. These must be further processed for
proper disposal.
Xanthates: The use of xanthates for the removal of metals from waste streams
appears to be a new, promising technology for treating metal-bearing wastewaters.
Xantbates contain functional groups capable of forming insoluble complexes with metals,
and the sludge so formed can be separated by conventional means.
Xanthates can be generated by mixing starch or cellulose with carbon disulfide in a
 Chemical Technology 91

caustic medium. Three types of xanthates have been proven in bench pilot scale studies
to be effective in removing cadmium, chromium, copper, iron, lead, mercury, nickel,
silver and zinc from industrial wastewaters. These are:
1. Soluble starch xanthate with a cationic polymer,
2. Insoluble starch xanthate, and
3. Fibrous cellulose xanthate.
Insoluble starch xanthate is essentially an ion exchange medium used to remove
dissolved heavy metals from wastewater. The water may then either be reused (recovery
application) or discharged (end-of-pipe application). In a commercial electroplating
operation, starch xanthate is coated on a filter medium. Rinse water containing dragged
out heavy metals is circulated through the filters and then reused for rinsing. The starch-
heavy metal complex is disposed of an replaced periodically. Laboratory tests indicate that
recovery of metals from the complex is feasible, with regeneration of the starch xanthate.
Besides electroplating, starch xanthate is potentially applicable to any other industrial
plants where dilute metal wastewater streams are generated. Its present use is limited to
one electroplating plant.
Unlike hydroxide precipitation, this process is reported to be effective in removing
metals over a wide pH range of 3 to 11, with an optimum range between 7 and 9.
CelJulose xanthate is as effective as starch xanthate in removing trace metals, and is
superior to starch xanthate in terms of sludge settling characteristics, filterability, and
handling.
Xanthate may also be used as a complexing agent to prevent the formation of soluble
anions from insoluble amphoteric metal hydroxides.
Xanthate treatment offers advantages over hydroxide precipitation, including the
following:
1. A higher degree of metal removal;
2. Less sensitivity to pH fluctuation (metal xanthates do not exhibit
amphoteric solubilities;
3. Less sensitivity to the presence of complexing agents;
4. Improved sludge dewatering properties; and
5. The capability of the selective removal of metals.
DeVoe-Holbein Technology: DeVoe-Holbein technology uses coordinating
compounds covalently bonded to the surface of an inert carrier material to capture metal
ions. In waste treatment applications, the reactants are used in equipment similar to that
employed for ion exchange resins.
The technology was originally developed by DeVoe-Holbein as an adaptation of
biological mechanisms in which living cells selectively extract a variety of metal nutrients
from their environment. Cells can acquire target metals by means of specialized molecular
sites on their surfaces that recognize and bind only that species. Examples of such
selective reactants are the nonprotein iron-binding molecules, collectively known as
"siderophores."
One of the reported advantages of the DeVoe-Holbein system is that it is capable of
yielding a more highly concentrated regenerant than ion exchange. Several options for
downstream utilization of the concentrated metal regenerant are therefore possible. The
process appears most applicable to the selective removal of valuable metals, e.g., silver,
from waste streams.