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United States Industrial Environmental Research

Environmental Protection Laboratow


Agency Cincinnati OH 45268

_.

LEPA Summary Report

Control and Treatment


Technology for the
Metal Finishing Industry

Ion Exchange
i
Technology Transfer EPA 62518-81-007

Summary Report

Control and Treatment


Technology for the
Metal Finishing Industry

Ion Exchange

June 1981

This report was developed by the


Industrial Environmental Research Laboratory
Cincinnati OH 45268
Environmental research and development in the metal finishing industry is
the responsibility of the Nonferrous Metals and Minerals Branch, Industrial
Environmental Research Laboratory, Cincinnati OH. The U.S. Environmental
Protection Agency hired the Centec Corporation, Fort Lauderdale FL and
RestonVA, to prepare this report. RogerC. Wilmoth is the €PA Project Officer.

Requests for further information can be addressed to:


Nonferrous Metals and Minerals Branch
IERL-USEPA
Cincinnati OH 45268

EPA thanks the following companies and organizations for providing


information and technical review: American Electroplaters’ Society; Best
Technology, Inc.,Villa Park II; Dow Chemical Company, Midland MI: Institute
of Precision Mechanics, Warsaw, Poland; Raytheon Ocean Systems
Company, Portsmouth RI; and Rohm and Haas Co., Philadelphia PA.

Photographs were supplied by Best Technology, Inc., of Villa Park IL and


Eco-Tec Limited of Toronto ON.

This report has been reviewed by the Industrial Environmental Research


Laboratory, US. Environmental Protection Agency, Cincinnati OH, and
approved for publication. Approval does not signify that the contents
-necessarily reflect the views and policies of the US. EnvironmentalProtection
A ency, nor does mention of trade names or commercial products constitute
5
en orsement or recommendation for use. -

COVER PHOTOGRAPH: Reciprocating Flow Ion Exchanger used for chromic


acid recovery.

ii
Overview Ion exchange is a versatile Water Purification and Recycle
separation process with potential
for broad application in the metal fin- In the first area of application,
ishing industry, both for raw mixed rinse solutions are deionized
material recovery and reuse and to permit reuse of the treated
for water pollution control. Three water. The contaminants in the
major areas of application have been rinses are concentrated in the small
demonstrated: volume purge streams, and are
thereby made more economical to
Wastewater purification and treat.
recycle
End-of-pipe pollution control
Because ion exchange is efficient
Chemical recovery
in removing dissolved solids
from normally dilute spent rinse
Although the ion exchange process waters, it is well suited for use
has been commercially available
in water purification and recycle.
for many years, widespread interest
Most of the plating chemicals, acids,
in its use for metal finishing pol- and bases used in metal finishing
lution control has developed are ionized in water solutions
only recently. and can be removed by ion ex-
change. Several factors make the ion
The main impetus for the interest in exchange process effective for
ion exchange technology is the this application:
broad range of resins manufactured
today. With proper resin selection, Ion exchange can economically
ion exchange can provide an separate dilute concentrations of
effective and economical solution to ionic compounds from water
pollution control requirements. solutions.
As a further stimulus to the use of The process can consistently
the process, the metal-bearing provide high purity water over a
sludge generated by hydroxide treat- broad range of loading conditions.
ment systems is considered a The resins used for separation
hazardous material and must be are durable in severe chemical en-
disposed of in an environmentally vironments.
safe manner. The ion exchange 4pplication of the ion exchange
process can concentrate the heavy process in a wastewater purification
metals in a dilute wastewater into
and recycle system will signifi-
a concentrated metal solution that is
cantly reduce water consumption
more amenable to metal recovery
and the volume of wastewater
than is a sludge, and this ability discharged, thus reducing water use
should lead to more widespread use
and sewer fees and the size and
of the technology. cost of the pollution control system.
Also, for plants that discharge
This summary report is intended wastewater directly to waterways
to promote an understanding of the and that are regulated by mass-
use of ion exchange in the metal based pollutant discharge limits, the
finishing industry. The sec- reduction of discharge volume
tions that follow discuss ion ex- will allow for higher concentrations
change process theory in general of pollutants in the discharge
and evaluate each of the three majoi and facilitate compliance with these
areas of application in terms of limits.
performance, state of development,
- -~
~ fim&@_1989dollars), and operating
reliability.

1
Ion exchange acid purification unit used for sulfuric acid anodizing solutions

End-of-Pipe Pollution Control conventional hydroxide precipitation the discharge limits. Ion exchange
to lower the metal concentration can be used in such cases to
In the second application, toxic in the discharge; it has also been ap- polish the effluent from the conven-
heavy metals and metal cyanide plied as a means of directly treat- tional treatment and reduce the
complexes are removed selectively ing wastewaters to remove heavy metal concentration further. In this
from combined waste streams metal and metal cyanide pollutants. application, the process can provide
before discharge. The key to this ap- a relatively inexpensive means
plication is that the i o n exchange Most plating shops can remove of upgrading system performancefor
resins remove only the toxic sufficient metal to comply with compliance with the discharge
compounds and allow the nontoxic wastewater discharge regulations regulations.
dissolved ionic solids to remain using the conventional hydroxide
in solution. precipitation process. Where Ion exchange has been used to a
unusually strict limits are placed on limited extent to remove toxic pol-
The ion exchange process can be the effluent metal concentration, lutants selectively from an untreated
used in two different forms for however, or where the metals wastewater while allowing most of
end-of-pipe pollution control: it has are complexed with chemical con- the nontoxic ions to pass through.
been demonstrated as a means stituents that interfere with their Approaches employed to facil-
of polishing the effluent from precipitation as metal hydroxides,
conventional treatment may
not be reliable for compliance with

2
itate this application include dispose of the regenerant s o b bath and the purified water is
using: tions resulting from treatment would reused for rinsing. Determination of
not need to install chemical de- the separation process best suited
Weak acid cation resin in an
struct systems. In neithercase would for a particular chemical recovery
application of the wastewater-
it be necessary to invest in sophis- application usually requires evaluat-
softening type to remove
ticated pH control systems, floc- ing both general and site-specific
heavy metals and other divalent
culant feed systems. clarifiers, factors:
cations from a. wastewater
and other process equipment asso-
solution with a high concentra- General factors include rinse
ciated with conventional metal
tion of sodium ions water concentration, volume, and
precipitation systems. And, as a
Heavy-metal-selective weak acid corrosivity, among others.
further advantage, ion exchange
or chelating cation resin t o Site-specific factors include, for
units are compact and easy to
remove only the heavy metal example, availability of floor
automate compared with conven-
ions while allowing sodium, cal- space and utilities (steam,
tional precipitation systems.
cium, and magnesium ions t o chemical reagents, electricity, and
pass through so forth) and the degree of
A stratified bed of resin containing Chemical Recovery concentration needed to recycle
strong and weak acid cation the chemicals to the bath.
and strong base anion resins to In the chemical recoveryapplication,
remove heavy metal and metal cy- segregated plating rinse waters are As a rule. ion exchange systems are
anide complex ions from solu- treated to concentrate the plating suitable for chemical recovery
tion while allowing most of chemicals for recycle to the plating applications where the rinse
the wastewater ionic constituents bath. The purified rinse water water feed hasa relativelydilute con-
to pass through is also recycled. centration of plating chemicals
and a relatively low degree of
In each of these approaches, Ion exchange. evaporation, reverse concentration is required for recycle
wastewater pretreatment entails pH osmosis, and electrodialysis of the concentrate. Ion exchange
adjustment, to ensure that pH is have all been used in the plating is well suited for processing cor-
within the operating range of the industry to recover chemicals from rosive solutions. Ion exchange has
resin, and filtration, to remove rinse solutions. These processes been demonstrated commercially
suspended solids that would foul the have in common the ability to for recovery of plating chemicals
resin bed. The pollutants removed separate specific compounds from from acid-copper, acid-zinc, nickel,
from the wastewater are con- a water solution, yielding a con- tin, cobalt, and chromium plating
centrated in the ion exchange regen- centrate of those compounds baths. The process has also
erant solutions. The regenerants and relatively pure water. The con- been used to recover spent acid
can be treated in a small batch treat- centrate is recycled to the plating solutions and to purify plating soh-
ment system using conventional tions for longer sewice life.
processes. Firms with access
to a centralized treatment system to

3
Ion Exchange Reactions solution phase reactions. For
Basic Concepts example:
Ion exchange is a reversible NiS04 +Ca(OH), Z Ni(OH),
chemical reaction wherein an ion
(an atom or molecule that has lost or
+CaSO, (1)
gained an electron and thus acquired In this reaction, the nickel ions of the . ~

an electrical charge) from solution nickel sulfate (NiSO,) are ex-


is exchanged for a similarly charged changed for the calcium ions of the
ion attached to an immobile solid calcium hydroxide [Ca(OH),] mole-
particle. These solid ion exchange cule, Similarly, a resin with hydrogen __
particles are either naturally ions available for exchange will
occurring inorganic zeolites or exchange those ions for nickel ions
synthetically produced organic from solution, The reaction can be
resins. The synthetic organic resins written as follows:
are the predominant type used 2(R-S03H) + NiS0, Z
today because their characteristics
can be tailored to specific appli-
(R-SO,),Ni + H,SO, (2)
cations. R indicates the organic portion of
the resin and SO, is the immobile
An organic ion exchange resin is portion of the ion active group.
composed of high-molecular-weight Two resin sites are needed for
polyelectrolytes that can exchange nickel ions with a plus 2 valence
their mobile ions for ions of similar ( N F ) . Trivalent ferric ions would
charge from the surrounding require three resin sites.
medium. Each resin has a distinct
number of mobile ion sites that As shown, the ion exchange reaction
set the maximum quantity of ex- is reversible. The degree the reac-
changes per unit of resin. tion proceeds to the right will
depend on the resin’s preference. Or
Most plating process water is used selectivity, for nickel ions com-
to cleanse the surface of the parts pared with its preference for
after each process bath. To main- hydrogen ions. The selectivity of a
tain quality standards, the level resin for a given ion is measured
of dissolved solids in the rinse by the selectivity coefficient, K.
water must be regulated. Fresh water which in its simplest form for the
added t o the rinse tank accom- reaction
plishes this purpose, and the
overflow water is treated to remove
R-A+ 4- B+ Z R-B+ -k A+ (3)
pollutants and then discharged. As is expressed as: K =(concentration
the metal salts, acids, and bases of B+ in resin/concentration of A+
used in metal finishing are pri- in resin) X (concentration of A+ in
marily inorganic compounds, they soIution/concentration of B+ in
are ionized in water and could be solution).
removed by contact with ion ex-
change resins. In a water deioniza- The selectivity coefficient expresses
tion process, the resins exchange the relative distribution of the ions
hydrogen ions (H+) for the posi- when a resin in the A+ form is
tively charged ions (such as nickel, placed in a solution containing B+
copper, and sodium), and hydroxyl ions. Table 1 gives the selectivities
ions (OH-) for negatively charged of strong acid and strong base ion
sulfates, chromates. and chlorides. exchange resins for various ionic
Because the quantity of H+ and OH- compounds. It should be pointed
.. . .. . . . . .... . ~. . .. .. . ..
~

ions is balanced, the result of the out that the selectivity coefficient is
ion exchange treatment is relatively not constant but varies with changes __
pure, neutral water. in solution conditions. It does
provide a means of determining
Ion exchange reactions are stoichi- what to expect when various ions
ometric and reversible, and in that
way they are similar to other

4
are involved. As indicated in Table 1, Resin Types to the sulfonic acid group (S0,H)
strong acid resins have a preference used in strong acid resins. These
for nickel over hydrogen. Despite Ion exchange resins are classified resins behave similarly to weak
this preference, the resin can be as cation exchangers, which organic acids that are weakly
converted back tg the hydrogen form have positively charged mobile dissociated.
by contact with a concentrated ions available for exchange, and

-
solution of sulfuric acid (H,SO,): anion exchangers, whose exchange- Weak acid resins exhibit a much
(R--SO,),Ni +
H,SO,
able ions are negatively charged.
Both anion and cation resins are
higher affinityfor hydrogen ions than
do strong acid resins. This charac-
2(R-S03H) +
NiSO, 14) produced from the same basic teristic allows for regeneration to
This step is known as regeneration. organic polymers. They differ in the hydrogen form with significantly
In general terms, the higher the the ionizable group attached to the less acid than is required for strong
preference a resin exhibits for hydrocarbon network. It is this acid resins. Almost complete
a particular ion, the greater the functional group that determines regeneration can be accomplished
exchange efficiency in terms of resin the chemical behavior of the resin. with stoichiometric amounts of acid.
capacity for removal of that ion Resins can be broadly classified The degree of dissociation of a
from solution. Greater preference as strong or weak acid cation ex- weak acid resin is strongly influ-
for a particular ion, however, will changers or strong or weak base enced by the solution pH. Conse-
result in increased consumption of anion exchangers. quently, resin capacity depends
chemicals for regeneration. in part on solution pH. Figure 1
Strong Acid Cation Resins. Strong shows that a typical weak acid resin
Resins currently available exhibit a acid resins are so named because has limited capacity below a pH
range of selectivities and thus their chemical behavior is similar to of 6.0, making it unsuitable for
have broad application. As an exam- that of a strong acid. The resins deionizing acidic metal finishing
ple, for a strong acid resin, the are highly ionized in both the acid wastewater.
relative preference for divalent (R-SO,H) and salt (R-S0,Na) form.
calcium ions (Ca+,) over divalent They can convert a metal salt to Strong Base Anion Resins. Like
copper ions (Cu+,) is approximately the corresponding acid by the reac- strong acid resins, strong base resins
1.5 to 1. For a heavy-metal-selective tion:
resin. the preference is reversed
and favors copper by a ratio of
2.300 to 1.
2(R-S03H)
(R-SO,),Ni
+
NiCI,
+
2HCI
- (5)
are highly ionized and can be used
over the entire pH range. These
resins are used in the hydroxide (OH)
form for water deionization. They
The hydrogen and sodium forms of will react with anions in solution
strong acid resins are highly dis- and can convert an acid solution to

-
Table 1. sociated and the exchangeable Na+ pure water:
Selectivity of Ion Exchange Resins, and H+ are readily available for
exchange over the entire pH range.
R-NH,OH + HCI
in Order of Decreasing Preference
Consequently, the exchange R-NH,CI + HOH (6)
capacity of strong acid resins is Regeneration with concentrated
Strong acid cation Strong base anion
exchanger
independent of solution pH. These sodium hydroxide (NaOH) converts
exchanger
resins would be used in the hydrogen the exhausted resin to the hydroxide
Barium Iodide form for complete deionization; form.
Lead Nitrate they are used in the sodium form for
Calcium Bisulfite water softening (calcium and Weak Base Anion Resins. Weak
Nickel Chloride
Cadmium Cyanide
magnesium removal). After exhaus- base resins are like weak acid resins,
Copper Bicarbonate tion, the resin is eonverted back to in that the degree of ionization is
Zinc Hydroxide the hydrogen form (regenerated) strongly influenced by pH. Conse-
Magnesium Fluoride by contact with a strong acid solu- quently. weak base resins exhibit
Potassium Sulfate
Ammonia
tion, or the resin can be converted to minimum exchange capacityabove a
Sodium the sodium form with a sodium pH of 7.0 (Figure 1). These resins
Hydrogen chloride solution. For Equation 5. merely sorb strong acids; they
hydrochloric acid (HCI) regeneration cannot split salts.
would result in a concentrated
nickel chloride (NiCI,) solution. In an ion exchange wastewater
deionization unit, the wastewater
Weak Acid Cation Resins. In a weak would pass first through a bed of
acid resin, the ionizable group is a
carboxylic acid (COOH) as opposed

5
-
Legend:

I I
weak acid cation resin
weak base anion resin
The high degree of selectivity for
heavy metals permits separation of
these ionic compounds from
solutions containing high back-
ground levels of calcium, magnesium,
and sodium ions. A chelating resin
exhibits greater selectivity for
heavy metals in its sodium form than
in its hydrogen form. Regeneration
properties are similar to those
of a weak acid resin; the chelating
resin can be converted to the
hydrogen form with slightly greater
than stoichiometric doses of acid
because of the fortunate tendency of
the heavy metal complex to
become less stable under low pH
conditions. Potential applications of
the chelating resin include polish-
ing t o lower the heavy metal
concentration in the effluent from
a hydroxide treatment process, or
directly removing toric heavy
metal cations from wastewaters
" containing a high concentration of
3 4 5 6 7 8 9 10 11 nontoxic, multivalent cations.
SOLUTION pH
SOURCE Adapted from Schweitrer, P. A,. Handbook o f Separation 7echniqusr for Table 2 shows the preference of a
Chemical Engineers, New York NY. McGraw-Hill. 1979. commercially available chelating
resin for heavy metal cations
over calcium ions. (The chelating
Figure 1. resins exhibit a similar magnitude of
Exchange Capacity of Weak Acid Cation and Weak Base Anion Resins selectivity for heavy metals over
as a Function of Solution pH sodium or magnesium ions.) The
selectivity coefficient defines
the relative preference the resin
strong acid resin. Replacement of provide hydroxide ions. Less exhibits for different ions. The
the metal cations ( N P , Cu+,) with expensive weakly basic reagents preference for copper (shown in
hydrogen ions would lowerthe solu- such as ammonia (NH,) or sodium Table 2) is 2,300 times that
tion pH. The anions (SO;,, CI-) can carbonate can be employed.
then be removed with a weak
base resin because the entering Heavy-Metal-Selective Chelating Table 2.
wastewater will normally be Resins. Chelating resins behave Chelating Cation Resin Selectivities
acidic and weak base resins sorb similarly to weak acid cation resins for Metal Ions
acids. Weak base resins are pre- but exhibit a high degree of selec-
ferred over strong base resins tivif/ for heavy metal cations.
Metal ion KM/Ca'
because they require less regenerant Chelating resins are analogous to
chemical. A reaction between the chelating compounds found in
resin in the free base form and metal finishing wastewater; that is,
HCI would proceed as follows: they tend to form stable complexes
with the heavy metals. In fact.
R-NH, f HCI -+ R-NHJI (7) ........................
__ the functional group used in these
The weak base resin does not have resins is an EDTABcompound. The
a hydroxide ion form as does the resin structure in the sodium form is .........................
strong base resin. Consequently. exoressed as R-EDTA-Na. MnCZ ........................ 1.2 -
C8+2 ...... 1
regeneration needs only to neutral-
ize the absorbed acid: it need not 'Selectivity coefficient for the metal over tal-
cium ions at a pH of 4.
'Ethylenedisminetetrsacetic acid.

6
~~~~ ~ _ _
for calcium. Therefore, when a soh- costs of the other commercially tanks each containing 1 equivalent
tion is treated that contains equal available resins. (eq) of resin in the X ion form
molar concentrations of copper and (see Figure 2).A volume of solution
calcium ions, at equilibrium, containing 1 eq of Y ions is charged
the molar concenrration of copper Batch and columnExchange into the first tank. Assuming the
ions on the resin will be 2,300 times systems resin to have an equal preference for
the concentration of calcium ions. ions X and Y. when equilibrium is
Or, when solution is treated that lonexchange processing can be reached the solution phase will
contains a calcium ion molarconcen- accomplished by either a batch contain 0.5 eq of X and Y. Similarly,
tration 2,300 times that of the method or a column method. In the the resin phase will contain 0.5
copper ion concentration, a t first method, the resin and solution eq of X and Y. This separation is
equilibrium, the resin would hold are mixed in a batch tank, the the equivalent of that achieved in a
an equal concentration of copper exchange is allowed to come to batch process.
and calcium. equilibrium, then the resin is
separated from solution. The degree If the solution were removed from
Their high COSt is the disadvantage to which the exchange takes Tank 1 and added to Tank 2. which
of using the heavy-metal-selective place islimited by the preference also contained 1 eq of resin in the
chelating resins. Table 3 com- the resin exhibits for the ion in X ion form, the solution and resin
Pares the of these with the solution. Consequently, the use phase would both contain 0.25 eq
of the resin's exchange capacity will of Y ion and 0.75 eq of X ion. Re-
be limited unless the selectivity peating the procedure in a third and
Table 3. for the ion in solution is far greater fourth tank would reduce the
than for the exchangeable ion solution content of Y ions to 0.125
Cost of Commercially Available attached to the resin. Because and 0.0625 eq. respectively.
Resins batch regeneration of the resin is Despite an unfavorable resin prefer-
chemically inefficient, batch ence, using a sufficient number
Resin Cast (S,ft31 processing by ion exchange has lim- of stages could reduce the ooncen-
ited potential for application. tration of Y ions in solution to any
Strong acid cation.. ....... . . 50-100 level desired.
Weak acid cation.. . . . . . . . . . . 100-150 passing a through a
Strong base anion.. . . . . . . . . .
Weak base anion ............
containing a bed of exchange This analysis simplifies the column
Chelating Cation.. . . , . . , . . . . . ~00-300 resin is analogous to treating the technique. but it does provide
solution in an infinite series of insiahts into the orocess
~ - ~ - - dvnamics.
-I
-
Note.-1 980 dollars. batch tanks. Consider a series of Separations are possible despite

I Solution
fesd (sq):
Y
X =0
= 1 .O Y =0.5
X=0.5
Y = 0.25
X=O.75
Y =0.125
X =0.875
Y = 0.0625
X = 0.9375

Resin after Y =0.5 Y =0.25 Y =0.125 Y =0.0625


mixing (eq): X=0.5 X =0.75 X=O.875 X = 0.9375

Note.-Resin has equal preference for X and Y ions. Solution feed Contains 1 eq of Y ions. Each batch tank initially contains 1 g q
of resin in X ion form.

Figure 2.
Concentration Profile in a Series of Ion Exchange Batch Tanks

7
poor selectivity for the ion being I 1
removed.

Ion Exchange Process


Equipment and Operation

Most industrial applications of ion


exchange use fixed-bed column
systems. the basic component of
which is the resin column (Figure 3).
The column design must: water outlet

0 Contain and support the ion


exchange resin wate
0 Uniformly distribute the service
and regeneration flowthrough the
resin bed
0 Provide space to fluidize the
Graded quartz
resin during backwash
0 Include the piping, valves, and B a dw a s h controller

instruments needed to regulate ewer manifold


flow of feed, regenerant, and
backwash solutions trainer nozzles

Backwash outlet
Regeneration Procedure. After the
feed solution is processed to the SOURCE Kunin, R. "Ion Exchange for the Metal Products Finishers.'' (3 pts.), Products
extent that the resin becomes Finishing. Apr.-MapJune 1969.
exhausted and cannot accomplish
any further ion exchange, the
resin must be regenerated. In normal Figure 3.
column operation, for a cation Typical Ion Exchange Resin Column
system being converted first to the
hydrogen then to the sodium
form, regeneration employs the gen form. A slow water rinse then Regeneration of a fixed-bed column
following basic steps: removes any residual acid. usually requires between 1 and
1, The column is backwashed to 3. The bed is brought in contact 2 h. Frequency depends on the vol-
remove suspended solids with a sodium hydroxide solution ume of resin in the exchange
collected by the bed during the to convert the resin to the columns and the quantity of heavy
sewice cycle and t o eliminate sodium form. Again, a slow water metals and other ionized com-
channels that may have formed rinse is used to remove residual pounds in the wastewater.
during this cycle. The back- caustic. The slow rinse pushes
wash flow fluidizes the bed, the last of the regenerant through Resin capacity is usually expressed
releases trapped particles, and the column. in terms of equivalents per liter (eq/L)
reorients the resin particles 4. The resin bed is subjected to a of resin. An equivalent is the
according to size. Doring fast rinse that removes the molecular weight in grams of the
backwash the larger, denser last traces of the regenerant compound divided by its electrical
particles will accumulate a t the solution and ensures good flow charge, or valence. For example,
base and the particle size will characteristics. a resin with an exchange capacity of
decrease moving up the column. 5. The column is returned to service. 1 eq/L could remove 37.5 g of
This distribution yields a good divalent zinc (Zn+z, molecular ~

hydraulic flow pattern and For resins that experience significant weight of 65) from solution. Much
resistance t o fouling by sus- swelling or shrinkage during regen- of the experience with ion exchange
pended solids. eration, a second backwash has been in the field of water
2. The resin bed is brought in con- shquld be performed after regenera- softening; therefore, capacities will __
tact with the regenerant solution. tion to eliminate channeling or frequently be expressed in terms
In the case of the cation resin, resin compression. of kilograins of calcium carbonate
acid elutes the collected ions and per cubic foot of resin. This unit
converts the bed t o the hydro- can be converted to equivalents per

8
liter by multiplying by 0.0458.
Typical capacities for commercially
available cation and anion resins
are shown in Figure 4. The
capacities are strongly influenced
by the quantity of acid or base used
3.0
-
Legend:

I
I
weak acid Cation resin
Iweak base anion resin
III strong acid cation resin
1 1 1 strong base anion resin

to regenerate the resin. Weak


acid and weak base systems are 2.5
more efficiently regenerated; their
capacity increases almost linearly
with regenerant dose.

Cocurrent and Countercurrent Re-


generation. Columns are designed to 2.0
use either cocurrent or counter-
current regeneration. In cocurrent
-
.
_I
D
units, both feed and regenerant -
solutions make contact with cu
the resin in a downflow mode. These
units are the less expensive of $ 1.5
the two in terms of initial equip- YI
W
ment cost. On the other hand, cocur- z
rent flow uses regenerant chemicals $
0
less efficiently than countercur- 5
rent flow; it has higher leakage
concentrations (the concentration 1 .o
of the feed solution ion being
removed in the column effluent), and
cannot achieve as high a product
concentration in the regenerant.

Efficient use of regenerant chemicals 0.5


is primarily a concern with strong
acid or strong base resins. The
weakly ionized resins require only
slightly greater than stoichiometric
chemical doses for complete
regeneration regardless of whether 0
0 2 4 6 8
cocurrent or countercurrent flow
REGENERATION LEVEL (Ib/fts)'
is used.
'Ib NaOH/ft3 for weak and strong base anion; Ib HCl/ft3 for week and strong acid Cation.
Regenerant Reuse. With strong acid SOURCES: Dow Chamical Company. Dower WGR-2 Weskly Basic Anion Exchange Resin,
or strong base resin systems, T.D. Index 330.1, Midland MI. DOWChemical Company, undated. Dow Chemical
improved chemical efficiency can Company. "Anion Resins: Selection Criteria for Water Treatment Applications," Idea
Exchsngs 5/21. undated. Rohm and Haas Company. Amberlitem 2W. Philadelphia PA,
be achieved by reusing a part
Rahm and Haas Company, No". 1978.
of the spent regenerants. In strongly
ionized resin systems. the degree
of column rege.neration is the- Figure 4.
major factor in determining the
Resin Exchange Capacities
chemical efficiency of the regenera-
-
tion orocess. lSee Fiaure 5.) To
realize 42 percent of the resin's theo- increases consumption to 2.45 tion of acid in the spent regenerant.
retical exchange requires times the stoichiometric dose [5 Ib Further, as the acid dose is
1.4 times the stoichiometric amount HCl/fi3 (80 HCI,L)~, increased incrementally, the con-
of reagent [2 Ib HCl/hJ (32g HCVL)]. centration of acid in the spent
To the exchange capacity The need foracid dosesconsiderably regenerant increases. By discarding
to 6o percent Of theoretical higher than stoichiometric means only the first part of the spent
that there is a significant concentra-

9
-
Legend:
with acid reuse
without acid r e w e
regenerant and saving and reusing
the rest, greater exchange capacity
can be realized with equal levels of
regenerant consumption. For
example, if a regenerant dose of 5 Ib
HCVW (80 g HCVL) were used in ~~~

the resin system in Figure 5, the


first 50 percent of spent regenerant
would contain only 29 percent of
the original acid concentration. The ~

rest of the acid regenerant would


contain 78 percent of the original
acid concentration. If this sec-
ond part of the regenerant is
reused in the next regeneration
cycle before the resin bed makes
contact with 5 lb/ft3 (80 g/L) of fresh
HCI, the exchange capacity would
increase to 67 percent of theoretical
capacity. The available capacity
would then increase from 60 to 67
percent a t equal chemical doses.
Figure 5 shows the improved
reagent utilization achieved by this
manner of reuse over a range of
regenerant doses.
0 2 4 6 8 10
REGENERANT CONSUMED (Ib HCl/ft’) Regenerant reuse has disadvantages
‘Eased on strong acid resin in calcium form
in that it is higher in initial cost
for chemical storage and feed
systems and regeneration proce-
Figure 5. dure is more complicated. Still,
where the chemical savings have
Effect of Reusing Acid Regenerant on Chemical Efficiency provided justification, systems have
been designed t o reuse parts
of the spent regenerant as many as
five times before discarding them.

10
Wastewater Recycle In usual practice, metal finishing incorporates wastewater pretreat-
wastewater is treated and then ment to remove constituents
Systems dischargedto a river or sewer system; that degrade the resins. When ion
as an alternative, the wastewater exchange is used to remove
can be deionized by ion exchange chromate and zinc from cooling
and reused in the plating process. tower blowdown there is similar
Wastewater deionization will potential for resin deterioration.
significantly reduce water consump- Nevertheless, the effects have not
tion and the volume of wastewater been found severe enough t o
requiring treatment, with the preclude the successful use of ion
following primary economic exchange for this application.
advantages:
Hexavalent chromium ( C e ) can be
Water use and sewer fees are removed if the mixed wastewater
reduced.
is passed through an anion column.
Although treatment of pollutants
Cyanide and metal cyanide
is not eliminated, the size and
complexes are ionized and could
cost of the pollution control
also be removed directly from
system is significantly reduced.
the wastewater by anion exchange.
Mixing cyanide wastes with the
The volume reduction resulting from
rest of the plant’s wastewater
wastewater recycling can also
is potentially hazardous, however;
make pollution discharge limits
toxic hydrocyanic gas (HCN) would
easier to achieve. For plants dis-
result from contact with acidic
charging wastewater to municipal
wastes. Therefore, cyanide waste-
treatment systems. the national
waters are normally pretreated
pretreatment standards call
before they are blended with the
for more lenient discharge limits it
rest of the wastewater. In many
a plant discharges less than
cases, an integrated chemical waste
10,000 gal/d (37.000 Ud). Plants
system (Figure 6) can provide
discharging directly to surface
cyanide pretreatment that is low
waters are typically regulated by
in cost and easy to operate.
mass-based pollutant discharge
limits. When translated to a
The usual ion exchange sequence
concentration limit based on a
is cationic exchange followed by
volume of discharge, these limits
anionic exchange. The reverse
may be difficult to achieve by sequence is avoided because pass-
conventional pollutant removal
ing the solution first through an
systems. The reduction of discharge
anion exchange column would
volumes resulting from water
increase pH and could precipitate
recycle will allow for higher concen-
heavy metal hydroxides.
trations of pollutants in the dis-
charge.
System Description
Inorganic plating chemicals such as
acids, bases, and metal salts are An ion exchange wastewater recycle
ionized in water solutions and can be system is shown in Figure 7. The
removed from process waters by major process components include:
ion exchange, Some dissolved
organic compounds, oils, and free 0 Wastewater storage
chlorine are typically present 0 Prefilters
in mixed wastewaters and their Ion exchange columns
presence constitutes a potential Regeneration system
for fouling or deterioration of the ion Batch treatment for regenerant
exchange resin. Electroplating solutions
facilities using ion exchange on Deionized water storage
mixed wastewaters have found the
resins to be operable and stable, Wastewater Storage. A collection
however, when the recycle system sump or storage tank is needed
to provide a surge volume in the

11
Regular skimming can then purge
Workpiece the oil from the recycle system.

Prefilters. Activated carbon columns


are commonly used as ion exchange
prefilters. The carbon columns ~

provide a versatile pretreatment


system; they can:

Cyanide plating bath Chemical rinse water


0 Filter out suspended solids that
with NaOCl rinse could hydraulically foul the ~

solution columns.
To wastewater
0 React with free chlorine or
4 purification and other strong oxidants that could
recycle physically degrade the resin.
0 Adsorb organics that would
otherwise build up in the recir-
Figure 6. culated wastewater.
Integrated Chemical Rinse to Oxidize Cyanide Compounds 0 Adsorb oils that would gradually
foul the resin.
The columns are typically back-
system and ellow the exchangers to solids can be pumped out a t washed daily to remove collected
be fed at a constant rate. The regular intelvals and disDosed of. susoended solids. The backwash
unagitated collection tank can also Tankdesign should allow any free oil water goes either to the waste-
be used to settle coarse solids to separate and then collect water storage tank or to the batch
in the wastewater. The collected on the surface of the wastewater. treatment tank. Carbon replace-

-Ion Exchange Columns-l

Wastewater

Wastewater
discharge
Collection w m p

COnCBntrates

Solids
separatio
T

Regensrant
solutions
I I

On atream
Anion

TO
30
Cation Anion

Off stream

process

Batch treatment Deionized water Legend


tank *tomge
Solids lo C = conductivity probe
disposal NC = normally closed

FiQure7.
Ion Exchange Wastewater Purification and Recycle System
12
mentfrequency depends primarily on In such a case, regeneration with quantity of ionic compounds the
loading of oils or organics. If the sulfuric acid can result in pre- resin bed can exchange.
carbon is not replaced, organic cipitation of calcium sulfate and
impurities can gradually build up in hydraulic fouling of the resin bed. For rinse water recovery, leak-
the recycle water. Some long Calcium sulfate precipitation can be age of small concentrations of
chain organic molecules will foul avoided by using dilute sulfuric acid ionic compounds would not signal
strong base resins. Oil not removed solutions (2 percent by weight). the end of the cycle. Therefore,
by pretreatment collects on the Strong base anion columns are rates should be selected from the
resin and reduces its exchange ca- regenerated with sodium hydroxide. higher end of the recommended
pacity, resulting in more frequent Weak base resins can be regen- range to minimize the initial cost of
regeneration and higher operating erated with sodium hydroxide or the system. Smaller columns will
costs. Cleaning solutions are less expensive basic reagents increase regeneration frequency and
available from resin manufacturers such as sodium carbonate. the associated labor cost. For
to restore the performance of columns with automated regenera-
oil-fouled resin beds. Batch Treatment for Regenerant tion packages, increased re-
Solutions. The pollutants removed generation frequency will not sig-
Ion Exchange Columns. In the most by the ion exchange system will nificantly increase operating costs.
common column configuration, be concentrated in the regenerant
wastewater passes in series through and wash solutions. These solutions
a strong acid cation resin column must undergo conventional treat-
cost
and then through either a strong or ment before being discharged. The
weak base anion resin column. Conventional end-of-pipe treatment
type of pollutants present ( C P and
Weak base resins have higher ex- requires removing pollutants
heavy metals would be most com-
change capacities and require less from large volumes of dilute
mon) dictates the treatment
regenerant than do strong base wastewater. When pollutants are
sequence that would be required.
resins. On the other hand, weak base concentrated into small volume
resins are not effective in removing regenerant solutions, treatment is
Deionized Water Storage. A storage
weakly ionized bicarbonates, usually more economical. More-
tank is used to provide an inventory
borates, and silicates, nor can they over, recycling the purified waste-
of water for process needs. The
operate effectively a t high pH. effluent from the ion exchange col- water reduces operating costs
These limitations may not be a con- associated with water consumption
umn should be monitored with a
cern for metal finishing waste- and sewer fees.
conductivity probe to provide a
waters, and weak base resins are relative index of the level of dissolved
recommended. If these anions solids in the treated water. When As a rule, treating the concentrated
are present in significant amounts, the water conductivity increases t o a regenerant solutions will con-
an anion bed containing both certain level, the columns are sume chemicals in quantities
strong and weak base resins can be smaller than are needed to treat the
switched and the spent columns
used. A bed of this kind will approach are regenerated. Because complete same mass of pollutants in a dilute
the higher exchange capacity and waste stream. Capital costs of
water deionization is not needed for
regeneration efficiency of a most process applications, the wastewater treatment systems
weak base system but provide com- depend primarily on the unit
columns are loaded until the maxi-
plete deionization. mum allowable level of impurity operations required and the volu-
is reached before they are re- metric flowrate of the wastewater.
To provide uninterrupted system generated; regeneration frequency Total investment for an ion ex-
operation when column regen- and system operating costs are thus change water recycle system
eration is required, two sets of col- reduced. and a simplified batch chemical
umns are frequently installed. When destrthct unit to treat concentrated
one set has been exhausted, solutions will often be less than
flow is switched to the off-stream Ion Exchange Column Specification that for a conventional chemical
set and the spent columns are regen- destruct system designed to treat the
erated. Columns are usually sized as a func- total volume of water consumed by
tion of the ratio of wastewater a plant.
volume to resin volume. Recom-
RegenerationSystem. The cation ex-
mended rates vary depending Operating Cost. Operating costs for
change column should be regen-
on the application but as a rule an ion exchange purification sys-
erated with hydrochloric acid after
range from 2 to 4 gal/min/W (0.26 to tem to treat wastewater containing e
exhaustion. Despite its higher
cost, HCI is favored over H,SO, for
0.52 L/min/L) of resin. Higher rates variety of heavy metals will include:
will usually result in higher
regeneration if the wastewater con- 0 Chemicals for column regen-
leakage, but will not affect the
tains a significant amount of calcium. eration

13
0 Destruct chemicals for treatment Table 4.
of concentrated regenerant
solutions and purged wash water Wastewater Characteristics and Ion Exchange Capacity Requirements
0 Disposal of the treatment residue
Treatment
0 Labor for column regeneration
Item
and operation of the batch treat- Ion exchange Conventional
ment system (if not automated)
0 Maintenance Wastewater characteristic:
0 Resin and activated carbon Flowrate (gallmin) . . . . . . . . . . . . . . . . . . 30 30
Constituent (ppm):
replacement 40
0 Utilities ........... 40 40
............................. 50
How these costs compare with the 20
costs of operating a conventional ..... 150 220
Total dissolved solids . . . . . . . . . . 470
hydroxide treatment process can be Alkalinity. as Ca(HCO,), (ppm). ...................... 10 70
determined by evaluating the Wastewatereoncentratians to be treated by ion exchange(eqlL1:
costs associated with each system Cations'. ............................. 0.0036 -
Anions ............................ 0.00423 -
treating the same waste stream.
Ion exchange resin capacity needed for 15-ft3 bed (eq/L):b
To simplify the analysis, equal labor, Cation resin'. ..................................... 0.92 -
maintenance, and utility charges Anion resin ................... 1 .OS -
are assumed for both systems.
.Does not include hydmgen ions.
A typical waste stream (Table 4) b16-h operating cycle.
consisting of rinses after nickel, cop-
per, and chromium plating baths
and acid and alkali process baths regenerated with sufficient acid and rate results from the anions
will be used in the cost analysis. base to provide 1 day's operating associated with the hydrogen ion
In a water recycle system, only capacity. The plant is assumed acidity. Adequate capacity would be
natural alkalinity brought in with to operate 16 h/d. Table 4 includes obtained in the cation column with
makeup water must be treated; the resin capacity needed for a regenerant level of 4 Ib HCl/fP
recycled water has already had its columns with 15 ft3 (425 L) of (64 g HCI/L) of resin. In this case,
initial alkalinity removed. The resin. however, the combined anion and
wastewater used in conventional cation column regenerant must
treatment, however, contains For the strong acidhtrong base be acidified to reduce Cr". There-
all the natural alkalinity brought in unit, sufficient capacity would be fore, excess acid regenerant [6.5
with the fresh water: as a result obtained in the anion column lb/ft3 (104 g/L)] can be used
more alkali reagent will be consumed with a regenerant level of 6.5 Ib to balance the excess NaOH in the
and more solid waste generated. NaOH/fP (104 g NaOH/L) of resin. anion regenerant.
The anion column would require
In light of the foregoing analysis, the greater capacity than the cation col- Table 5 shows the chemical content
next step is to determine the umn because the wastewater is and volumes of the regenerant
required column configuration acidic; the higher anionic loading solutions after they are mixed with
and size of the ion exchange unit.
Either of two column configurations
can be used: strong acid and Table 6.
strong base or strong acid and weak Regenerant Solution Chemical Content
base. In either case, ion exchange
column sizing is based on volumetric
Strong acid/ Strong acid/
loading. At the normally recom- Item
strona base weak base
mended sewice flowrate of 2 gal/
min/ft3 (0.26 L/min/L) of resin, col- Volume.. ........................................ 8 5 0 gel 800 gal
umns containing 15 fP (425 L) Cation column,, .................................. 20.3 Ib CuCI, 20.3 Ib CuCI,
21.1 Ib NiCI, 21.1 Ib NiCI,
--of resin will be needed. The ion ex- 12.1 Ib NaCl 12.1 Ib NaCl
change capacity of these columns 1.6 Ib CaCI, 1.6 Ib CaCI,
will depend on the quantity of 67.0 Ib HCI 29.5 Ib HCI
regenerant (dosage rate). Anion column.. ................................... 16.8 IbNa2Cr0, 16.81bNa2Cr0,
53.3 Ib Na2S04 53.8 Ib Na,SO,
3.0 Ib Na2C03 3.0 Ib Na2C03
Using the resin capacities given in 56.9 Ib NaOH 7.4 Ib NaOH
Figure 4, the columns will be

14
the volume of wash water 150 Table 6.
gal/f@(6.5 UL)of resin] u&ally
required for the backwash and rinse Chemical Prices
stages of regeneration. Chemical
cost of each regdneration cycle is Reagent Description Cost 15/lbla
$29.83forthe strong acid and strong Hydrochloric acid ................................. Carboys. 32% HCI 0.05
base system (based on Table 6). Sodium hydroxide.. ............................... Carboys. 50% NaOH 0.075
Hydrated lime .................................... 100-lb bags 0.05
Regeneration cost can be reduced if Sodium bisulfite .................................. 100-lb bags 0.20
a weak base resin is used in the Sulfuric acid.. .................................... Carboys. 97% H2S04 0.05
Polyelectrolyte.. .................................. Dry powder 2.50
anion column. A weak base resin
downstream of the strong acid '1980 dollars.
column is suited for this application
because the entering wastewater
would always be acidic. Based on the for regeneration should be reduced erant chemicals for this column
capacity shown in Figure 5, suf- to the minimum required for configuration would cost $1 6.56 for
ficient resin capacity could be column capacity, 4 Ib HCl/ft3 (64 g each cycle.
achieved with a sodium hydroxide HCI/L) of resin. Table 5 includes
dose equal to 3.2 Ib/ft3 (51 g/L) of the volume and chemical content of Based on treatment chemical
resin. The amount of acid consumed the regenerant solutions. Regen- consumption factors (Figure 8) and

Reduction (NsHSO,. HS
,O), Neutralization [Ca(OH),]

Chromium waste 1.7 Ib Ca(OH)2/l,000 gal

0.3 Ib NaHS0,/1.000 gal


0.2 Ib H,S0,/1.000 gal
.
A
Neutralization [Ca(OH),lb Precipitation [Ca[OH),] Flocculation

(gallmin. Ib metal'] 1.2 Ib Ca(OH)2/1.000 gal 2.6 Ib Ca(OH),/lb Cr 0.02 lbl1.000 gal
2.2 Ib Ca(OH)2/lb metal

I I

Neutralization [Ca(OH),lb 1

I
0.1 Ib dry solids generated
Solids generation factors Ib Ca(OH)?consumed Ib metal precipitated

-
Legend:

I
Process step (treatment reagent)

Figure 8.
Consumption factor
--1
Conventional Treatment Chemical Consumption Factors
'Ib metal8 expressed a8 Ib metal ions.
bAlkalinity Consumes lime and adds to solids generation rate.

15
Table 7. Effect of Pollutant Concentration.
The volume of wastewater that
Daily Treatment Cost Comparison: Ion Exchange and Conventional Systems can be deionized by an ion exchange
column is in direct proportion
Treatment cost ($Id) to the ionic concentration of the
Component wastewater and is not influenced by
Strong acid/ Strong acid/ Conventional
strong base weak base the volume needing treatment.
Consequently, when dilute solutions
Chromium reduction: are processed, a large volume can
NaHSO ............................. 3.34 3.34 3.82' be treated before column capacity is
n,so, ............................... (5 cbt 0.83
exhausted and regeneration is ~

Neutralization: Ca(OH1,. .................... 3.76 4.08 5.16


Sludge disposalC.. ........................ 3.70' 3.70' 4.97' required. On the other hand, conven-
Ian exchange regeneration: tional treatment processes-such
HCI ................................. 15.21 9.36 (7 as chromium reduction, cyanide
NaOH ............................... 14.62 7.20 (bl
oxidation, and metal precipitation-
Total chemical cost.. ................ 40.63 27.68 14.58 must adjust the chemistry of the
Waterand sewerfee at $l/l.OOO gal.. ....... 1.70 1.70 28.80 water solution to achieve the
desired reaction. The chemical con-
Total treatment cost.. ............... 42.33 29.38 43.38 sumption associated with these
processes therefore depends
'Assumes 1 0 gallmi" of segregated Cr+6 Wastewater
on both the mass of pollutant and
bNot required. the volume of solution to be treated.
'25% solids by weight at $O.ZO/gal. Because its cost is independent
of solution volume, ion exchange
dFot 46.3 Ib dry solids.
processing is highly efficient
'For 62.2 Ib dry solids. in terms of chemical consumption
Note.-1980 dollars. when used to treat dilute con-
centrations of ionic contaminants.

chemical costs (Table 6). Table 7 ing every 2 to 5 years, depending Figure 9a shows the relative costs of
compares the daily cost to operate on the type of resin and the process deionization and conventional
the two ion exchange systems application. Resins can be dam- treatment techniques as a function
with thecostfora conventional treat- aged by exposure to strong oxidants. of the concentration of waste-
ment system. Although the chem- long chain organic compounds, water contaminants for acid-alkali
ical costs are higher for the ion oroil. With properselection of resins waste streams and for hexavalent
exchange systems. when the and effective pretreatment of the chromium wastewater. Only chem-
savings in water and sewer fees wastewater, the potential for ical treatment costs are included,
(assuming $1/1,ooO gal) are resin deterioration and the cost not water and sewer use fees.
considered, the total cost is less for replacement will be reduced. The treatment steps and assump-
than that of conventional treatment. tions used to derive the conventional
The data also indicate that a strong Granular activated carbon must be treatment cost are presented in
acidlweak base column config- replaced when its adsorption Table 6 and Figure 0. Also assumed
uration is considerably less expen- capacity is spent. For small scale is removal of natural alkalinity
sive t o operate than the strong applications, regenerating the during treatment.
acidlstrong base configuration. The carbon is not economically feasible.
economics of the ion exchange Replacementfrequency for activated ton exchange does not compare
system could be improved further if carbon will depend on the level favorably with hydroxide precipita-
the strong acid column regen- of organic compounds in the tion of acid-alkali waste streams
want were reused,. wastewater. Carbon adsorption is an except at very dilute concentrations.
economical means of removing For treating typical metal finishing
For deionization applications, trace amounts of organic compounds wastewater, hydroxide precipi-
commercially available resins cost from solution. If high levels of tation will usually have lower
~~~'Eiifieen~$3OlfPand $200/ff3. Ion organics are present, however, the
exchange resins usually need replac- cost becomes excessive and alterna-
tive removal techniques should be
eva Iuated.

16
(a) 2.00
- hexavalent chromium wastewater (H,CrO,)
acidlalkali wastewater (CuSO,)
~~~~

chemical costs. For hexavalent


chromium wastewater, however, ion
exchange has a treatment cost
advantage up to a concentration of
440 ppm of chromic acid (H,CrO,).

:
& 1.50

..
.
e
Ion exchange treatment is effi-
cient for this application partly be-
cause, except for contaminants,
chromic acid wastewater has
no cations other than hydrosen;
b 1.00 consequently, treatment by ion
8 exchange would not affect cation
5
: column operating costs.

5 0.50 In Figure 9a the cost for con-


ventional treatment of acid-alkali
wastes includes the volume-related
cost for lime to adjust solution pH
and to react with naturally occurring
0 bicarbonate alkalinity, and for
0 100 200 300 400 50C polyelectrolyte conditioners to aid
CONCENTRATION (ppm) in precipitant settling. The curve for
chromium reduction using bi-

'L
sulfite includes these cost compo-
nents plus costs for acid needed
to bring the wastewater t o required
reaction pH and base for subse-
2.50
quent neutralization.

I The ion exchange system costs


are based on 90 percent water
recycle; they include the cost for
column regeneration and treatment
of regenerant solutions by con-
ventional techniques. The regener-
ant chemical consumption is
based on a strong acidlweak base
column configuration.

An ion exchange water recycle


5E 1.00
System becomes considerably more
attractive than conventional
treatment techniques if the credit for
savings in water and sewer fees
is included in the analysis. Figure 9b
0.50 compares treatment costs of the
same two waste streams but
includes a cost equal to $1 11,000gal
water consumed.

0 1 1 I 1 I I Waste Reduction. The waste


0 100 200 300 400 500 Stream volume reduction achieved
CONCENTRATION (ppm) by a wastewater deionization
vgao dollars. system relates directly to the con-
w a t e r and sewer fees assumed at $111 .ooO gal.

Figure 9.
Cost Comparisons for Ion Exchange and Conventional Treatment Systems:
(a) Chemical Cost Only and (b) Chemical Cost and Water Use Fees

17
centration level of the dissolved
ionic solids in the wastewater. WASTEWATER CONCENTRATION (eq/L)
The reduction in volume of the waste 0.01 0.02 0.03 0.04 0.05
stream and its favorable effect on I I I I I
both the initial and operating
cost of wastewater treatment are
part of the justification for using ion
exchange.

Each cubic foot of resin in a column


system can remove a specific
quantity of ions; regenerating and
washing that volume of resin
will result in a purge stream of limited
concentration.

Consider an ion exchange system


with a strong acid/weak base
column configuration. Assume the
resin in each column has a capacity
of 1.5 eq/L, and that regenerat-
ing the columns produces purge
(regeneration plus rinsing) in
the amount of 50 gal/ft3 (6.5 VL)
of resin. The maximum concentration
of the ionic solids in the combined
purge streams from both cob
umns, then, would be 0.11 eq/L. 0 1,600 3.200 4,800 6,400 8,000
Expressed in terms of a typical metal
salt, the maximum concentration WASTEWATER CONCENTRATION [ppm CuSO,)
of copper sulfate (CuSO,) in the
purge solution would be 1.75 per- Figure 10.
cent. Using this relationship, Figure
10 presents the volume reduction Relationship of Waste Volume Reduction to Wastewater Ionic
for treating wastewater over a range Concentration
of ionic concentrations.

The relationship developed in considerable savings in the invest- continued operation during regen-
Figure 10 is based on normal operat- ment necessaw for end-of-pipe eration. AutOmatlOn adds con-
ing procedures. Concentration treatment systems. This investment siderably to the initial cost of the unit
can be improved by selective recycle is usually a function of wastewater but, in addition to savings in labor,
of part of the purge stream; how- flowrate and the required unit can permit the use of smaller
ever, the poor chemical efficiency of operations. For flows above 15 to 20 columns with more frequent regen-
the ion exchange process for gal/min (57 to 76 Wmin), auto- eration. Figure 11 compares costs
treating concentrated solutions mated continuous treatment for two- and four-column ion
and the poor degree of concentration systems are usually recommended. exchange units, automated and
achieved make other methods of A deionization water reuse sys- nonautomated, as a function of resin
treatment more suitable. tem can result in flow reduction suf- volume in each column. The systems
ficient to make a single batch illustrated are skid mounted and
treatment tank feasible for treating preengineered; costs include
Capital Cost. In the metal finishing
regenerant solutions and any the columns, an initial supply of ~~

industw, most of the wastewater


concentrated process dumps. resin, reagent storage, and internal
~.. requiring treatment results from
piping and valves necessary for ser-
rinsing operations. Selective
The cost for ion exchange column vice and regeneration flow.
treatment and reuse of rinse streams -
systems is increased significant-
by ion exchange can result in
ly when dual cation-anion column
configurations are needed for

18
The cost of the auxiliary equipment
60 described earlier for ion exchange
water recycle will add consider-
ably to the total capital cost asso-
ciated with using the technol-
ogy. The total cost, however, may
50
still compare favorably with that for a
conventional end-of-pipe treat-
ment system.

40

-
e
30
8
t
z
3

20

10

0
I
--I
dual cstionlanian column8 (4 columns)
cstian/anian columns (2 columns)

I I 1
0 4 8 12 10 20
RESIN VOLUME PER COLUMN in31

alSBO dollars.
Note.-Skid-mounted, preengineered packaos unit. Includes acid and base
regenerant storage and all internal pipes an0 valves.
SOURCE: Equipment vendor.

Figure 11.
Cost for Deionization Units With and Without Automation

19
En&&Pipe Systems Ion exchange can be used in two treated per unit of resin volume
..
different wavs for end-of-DiDe before the resin must be regener-
pollution control. The process has ated. The regenerant solution,
been demonstrated as a means which contains a high concentration
of polishing the effluent from con- of metal ions, is treated upstream
ventional hydroxide precipitation in the conventional process (Figure
to lower the heavy metal concentra- 12a).
tion further, and it has been used
to process untreated wastewaters Ion exchange has received limited
directly for removal of heavy commercial application for selective -
metals and other regulated pol- removal of heavy metal and metal
lutants. cyanide pollutants from an un-
treated wastewater while allowing
Most plating shops can achieve most of the nontoxic ions to pass
sufficient metal removal to comply through. Various approaches
with discharge regulations by have been employed to facilitate this
employing the conventional hydrox- application:
ide precipitation process. Conven-
tional treatment may not be reliable, A weak acid cation resin has
however, in achieving compliance been used in wastewater soften-
with discharge limits in certain ing to remove heavy metals
cases, including where: and other divalent cations from a
wastewater solution with a
Unusually strict limits are placed high concentration of sodium
on the effluent metal concen- cations.
tration. Heavy-metal-selective weak
a The metals are complexed with acid or chelating cation resin has
chemical constituents that been used to remove the heavy
interfere with their precipitation metal ions while allowing
as metal hydroxides. sodium, calcium, and magnesium
ions to pass throuah.
In such cases, the use of ion ex-
A stratified resin bed, containing
change to polish the effluent can pro-
strong and weak acid cation
vide relatively inexpensive up-
resins and strong base anion
grading of system performance for
resins, has been employed to re-
compliance with the regulations.
move heavy metal cations and
metal cyanide complex anions
The development of special chelat-
while allowing other ions to pass
ing resins made ion exchange
through.
feasible for selective removal of
trace heavy metals from a water solu-
In each of these approaches,
tion containing a high concentra-
wastewater pretreatment require-
tion of similarly charged, nontoxic
ments consist of pH adjustment to
ions. These resins exhibit a strong
ensure that pH is within the operat-
selectivity, or preference, for
ing range of the resin, and filtration to
heavy metal ions over sodium,
remove suspended solids that
calcium, or magnesium ions. Weak
wouldfoul the resin bed(Figure 12b).
acid cation resins also display
The pollutants removed from the
a significant preference for heavy
wastewater are concentrated
metal ions, and in some applications
in the ion exchange regenerant
they are superior to the chelating
solutions. The regenerants can be
~~

resins in performance character-


treated in a small batch treatment
.istics. In a polishing applica-
system using conventional proces-
tion, both resins can remove the
ses. Firms with access to a cen-
heavy metal ions from the waste-
tralized treatment facility that -
water while leaving most of the
accepts industrial wastes can use the
nontoxic ions in solution. The
preference for heavy metal ions
allows a large volume of water to be

20
(a)

wastewater Discharge

Metal Regenerant

-
hydroxide chemicals
sludge

I b) I
Collection
10"
wastewater and & Filtration -I, exchange . Discharge
PH treatment
adjustment

f
Regenerant
Sludge chemicals

To centralized
treatment
facility
Metal
hydroxide
sludge
-
Legend:
sewice
regeneration

Figure 12.
Ion Exchange Systems: (a) Polishing and (b) End-of-Pipe Treatment

facility to dispose of the regenerant Ion Exchange Polishing Systems 0 Ion exchange polishing to
solutions and need not install reduce residual metal solubility
chemical destruct systems. In either Process Description. Figure 13 before the water is discharged
case, no investment is needed shows a treatment system employ-
forsoohisticated DHcontrol Svstems. ino:I
For effective metal removal bv
floccuiant feed systems, clarifiers, hydroxide precipitation, pH must be
0 Hydroxide neutralization to controlled within the narrow
and other process equipment
control pH and to precipitate range where the metals are least
associated with conventional con-
heavy metals as metal hydroxides soluble. Such narrow control
tinuous treatment systems, and
0 Flocculation t o agglomerate usually requires sufficient retention
- ion exchange becomes attractive
the suspended solids time within the pH adjustment
in terms of cost. And, as a further ad-
Clarification and deep-bed tank to ensure minimum variation in
vantage, ion exchange units are
filtration to remove the precipi- neutralizing reagent demand.
compact and easy to automate
tated metals and suspended Multistage neutralizers and sophisti-
compared with conventional treat-
solids cated control loops are also used
ment systems.
to minimize deviation from the pH

21
NaOH
I

I
Feed

I
Flocculant
Mixer-clarifier tank

Collectlo"
Sump
.
I
Regeneration pI Sewice

HCI
hl.nY
I."_..
4 Wastewater
discharoe
"
Ion exchange columns

Figure 13.
Conventional Treatment System With Ion Exchange Polishing

control set-point. With effective For most waste streams, the unit e The presence of chelating
pH control, most of the metals operation sequence of hydroxide pre- compounds that combine with
in the wastewater will precipitate as cipitation, fluocculation. clarifi- metals to form complexes not
metal hydroxides. cation, and filtration will produce effectively removed by hydroxide
an effluent with a minimum precipitation
To provide effective removal of heavy metal content and achieve e Discharge limits requiring metal
precipitated metals and other compliance with discharge permit concentrations below those
suspended solids, coagulating- regulations. In cases where the which a hydroxide treatment
flocculating compounds are added t o metal content exceeds the permit system can achieve consistently
the neutralized wastewater to limit, and the excess is in the and reliably
agglomerate the solids and facilitate form of dissolved metals (as opposed
their removal. Most of thesuspended to metal hydroxide particles not Resin Selection. Ion exchange
solids can be removed by clarifica- removed during solids separation), a heavy-metal polishing systems will
tion: however, removal of fine polishing treatment using ion usually use a chelating heavy-metal-
particles (includirlg precipitated exchange resins will reduce the selective cation resin. A resin of
metals) requires filtration. Deep-bed effluent metal concentrations. this kind forms an essentially ~~ ~

filters, which remove solids by nonionized complex with divalent


passing the wastewater through a The failure of hydroxide precipitation metal ions. Consequently, once an
-bed of sand and gravel, are used to reduce metal solubility to the exchanger group is converted to the
most frequently. required level can be caused by one heavy metal form, it is relatively -
of the following: unreactive with other similarly
charged ions in solution. Despite
e Failure to control pH within the high concentrations of non-heavy-
narrow range necessary for
minimal metal solubility

22
metal cations competing for the ex- off stream 10 percent of the time Operating Procedure. Operation of
change sites, the resin has suffi- for regeneration in any given an ion exchange polishing system is
cient preference for the heavy day will achieve the discharge per- complicated by the lack of prac-
metal ions to exhibit a high metal- mit limits. Mechanical failures tical meansfordeterminingwhen the
holding capacity'per unit of resin and system maintenance are inevi- column is exhausted and metal
volume. The chelating resins table consequences of using the breakthrough occurs. Unlike
will effectively remove heavy metal process, however, and the reliability deionization systems, where a con-
cations from solutions with a of a single column design is prob- ductivity probe will signal the
pH above 4.0. ablyinadequate in most applications. end of a column cycle, polishing
systems have no simple, direct
Weak acid cation resins also have In none of the polishing system technique for continuously monitor-
potential for use in ion exchange column configurations is there a ing the levels of heavy metals
polishing systems.These resins have simple means of detecting the in the effluent. To compensate for
the advantage of being less breakthrough of metal ions that this lack, the columns are operated
expensive than chelating cation would indicate a need for column on either a time or flow cycle.
resins, and they require less chemi- regeneration. Metal breakthrough is This approach requires determining
cals for regeneration. On the other avoided by loading the column the column exchange capacity
hand, weak acid resins are not only to some fraction of its and the loading per unit volume of
effective in acidic solutions; exchange capacity. A series cob wastewater. Then, based on the
moreover, they are less selective for umn configuration, where the resin volume in the column,
heavy metal cations over other total flow of wastewater passes the volume of wastewater that can
divalent calcium and magnesium through each column, is particularly be processed before exhausting
ions than are chelating resins. reliable in ensuring contact of the exchange sites can be estimated.
the wastewater with a large volume As a rule, to provide a factor
Polishing System Equipment and of unreacted resin. After the of safety, a capacity equal to three-
Auxiliaries. The ion exchange polish- upstream column is exhausted, it quarters of the actual exchange
ing system consists of: is taken off stream. regenerated, capacity is used to determine the
and returned to senice as the volume that can be processed
Column or columns containing
down-stream column. This configu- per cycle.
the resin
ration minimizes the possibility
Acid regenerant storage that the resin will be exhausted and For a constant flow system, the
Sodium hydroxide regenerant
that metal breakthrough will volume capacity can be converted
storage occur. On the other hand, pressure to a cycle time. A flow totalizer can
0 Piping and valving to facilitate
drop over the system will be be used for variable flow systems
on-stream wastewater treatment,
high and each column must be sized to monitor the cumulative volume
and regeneration and back-
to process the total flow. and indicate when the column
washing of the resin bed
should be regenerated. Many manu-
Three ion exchange column configu- A parallel column configuration facturers provide automatic
rations for a polishing system are: employing three or more columns regeneration capabilities with
has advantages, particularly for their column systems. For such sys-
Single column larger flows. Both equipment cost tems, the control mechanism
Series column and reliability are intermediate can be directed to begin regenera-
Parallel column between the single and series col- tion by either a timing device
umn configurations. In a parallel or a flow totalizer.
Unlike deionization systems. which configuration, each column is
require both a cation and an anion sized based on the assumption that The regeneration sequence for a
resin column, the polishing system one column is always off stream chelating and a weak acid cation
usually requires only one kind for regeneration. This design resin is:
of resin. Consequently, a single reduces the total resin volume re-
column design is feasible for small 1. Water backwash to remove sus-
quirements compared with those of
flows where the wastewater dis- pended solids from resin bed
a series column design. Using a
charge can be interrupted to allow bank of small columns does increase
2. Acid regeneration
-for column regeneration. Discharge regeneration frequency; many of the
3. Water wash to remove residual
permits are usually based on a acid
units are designed with automated
daily composite sample, and this regeneration capabilities, how- 4. Sodium hydroxide regeneration
factor should be considered in ever, and more frequent regeneration 5. Water backwash to remove
evaluating use of a single column. residual caustic and reclassifv
does not increase the need for
Often the composite effluent the resin particles
operating labor.
quality of a treatment system that is 6. Cocurrent fast rinse to ensure
that the resin bed's flow charac-

23
teristics are adequate and to Table 8.
remove any unused reagents
7. Return to service Ion Exchange Polishing System Performance Characteristics

The resin is used in the sodium form Item Characteristic Value


even though it adds extra steps
Ion exchange column Chelating resin 10 n3
to the regeneration process
Wastewater volume 120.000 gallcycle
and increases the chemical con- Resin capacity 0.87 Ib Ni/ft3
sumption. Treating an alkaline 0.03 Ib Culft3
waste stream with a resin in the hy- Service:
-
drogen form would gradually result Wastewater to column.. ................. pH 8.4
Ni" 8.9 ppm
in conversion of the resin to C"+2 0.3 ppm
either the sodium or calcium form: Dischsnge.............................. pH 8.4
however, the exchange for hydro- Ni" 0.16 ppm
gen ions would depress the effluent CU+Z 0.02 ppm
Regeneration:
pH below the control limitations Flow to column.. ....................... Wash water 500 gallcycle
and result in a period of noncom- 5% NsOH 68 gallcycle
pliance. Also, the resin exhibits 5% nci 65 gai/cycle
a greater selectivity for heavy Purge streams.. ........................ Volume 633 gallcycle
metals in the sodium form. Nickel 0.16%
Copper 0.006%
Hydrochloric acid is normally
used for acid regeneration although
it is more expensive than sulfuric quentlyshrink when converted tothe of time. In essence. they define
acid. Sulfuric acid regeneration sodium form, which necessitates the length of time the solution is in
could result in the precipitation of a final backwash before the column contact with the resin.
magnesium or calcium sulfate is returned to service.
during regeneration, and the resin Figure 14 shows the concentration
bed could thus be hydraulically All regenerant and wash solutions profile of the effluent from a pilot
fouled. This effect can be avoided, are sent to the hydroxide treat- test column containing a chelating
however, if a dilute (2-percent) ment system for processing. resin. The feed solution has an
sulfuric acid regenerant solution is Table 8 presents a typical polishing initial cadmium concentration of 50
used. system performance with volume ppm, a calcium chloride (CaCI,)
of wastewater processed and the concentration of 1,000 ppm. and a
The final backwash t o reclassify the relative volumes of the regenerant pH of 4.0. Tests were run at two
resin bed is critical. "Classifi- streams. different volumetric loadings:
cation" refers to positioning the 8 bv/h (1 gal/min/ff (0.13 L/min/L)]
resin particles so that the largest System Performance. The number of and 16 bv/h [2gal/min/W (0.26
particles are at the base of the ion exchange polishing systems L/min/L)]. The higher loading
column and the particle size installed to date is limited; resulted in earlier breakthrough.
gradually decreases as distance however, abundant pilot test data Assuming the column cycle is
from the base increases. This verify system effectiveness in terminated at a cadmium concen-
arrangement results in maximum reducing the soluble metal content tration of 2.0 ppm in the effluent, the
flowrate per unit of pressure drop of a neutralized waste stream. 8-bvlh system could treat 400 bv
ariu makes the bed more resistant The data from these controlled before regeneration. compared
to fouling from suspended solids experiments can lead t o a better with 325 bv for a system operating
in the column feed. understanding of how process vari- at 16 bvlh.
ables and design factors influence
With strong acid and base resins. performance. The influence of volumetric loading
an initial backwash before regenera- on capacity results in a trade-off -~
Volumetric loading for ion exchange
~

tion is usually sufficient to ensure between investment and operating


good flow characteristics during systems is usually expressed in cost. Specifying a larger, more
the service cycle. In the case bed volumes (bv) of solution expensive column will result
of weak acid or chelating resins. treated per hour or in gallons per in greater capacity per unit volume
however, the resin beads swell minute per cubic foot (liters of resin and less frequent and -
considerably when converted per minute per liter) of resin. Both more efficient regeneration.
to the hydrogen torm and subse- measures describe loading in
terms of the volume of solution
treated per volume of resin in a unit

24
Pilot evaluations have also been
performed with actual plating waste-
water. Figure 17 shows the feed and
effluent concentrations of copper
and nickel when the effluent
from a hydroxide precipitation
system was treated by ion exchange
polishing. After adjustment to
a pH of 8.4, the wastewater still
contained a high level of nickel,
although copperwas removed to less
than 1 ppm. Dissolved ammonia
content was approximately 80
ppm. The weak acid cation resin in
sodium form was ineffective in
removing the nickel and the
0 100 200 300 400 500 test was terminated after 700 bv of
B E 0 VOLUMES TREATED solution had been treated. The
chelating resin in sodium form
Note.-Feed solution: 50 ppm Cd". 1,000 ppm CaC12, pH =4.0. consistently removed the nickel to
SOURCE: Adapted from Rohm and Haas Company, "Ion Exchange in HBBW Metals levels below 0.5 ppm and the
Removal and Recovery."AmberHilite No. 162, Philadelphia PA, Rohmand HassCompany. copper to below 0.1 ppm until 1,600
1979. bv of solution had been treated.
The equivalent would be processing
Figure 14. 12,000 gal/ft3 (1,600 VL) of resin
before regeneration would be
Influence of Flowrate on Chelating Resin Capacity needed.

When the resin is selected for a


Figure 15 shows concentration stable complexes with the heavy polishing application both weak acid
pFofiles of the effluent from two metals. Ammonia, a common and chelating cation resins should
pilot test columns. One column constituent of many plating waste- be tested. The lower initial cost,
contained a chelating resin, waters, tends to increase metal greater capacity, and more efficient
the other a weak acid resin. Each hydroxide solubility. For example, in use of regeneration chemicals
column treated a solution with a copper solution containing make weak acid resins the choice for
50 ppm cadmium and 1,000 ppm dissolved ammonia, the ammonia those applications where they
calcium chloride a t pH 2.07,4.0. and would compete for copper ions are effective in metal removal. Many
8.0. Neither resin is effective as follows: wastewater applications, how-
a t a pH of 2.07. The chelating ever, wilt require the chelating
Cu(OH), -t4NH3 t Cu(NH3)~*
resin shows approximately equal resins' greater affinity for heavy
capacity at pH 4.0 and 8.0. The weak + 20H- ( 8 ) metals to achieve the necessary
acid resin shows a capacity effluent quality.
In the presence of many chelating
increase when pH is increased from
compounds, a chelating resin
4.0 to 8.0. It is significant that
is more effective in removing Ion Exchange Wastewater
the weak acid resin showed
heavy metals than a weak acid resin Treatment Systems
greater capacity than the chelating
because it forms a less-ionized
resin at pH 4.0 and 8.0. Where
complex with the heavy metal ion. The conventional practice of con-
they are suitable, the less expensive
This effect is demonstrated in verting the heavy metal pollutants
weak acid rasins are the resins
Figure 16, which shows the superi- in metal finishing wastewater to
of choice in metal removal applica-
ority of the chelating resin in a hydroxide sludge was thought to be
tions.
removing copper from solutions a means of eliminating any envi-
containing ammonia. A similar ronmental hazard the metals might
Ion exchange polishing is often situation would be expected for
considered because hydroxide pre- pose. In fact, a solid waste stream is
other complexed metal ions. generated that, although its
cipitation cannot effectively
reduce metal solubility in the pres- volume is much smaller than that of
ence of comDounds that form the wastewater, requires further
controls to ensure that disDosal of

25
pH =2.07 PH =4., pH =a.o
-
Legend

0
chelating resin
weak acid resin
resin capacity (Ib Cd/ft31

pH = 2.07

0 100 200 300 400 500 600 700 800


BE0 VOLUMES TREATED

Note.-Feed solution: 50 ppm Cdt2. 1,000 ppm CaCI2. 8 bv/h


SOURCE Adapted from Rohm and HaasCompany, "Ion Exchange in Heavy Metals Removal and Recavety,"Amber Hilite No. 162, Philadelphia
PA, Rohm and Haas Company. 1979.

Figure 15.
Influence of Solution pH on Chelating and Weak Acid Cation Resin Capacity

the metal residue is environmentally metal waste disposal, the devel- which use conventional destruct
acceptable. opment of processes that recover processes, result in a residue with
metals from mixed metal wastes the same disposal criteria as
Ion exchange represents an alterna- is inevitable. When metal recovery the sludge from a conventional
tive means of concentrating the is commercialized on a wide treatment process. The ion exchange
pollutants. The metals are concen- scale, the ion exchange regenerant system may still present a less ~~

trated in the regenerant solutions solutions will represent a byproduct costly means of complying with
. and are then in a form more of metal finishing operations, not pollution control regulations. The
easily handled and more amenable a waste product. key to using ion exchange for waste
to further processing. With the treatment is to remove only the -
increasing cost of virgin metals Currently, firms using ion exchange toxic pollutants while allowing most
and the significant cost of heavy for end-of-pipe pollution control of the nontoxic ions in solution to
must also install small batch treat- pass through the column. Normally,
ment systems to treat the regenerant the toxic compounds represent
and wash solutions. These systems.

26
-
Legend:

0
weak acid cation resin
chelating resin
resin capacity (Ib Cu/ft3)
requirement is substantially dif-
ferent from those of hydroxide pre-
cipitation systems, which need
minimum deviation from the control
set-point.

As a rule, filtration to remove


suspended solids is the only other
pretreatment required. Suspended
solids in the feed would hydraulically
foul the resin bed. Different filters
have been employed, including
deep bed, diatomaceous earth pre-
LT
Y
0.
II Breakthrough coat, and activated carbon filters.
In one approach, a filter with
e
8 fine resin particles is used to trap
suspended solids. Regardless of the
filter type, the resulting purge
I I stream containing the suspended
0 solids must be processed and
0 100 200 300 400 500
disposed of.
B E 0 VOLUMES TREATED

Note.-Feed solution: 5 0 ppm CU''. 1,000 ppm CsCI,. pH =4.0. 8 bdh. The specifications of the column
SOURCE Adapted from Rohm and Haas Company. "Ion Exchange in Heavy Metals system containing the ion exchange
Removal and Recovely,"Amber Hilite No. 162. Philadelphia PA, Rohm and Haas Company. resin depend on the flowrate
1979. and the pollutants in the wastewater.
Two potential cases emerge with
respect to pollutants:
Figure 16.
Heavy metal cations alone
Influence of Ammonia on Chelating and Weak Acid Cation Resin Capacity Heavy metal cations along
with cyanides. and complex metal
anions
only a small percentage of the ionic Ion exchange column regenera-
solids in the wastewater, If the tion system In the case of wastewater containing
ion exchange system is not selective 0 Batch treatment for regenerants only heavy metal cations, a column
in the species it removes from the (or waste storage if regenerants with the sodium form of a weak
wastewater, the column capacity are shipped off site for treat- acid or heavy-metal-selective chelat-
required and the regenerant chem- ment or recoven/) ing cation resin would be employed.
icals consumed will result in prohibi- For a weak acid resin, a pH close
tive costs. Wastewater collection most to neutral is recommended. If
frequently consists of gravity drain- a chelating resin is used, the pH can
Ion exchange has proved successful age of rinses to a collection sump be slightly acidic (>4.0). In both
in selectively removing many of below ground. The sump provides a cases, strongly basic conditions
the pollutants encountered in storage volume to allow the flow should be avoided because
metal finishing wastes. Proper appli- to the treatment system to be such conditions favor formation
cation of the process requires controlled at a constant rate. If the of anionic metal complexes.
selecting the appropriate resin and ion exchange columns employ either
regeneration sequence and, usually, weak acid or weak base resins, the For waste streams containing both
some pretreatment of the waste- capacity and performance of the heavy metals and cyanides, a
water before ion exchange. resins will be influenced by pH. stratified bed of resin has proven
Consequently. the collection effective. This patented approach
Process Description. Wastewater sump should include coarse pH uses a bed of resin with successive
-treatment systems employing adjustment capabilities. The pH ad- layers of strong base anion, weak
ion exchange include the following justment system must only ensure acid cation, and strong acid cation
components: that the solution pH does not resins.The wastewater first comes in
deviate from the broad operating contact with the strong base resin,
Wastewater collection range of the resin. This pH control
Wastewater pretreatment which selectively adsorbs the
complex metal cyanide ions but
Ion exchange columns

27
allows the rest of the negatively
(a) 20.0 charged ions to pass through.
It should be noted that, although the
resin will remove complexed
10.0
metal cyanides selectively, the
presence of free cyanide will result ~

in early cyanide breakthrough.


I
The strong base resin does not show
significant selectivity for hexavalent
-zk
P
chromium or free cyanide over
the sulfate, chloride, and other non-
~

P toxic anions in a wastewater. For


s
k effective use of this type of resin
5
V system, hexavalent chromium
e=
2
1.0 wastes should be treated to reduce
the chromium to the trivalent form
Y
Y before they are mixed with the
uz rest of the wastewater. The trivalent
chromium will be removed selec-
tively by the weak acid resin.

The wastewater then comes in


contact with the weak acid cation
resin in the sodium form. The resin
0.1 employed exhibits a strong pref-
erence for multivalent cations. Con-
BE0 VOLUMES TREATED sequently, cation resin capacity
(b) 2.0 is a function of the concentration of
calcium, magnesium, and heavy
metal cations. Finally, the resin
weak acid cation resin column effluent
1.o chelating resin column effluent
makes contact with a layer of
strong acid cation resin that is pre-
dominantly in the hydrogen form.
The exchange of the hydrogen ions
I
tends to balance the pH rise that
-zka normally would occur a t the
beginning of the cycle.
;
25 The system also employs a novel
regeneration sequence for the
V
stratified resin bed. In a conventional
e
z
0.1
mixed bed system, cationic and
e anionic resins are separated by being
Y
L
P backwashed into discrete layers.
e Each layer is then regenerated
independently; acid is brought
in contact with the cation resin and
sodium hydroxide regenerates
the anion bed. The bed is then mixed
with air and the resin types are
distributed equally throughout the
0.01 bed.
0 200 400 600 8M) 1.000 1.200 1,400 1,600 1,800 2.000
BE0 VOLUMES TREATED With the stratified bed usedforheavy
Note.-Feed conditions (average): 0.1 ppm Cr. 275 ppm Ca, 2,200 Ppm Na, 0.05 Ppm Zn. metals and metal cyanide, the -
80 ppm NH,. pH =8.4. 8 bvlh. resin bed is first backwashed gently
to remove suspended solids and
Figure 17. the resin bed is fluidized. Because
the three types of resins have
Metals Removal Data: (a) Nickel and (b) Coppei

28
t!
HCI and

Resin
COlUnI”

NaOH
Compressed air

NaCN for
chemical
SOURCE: C. Terrian: Best Technology. Inc.. personal communication to P. Crampton. Aug. 10. 1980. makeup

Figure 18.
Sodium Cyanide Recovery

different densities, the resin stratifi. by the time it reaches the strong acid treated in a small batch treatment
cation can be maintained with resin. After another water wash, system. Depending on the pollu-
proper backwashing. The strong the column is returned to service tants present, the system may need
base resin is least dense, the weak capability for cyanide oxidation,
acid resin is intermediate, and The stratified bed system also fea- chromium reduction, and metal pre-
the strong acid resin most dense. tures cyanide recovery to avoid cipitation. The sludge resulting
After backwash, the bed makes the significant cost of treating the from batch treatment can be either
cocurrent contact with a 20-percent cyanide contained in the acid settled and disposed of or mechan-
HCI solution. The acid elutes regenerant. The acid regenerant and ically dewatered before disposal.
the metal cyanide complexes from the subsequent water wash are
the anion resin and replaces routed to a closed-top vessel (Figure A system treating a combined
them with chloride ions. The heavy 18) where heat is supplied to wastewater containing both ferrous
metals and divalent cations are raise the solution temperature to ions and cyanides will have a
removed from the weak acid 140” F (60’ C) and air is bubbled significant concentration of ferro-
cation resin and replaced with into the solution. The result is a cyanides in the regenerant solution.
hydrogen ions. The strong acid resin rapid release of HCN gas. The These difficult-to-treat cyanide
is also converted to the hydrogen liberated gas is brought in contact complexes result from mixing
form. with a caustic soda solution; the of the cyanide wastewater with
caustic soda absorbs the cyanide. acidic streams containing dissolved
After a water wash, the bed is yielding a sodium cyanide (NaCN) iron. An additional treatment step
washed with a 20-percent sodium solution that can be used for chem- is needed to oxidize the ferro-
hydroxide solution. The sodium ical makeup in the cyanide plating cyanides. In this step hydrogen per-
hydroxide converts the anion baths. oxide is added to the wastewater,
resin to the hydroxide form and which is subjected to irradiation by
elutes any metal chloride complexes Regenerant solutions from the ion ultraviolet light. The strong oxidiz-
formed during the acid wash. The exchange column are usually ing power of this system is effective
weak acid cation resin is converted in treating the ferrocyanides.
to the sodium form. The sodium
hydroxide is essentially depleted

29
When ion exchange column size is Table 9.
determined, hydraulic and con-
taminant loadings must be consid- Removal of Zinc and Cadmium from Wastewater by Weak Acid Cation Resins
ered. Resin manufacturers recom-
mend volumetric loading rates Leakage (ppm)
Total loading
Bed volume Sampled
in the range of 1 t o 2 gal/min/W (ga11ft3resin) pH
Zinc Cadmium Calcium
(0.13 to 0.26 Vmin/L) of resin.
Unless the contaminant loading 10.............................. 75 10.1 0.01 0.01 1
results in unmanageable regenera- 25 .............................. 190 10.1 0.01 0.01 3
tion frequency. the hydraulic 35 .............................. 260 8.3 0.01 0.01 53
55. ............................. 410 7.2 0.01 0.01 303
loading should be selected from
~

70 .............................. 520 6.0 0.16 0.01 338


the high end of the range. 100............................. 750 7.0 0.1 0.01 385
...............................
150 ~
1.120 6.9 0.13 0.01 404
System Performance. Operating data lRO
i . . .. . . ... ... . . .. ... ... . . .. ... ... . ... ... . 1.zoo ~ 6.8 0.25 0.01 405
165 ............................. 1,230 6.8 0.37 0.01 407
from ion exchange wastewater 175 ............................. 1,300 6.7 0.56 0.01 404
treatment systems is scarce because 190. ............................ 1,420 6.8 0.64 0.01 395
of the small number of facilities 200............................. 1,500 6.8 1.3 0.01 394
employing the technology; however, 225... .......................... 1.680 6.9 6 0.01 395
the available performance data indi-
cate the potential for application aNs form.
in metal finishing wastewater Note.-Feed characteristics:391 ppm Ca, 91 ppm Zn. 0.1 2 ppm Cd. 350 ppm Mg. 57 ppm Ns. 3.5
treatment. ppm Mn. 0.12 ppm Ni: pH =4.7; 8-bvlh (l-gel/min/ft3) flowrate.

SOURCE Rohmand HaasCompany."lon Exchange in Heavy Metals Removaland Recovery,"Amber


In one case, treatment was of a Hilite No. 162. Philadelphia PA, Rohm and Haas Company. 1979.
slightly acidic heavy metal waste-
water containing a moderate
concentration of calcium, magne- Table IO.
sium, and sodium cations. A
Acid Regenerant Composition
weak acid cation resin in the sodium
form was evaluated for removing
the heavy metals. The resin was able Constituent (ppm)
Bed volume' PH
t o remove both the zinc and cad- Zinc Cadmium Calcium
mium selectively while allow-
ing most of the calcium ions to pass 1 ......................................... 6.0 600 3.2 3.380
through (Table 9). Initially, the .......... 2.4 13,000 14 6,944
resin exchanged its sodium ions for ... 0.4 3.000 1.8 1,003
1.3 677
calcium ions in solution: however, ........... 0.12 67
the resin then exchanged these 0.01 1.7
calcium ions for heavy metals. After 0.01 0
70 bv had been processed, the .......... 0.06 0.01 0.6
~~

effluent contained essentially the Averaae ............................... 2,440 2.6 1.500


same calcium concentration as
the column feed. The column was '3.6% HCI in bv 1 through 4; distilled water in bv 5 through 8.
regenerated with 3.6 percent HCI fol-
SOURCE: Rohm and HaasCompany."lon Exchangein Heavy Metals Ramovaland Recovery,"Amber
lowed by conversion to .the sodium Hilite No. 162, Philadelphia PA, Rohm and Haas Company. 1979.
form with NaOH. Table 10 shows
the composition of the acid
regenerant solution. In this case, The entire wastewater flow was water composition at various
ion exchange treatment reduced collected in a single sump equipped points in the treatment system and
the waste volume associated with with a pH control system to ensure the concentration of the purge
the pollutants t o less than 5 percent that cyanide wastes were not streams. Sample points are rawfeed, ~ ~

of the original volume. subjected to acidic conditions. The filtered feed, filter backwash,
. ................. ion exchange columns were strati- regenerant purge, and treated
In a second application, an ion ex- fied bed units containing strong effluent (see Figure 12b).
change waste treatment unit base, weak acid, and strong acid -
was installed t o treat the combined resins. Table 11 gives the waste- The design of the ion exchange
waste flow from a plating shop wastewater treatment system is es-
performing copper, nickel. and
assorted cyanide plating processes.

30
Table 11. To pretreat the wastewater before it
passes through the ion exchange
Treatment of Metal Cyanide Wastewater by Ion Exchange: PollutantAnalysis
column,suspended solids
and coarse DH adiustment are
Content (ppm) at sample point needed: removal of organic com-
Constituent pounds may also be required. (Foul-
Filtered Filter Regenerant Treated
Rswfeed feed
backwash purge effluent ing by organics is primarily a
problem with strong base anion
Total cyanide . . . . . . . . . . . . . . . - 31.4 - - 3 resins.) Organics can be removed
Cadmium . . . . . . . . . . . . . . . . . . . 0.8 0.4 0.13 0.295 0.0001 using activated carbon or synthetic
Calcium .................... 61.4 28.8 74.8 600 1.637
Chromium .................. 1.37 0.52 3.47 13.4 0.356
adsorbent materials. The syn-
capper.. . . . . . . . . . . . . . . . . . . . 2.11 0.28 3.8 4.57 ....
0.41 thetic materials have the advantage
Iron ....................... 14.2 3.3 65 11.5 0.195 of being regenerable; spent carbon
Nickel ..................... 3.14
Zinc ....................... 42
2.92 31.1 36.4 0.425 must be disposed of and replaced.
23 95 251 2.62 As a rule, filters that remove or-
SOURCE:C.Terrian,BeotTechnolagy,Inc.. PewOn.lcommUniCationtOp.~,smpton,~ug. 1980, ganics are also effective for remov-
ing suspended solids.

Table 12. Similarly in a polishing application


the upstream process can treat
Commercially Demonstrated Resin Systems for Wastewater Treatment the regeneration purge streams.
For direct treatment, a batch
Resin system Application destruct system is needed. Table 13
presents typical costs for the
Weak acid.. ......................... Selective removal of heavy metals from untreated auxiliaries commonly associated
wastes
with ion exchange systems.
Chelating cation ...................... Selective removal of heavy metals from untreated
waetes
Exchange column size and the asso-
Removal of trace concentrations of heavy metals
from solutions with high background cation con.
ciated resin volume specifications
centrations depend on the wastewater flowrate
Selective r e m O of
~ ~heavy
~ fmm 801utions and the contaminant loadings.
containing metal complexing compounds Resin manufacturers usually recom-
Stratified bed (strong base. weak acid. mend loadings for resin systems
strong acid). ....................... Selective removal of metal cyanide, anionic metal at about 2 gal/min/W (0.26 Umin/L)
complexes, and multivalent cationsfram solution of resin. Flowrate indicates the
flow of solution related to the aver-
age period of time it is in contact with
sentially uniform over the range of is applied to treat the waste the entire resin bed. However,
pollutant removal capabilities directly. the ion exchange unit is the active zone of an ion exchange
it exhibits. Proper resin selection, basically the same. The major system can be represented as
however. is the key to effective equipment cost differences between an exchange front proceeding down
and efficient pollutant removal. the two systems is in the auxiliaries. the column (Figure 19). The depth of
Testing t o verify performance of a For a polishing application after the active front is a function of
resin system is essential before conventional treatment, the auxiliary the volumetric loading and the
system selection. Table 12 presents requirements are provided by speed of the ion exchange reaction
varieties of resin systems in commer- the upstream process. In a direct kinetics. For ion exchange applica-
cial use for pollution control and treatment application, however, tions where the columns are
the pollutant removal capabilities these items add significantly to the run t o exhaustion, the benefits of
of each. total system cost. Determinants low loadings include greater
of the total system cost include: capacity per unit of resin and more
efficient use of regenerant chem-
Equipment Cost e Feed pretreatment requirements icals. In wastewater treatment,
e Volumetric and contaminant however, the lack of direct measure-
Whether ion exchange is used t o loadings (resin volume needed) ment techniques to signal column
polish the effluent of an existing 0 Regeneration mode breakthrough precludes load-
treatment system or whether it e Equipment needed to process or ing the column to exhaustion, and
store regeneration solutions and higher loading rates are recom-
purge streams

31
Table 13. mended. Regeneration is based
either on time or on cumulative
Typical Costs for Ion Exchange Equipment Auxiliaries volume interval. As the interval will
be based on assumed wastewater
Auxilisv Installed cost (0) concentration established by
earlier testing, a safety factor must
pH adjustment tank. by flowrate in gallmin:'
25,000 be used in determining the dura-
............................. 32.000 tion of the cycle.
................ 45.000
............................ 51,000 The columns would typically be
Deep bed sand filters. by flowrate in gal/mln:b
25 .......................... ........... 25.000
loaded to 75 percent of their actual
.............................. 3a.000 capacity before regeneration. That is
............................ 45,000 to say, there should usually be a
100. . . . . . . . . . 49.000 band of unreacted resin left over at
Batch treatment system. by volume in .... the end of the column on-stream
250. ........................................................ 7.000
500.. .......................................................
8.500 cycle. For both wastewater
1,000 ....................................................... 10.750 treatment and polishing, higher
1,500 ....................................................... 12.250 volumetric loading rates, if they
2,ow ....................................................... 13.500 still result in a manageable regenera-
tion frequency, offer the advantage
'20-min retention. pH-controlled addition of NaOH, skidmounted unit. of reduced equipment size and
bOual filters With backwash system and backwash storage. skidmounted unit. c p t . Loading rates as high as 20
'Agitated reaction tank. pH-controlled addition of H,SO, and N ~ O HORP-controlled
. addition of gal/min/ft3 (2.6 Umin/L) of cross
N ~ H S O manual
~, operation sectional area [equal to 5 gal/min/W
Note.-1 980 dollars.
(0.65 L/min/L)of resin volume.
assuming a bed 4 ft (1.2 m) deep]
have been used in some applications.
Legend High loading rates for polishing
Influent water. B+ ions
t resin containing A+ ions systems are particularly advanta-
@ resin containing a+ ions geous considering that the contami-
nant loading is usually low.

The regeneration sequence is labor


intensive and automation is cost
effective except where regeneration
is needed infrequently. Regen-
eration of a column normally takes
1 to 2 h. As a rule, columns in
multicolumn parallel flow arrange-
ments are designed to operate
@ + @ + + @ + + e t
at least 4 h before regeneration.

The costs for various column config-


t @ t t @ t t @ t t t urations are shown in Figure 20
~ t @ t t @ t t @ t for skid-mounted units that require
t t t t t t t t t t + only piping and utility connections
for installation. The regenerants
t t t t t t t t t t t
t t t t t t t t t t
are metered into the units by
t t t t t t t t t t t eductors. Regeneration is manual
t t t t t t t t t t for the single- and dual-bed units. ~~

The three-bed parallel flow unit is


sized based on two columns in ser-
vice while the third is being
regenerated; costs are with and
Treated water. A+ ions without automated regeneration. -

Figure 19.
Ion Exchange Column in Service

32
'
~

I hand, achieves much greater


3c
chemical efficiency per unit of
regenerant a t lower regenerant
doses. Consequently, weak acid
resin systems can be designed to
25 use the total resin exchange
capacity; this capability reduces
either required resin volume or
regeneration frequency. Strong
acid systems will realize greater
20 efficiency if they are designed to
use approximately 40 to 60 percent
e of the total resin exchange capacity.
8- Determining.exchange capacity
F
15 requirements requires analysis of the
0
0 wastewater feed and column
t effluent chemical concentrations.
z
3 Consider the weak acid resin system
whose performance for removal
10
of zinc and cadmium was described
in Table 9. Assuming that a concen-
tration of 1 ppm zinc in the efflu-

-
entsignaled the end of the cycle, 175
5 Legend: bv of solution could be treated
I I3-bed parallel flow, automated regeneration before regeneration. Table 14 gives
I I 3-bed parallel flow. manual regeneration the composite feed and effluent
2-column parallel flow, manual regeneration
1-column. manual regeneration
concentrations in milligrams
per liter and equivalents per liter of
I I I I 1
0 solution. The change in the equiva-
3 6 9 12 15 lents per liter represents the number
RESIN VOLUME PER COLUMN (n3) of resin exchange sites that would
'1980 dollars. Add $200/n3/column for chelating resin. be exhausted if 1 L or solution
were passed through me exchange
Note.-Skid-mounted unit with weak acid cation resin. mid and base regenerant.
storage. and all intemal piping and vslves.
column. The test indicated that
each lifer of solution treated would
exhaust 0.0145 eq of resin exchange
Figure 20. capacity. Breakthrough occurred
after 175 bv had been treated,
Ion Exchange Unit Costs indicating that the resin had a total
capacity of 2.5 eq/L, which is the
same as the resin manufacturer's
Operating Cost shown in Figure 21 for typical strong data indicated.
and weak acid cation resins over
The chemical cost of operating an a range of acid regenerant doses. Assuming a three-column parallel
ion exchange system relates The weak acid resin requires signifi- flow unit is selected to treat the
directly to the quantity of toxic cantly less regenerant per unit 50-galhin (190-Umin) waste
contaminants removed from the of exchange capacity. stream and that the columns
wastewater by the resin bed. The are operated on a 4-h cycle, the
chemical efficiency of the ion Figure 21 also shows that the capa- necessaty column size can be deter-
exchange reaction is a function of city of weak acid resin increases mined. It is assumed that the resin
the resin selected and of the per- almost linearly with the amount capacity is actually 80 percent
-centage of the resin's exchange of regenerant. That is to say, increas- of the theoretical capacity. This
capacity used. This relationship is ing the regenerant dose 50 adjustment is similar to applying a
percent increases the exchange fouling coefficient to a heat transfer
capacity by an almost equal ratio. surface and accounts for gradual
The strong acid resin, on the other

33
deterioration in resin performance.
2.5 The adjustment yields a resin
capacity of 2 eq/L.

The resin volume requirement


calculation per column is shown in
Table 15. The unit is designed
2.0 to have two of the three columns on
stream at any time. Assuming
that the column is run to exhaustion,
5.8ft3 (164 L) of resin would -

.
5
- 1.5
be needed per column.

No direct indication of column


cu breakthrough is available for
s end-of-pipe process applications.
To prevent discharging high concen-
9
YI
0
trations of regulated pollutants, the
z columns can only be operated to
9
0
1.0
some fraction oftheiractual capacity;
2 75 percent is a reasonable safety
factor. Required resin volume

-
would then increase to 7.8ft3 (220L)
per column.

0.5 Two safety factors, then, have


Legend:
weak acid cation resin been used in sizing the ion exchange
II111 strong acid cation resin system; one t o compensate for a
gradual deterioration of resin
exchange capacity and one to com-
pensate for lack of direct means
0 of determining column breakthrough.
0 2 4 6 8
REGENERANT LEVEL (Ib HClIft')
Table 15 shows regeneration
chemical consumption and cost,
Figure 21. the purge streams from the unit, and
the waste concentration factor.
Exchange Capacity versus Acid Regenerant Load for Cation Resins The purge stream containing the pol-
lutants is approximately 7 percent
of the original volume of wastewater.
Table 14. Consumption of HCI and NaOH for
Resin Capacity Based on Test Results the system was assumed at 120
percent of the stoichiometric reagent
requirement, based on the theo-
Feed Product
C0"Stlt"B"t Change (eq/L) retical resin exchange capacity of
g/L eq/L 9IL eq/L 2.5 eq/L. Sodium hydroxide needs
are only slightly above stoichiomet-
Calcium ........................ 0.39 0.0195 0.3 0.015 0.0045
ric amounts, despite the resin's
Magnesium ..................... 0.35 0.0292 0.27 0.0225 0.0067
Zlnc ........................... 0.09 0.0028 (8) TI 0.0028 preference for being in the hydrogen
Sodium ......................... 0.06 0.0026 0.32 0.0139 -0.0113 form, because the product of the
Manganese ..................... 0.03 0.001 0.02 0.0008 0.0004 caustic regeneration reaction is not
Cadmium ....................... 0.001 1') I=) I7 0.0001 ionized. The caustic regeneration
reaction is:
'Negligible.

Note.-Exchange requirements:perliteroffsed.0.0145 eq/L: per 175 bvoffeed. 2.53eq/Lof resin.


R-H + NaOH -+ R-Na + H,O (9) -
Once the resin's hydrogen ion
is exchanged, it combines with a

34
Table 15. resin exhaustion: forbreakthrough
the Dolishino
system fFigure 17) . - e

Column Size Determination for Three-Column Parallel Flow Unit


does not occur until 1.600 bv of
wastewater have been treated.
Item Factor

Flowrate: The longer column cycle associated


25 gallmin with polishing often eliminates
50 gallmin the justification for automated
...
d h
regeneration. If regeneration
Exchange capacity per liter of f e e d . . ............ 0.0145 eq
is manual, a two-column unit, oper-
4 X 60 X 25 X 3.79 X 0.0145 = 330 eq
Resin volume needed: ated in either parallel or series
Per column.. ............................ [330/(2eq/L)] X [1/(3.79)(7.48)] = 5.8 ft3 flow with each column sized to
With safety factor . . . . . . . . . 5.810.75 = 7.8 ft3 process the total flow, would
Regenerant consumption per column per cycle:
probably be most effective in terms
HCI (based on 100%) 45 Ib
NaOH (based on 100%). 50 Ib of regeneration frequency and
Wash water . . . . . . . . . . 390 gal reliability. For automated units, a
cost per cycles.. . . . . . . . . . . . $15.09 three-column parallel flow unit,
Waste Concentrstion factor (6.000 gal Wastewater pet cycle)1(40Ogal designed to have one column off
purge per cycle) = 15
stream for regeneration, would prob-
'1980 dollars.
ably be most effective.

Safety features similar to those


used in the direct treatment analysis
Table 16. will be applied to the polishing
Annual Cost of Ion Exchange Treatment System system. The theoretical capacity will
be reduced to 80 percent of the
capacity indicated in the test
Item cost
data to compensate for fouling,
lnvestmsnt~5)............................................................ 23.000 and the column will be exhausted
to only 75 percent of its actual
Operating oost ($/yr): capacity to avoid breakthrough
Labor. K h/shift at 581h ............................................... 2.000
Maintenance. 6% of investment.. ....................................... 1,400
before regeneration. These features
Regenerant chemicals. 4.000 h a t 2 hlcycle .............................. -
-30,180 will yield a volume-processing
capability of 960 bw of wastewater
Total operating cost.. ............................................... 33.580 before regeneration.
Fixed cost ($lyrJ:
DBpreCiation ......................................................... 2,300 Regenerationfrequency is a function
Taxes and insurance .................................................. - 230 of column size. Table 17 gives
regeneration frequencies, costs
Total fixed COst.. ................................................... 2.530 per regeneration cycle, and annual
Total BnnUsl COSt ................................................... 36.110
costs for units in three sizes, each
operating 4,000 h/yr. Operating
Note.-1 980 dollars. Operation 4.000 hlyr. Does not include water pretreatment or batch treat- time for each regeneration cycle was
ment system. assumed at 1 h. Operating costs
are approximately the same for
all three units, and would therefore
hydroxide ion to form a non-ionized treatment and batch treatment favor the smaller unit, which requires
water molecule and no longer are not included. the least capital outlay. The chem-
competes for exchange sites. ical cost for a polishing system
A similar analysis can be performed is significantly lower than that
The installed cost of a three-column for a polishing system using per- for the direct treatment system (Table
- parallel flow ion exchange system formance data from Figure 17 16) because most of the metals
with 7.8 h3 (220 L) of resin and a flowrate of 50 gallmin (190 are removed during conventional
per column, skid-mounted with Umin). The major difference treatment.
automated regeneration, is $23,000 is in the large volume of solution
(Figure 20).Table 16 shows the that can be treated per unit volume Evaluating resin capacity by running
total annual cost for a system of resin. In the direct treatment a test column to exhaustion (Figure
operating 4,000 h/yr. Capital and case, 175 bv could be treated before 17). is time consuming, particu-
operating costs of wastewater pre- larly for a polishing application

35
Table 17. where the resin can process a
large volume of solution before
Annual Cost for Ion Exchange Polishing Systems exhaustion. It is more expedient to
pass only sufficient volume through
Regeneration frequency the column until the column effluent
Item reaches equilibrium, then analyze
16 h 24 h 36 h
the feed and product for ionic
Column resin volume (ft3)'. ......................... 6.7 10.0 15.0 constituents. The exchange per unit
Ion exchange unit cost I$),. ........................ 15,700 19,000 24.000 of feed solution will thus be deter-
mined and, when compared to
Operating casts ($/yr): the resin's theoretical exchange
Labor, at $8/hb.. ............................. 2.ooO 1,330 890
capacity (from manufacturer's
Maintenance. at 6% of unit cost.. ............... 780 900 1.140
Regeneration chemicals'. ...................... 1,660 1,660 1,660 literature), can be used to predict
the solution volume the resin
Total operating cost.. .. 4,440 3,890 3,690 can process before exhaustion! The
safety factors described earlier
Fixed Costs ($lyr):
Depreciation ................................. 1,570 1.900 2.400 should be used with this approach.
Taxes and insurance .......................... 160 190 240
~

The foregoing, then, are some of the


Total fixed cost.. ........................... 1,730 2,090 2.640
alternatives and process variables
......................... 5,980 6,330 to be considered in evaluating
Total annual c o s t . . 6,170
ion exchange systems. Actual test-
.For chelating resin column. 5O-gsl/mln flowrate. ing, decisions regarding system
specification, and type of resin
bl
h labor per regeneration.
should be left to experts in use of the
%sed on 120% theoretical resin capacitv = 1 sq/L. technology. An awareness of the
Note.-1 980 dollars. Systems operating 4,000 hlyr. flexibility and power of the ion
exchange process for waste
treatment applications. however,
can aid the metal finisher in obtaining
the most effective system for the
least total cost.

36
Chemical Recovery Pollution control legislation has plating chemicals and the degree of
and ~~~~~l~systems affected industry by increasing
the economic penalty associated
concentration needed for recycle
is not great. Ion exchange is
with inefficient use of raw materials. well suited for processing corrosive
In the plating industry, for example, solutions. The process has been
loss of raw material in the waste- demonstrated commercially
water can result in costs in three dis- for chemisal recovery from acid
tinct areas: copper, acid zinc, nickel, cobalt, tin,
and chromium plating baths. It
Replacement of the material
has also been used to recover spent
Removal of the material from the
acid solutions and for purifying
wastewater before discharge
plating solutions to prolong their
Disposal of the solid waste
service life.
residue

In response to the increased cost Economic Analysis of Recovery


of raw materials, plating shops Systems
are modifying their processes
to reduce their losses. Recent years To evaluate the economic benefit of
also have seen the cost-effective installing ion exchange or other
application of various separa- recovery processes, the following
tion processes that reclaim plating determination must be made:
chemicals from rinse waters,
Quantity and replacement
permitting reuse of both the raw
cost of the chemicals and water to
material and the water.
be recovered
Savings in wastewater treatment
Ion exchange, evaporation, reverse
cost expected to result from
osmosis, and electrodialysis have all
recovery unit installation
been used in the plating industry
Reduction in solid waste and cost
to recover chemicals from rinse
of sludge disposal expected to
solutions. These processes have in
result from recovery unit installa-
common the ability to separate
tion
specific compounds from a water
solution, yielding a concentrate
of those compounds and relatively In evaluating a plating cnemical
pure water. The concentrate is drag-out recovery system, the rinse
recycled to the plating bath and the water volume and chemical con-
purified water is reused for rinsing. centration must first be measured.
To determine which separation This step will establish the quantity
process is best suited for a particular of chemicals available for recovery.
chemical recovery application, it When the relationships of waste-
is usually necessary to evaluate both water volume and metal content to
general and site-specific factors, the associated wastewater treatment
for example: and sludge disposal cost have
been determined, the potential
General factors would include savings can be determined. Table 18
rinse water concentration. shows the economic penalties for
volume, and corrosivity. losses of typical plating chemicals.
Among site-specific factors are
floor space available, utilities The high. investment cost for
(such as steam, chemical installing an automated recovery
reagents, electricity) available, process limits application of
.. . . . . and degree of concentration this process to plating operations
needed to recycle the chemicals with high drag-out rates, as illus-
to the bath. trated for chromic acid recovery in
Figure 22. The analysis assumed an
As a rule, ion exchange systems are
suitable for chemical recovery
when the rinse water feed has a
relatively dilute concentration of

37
Table 18. investment cost for the recovely
system of $30,000,with the
Economic Penalty for Losses of Plating Chemicals
unit depreciated over 10 years.
Typical operating, labor, and mainte-
Cost [$/lb)
nance costs for an ion exchange
Chemical
Replacement Treatment. Disposalb Total system were used to determine
operating costs. Chemical savings
Nickel:
........ were derived from Table 18,
As NiS0 ........................ 0.84 0.31 0.38 1.53
which indicated a total saving of
As NiCl ......................... 1.14 0.34 0.52 2.00
Zinc cyanide. as Zn(CN)2:
$2.15/lb of H,CrO, recovered (equal ~

Using CI, for cyanide oxidation., .... 1.55 0.80 0.50 2.85 to $2.50/lb of CrO,). From the
Usino NaOCl for cvanids oxidation., .
- 1.55 1.68 0.50 3.73 foregoing, a reasonable rate of return
Chromic acid. as H2Cr0,: is achieved for a CrO, drag-out rate
Using SO, for chromium reduction.. . 0.98 0.53 0.64 2.15
above 3 Ib/h (1.4 kg/h), for which
Using NaHSOJ for chromium reduc-
tion.. ......................... 0.98 0.76 0.64 2.38 payback equals 2.8 years. Plating
Copper cyanide, a s CU(CN)2: operations with rates significantly
Using C12 for cyanide oxidation.. .... 2.05 0.80 0.50 3.35 lower than 3 Ib/h (1.4 kg/h)
Usino -
Using NaOCl for cvanide
cyanide oxidation.. . 2.05 1.68 0.50 4.23 would not be economically justified
coooer sulfate. as CUSO.. .............. 0.62 0.31 0.34 1.27
in installing this recovely system.
*At concentration Of 1W mglL in wastewater.
Tax credits associated with invest-
b4% solids by weight a t $0.20/gal. ments in pollution control hard-
Note.-1 980 dollars. ware were not included in the
foregoing analysis. The credits would
improve the economy of othelwise
marginal investments, but not
50 enough to justify installing an auto-
mated recovery system in an
operation with low drag-out rates.

Drag-out Recoven/
40
-z by Ion Exchange
2
The Reciprocating Flow Ion Ex-
5
D
changer (RFIE) is the kina of ion ex-
$ 30 change system most widely used
for chemical recovery from plating
c
5I rinses. This proprietary unit was
especiallydeveloped for purifying the
5
5 20
bleed stream of a large volume
solution such as the overflow from a
z plating rinse tank. It operates
0
z on the principle that, for the short
U
period of time the unit goes off
E
U stream for regeneration, the buildup
10
of contaminants in the rinse sys-
tem is negligible.

The RFIE units are more attractive


than fixed bed systems for plat-
~~~ ~~

0
0 1 2 3 4 5 ing chemical recovery because the
columns use smaller resin vol-
DRAG-OUT RATE (Ib CrO,/h) umes and, therefore, capital costs
Note.-Operating 4.000 hlyr. 530,000 mwstmnnt cost. Tax rate at 48% of profit. and space requirements are usually -
lower. The units incorporate
regenerant chemical reuse tech-
Figure 22. niques to reduce operating costs and
Return on Investment in Chromic Acid Recovew Unit

30
H*SO, -- NsOH
Purified
rinse

A
Spent rinse
water

--------- -----------_--- 1
I I
I
1. 4 .
I
I
Cation Anion
I
I I
I
I

Nom-Automatt

(b)
-ON STREAM (LOADING) REGENERATION - --I WASHING 1-

k+
Rinse
Exhaust
Product (to waste water
A treatment)

Cation Anion Cation CBtlO" Anion Catlo"

NaOH water
Purified
Exhaust water
(to w*ste
tf881me"l

Figure 23.
Chromic Acid Recovery RFlE System: (a) Hardware Components and (b) Operating Cycle

yield higher product concentration recover only the water and concen- chromium plating bath (or baths) is
for recycle. They are sold as skid- trate the metals before treatment. pumped to the ion exchange
mounted package units, which unit and passes in series through a
are automated to minimize operating Chromic Acid. Figure 23 shows cartridge filter, a strong acid
_labor requirements. Two basic the hardware components of an RFlE cation resin bed, and a strong base
units are available for drag-out re- chromic acid recovery system anion bed. The demineralized water
covery: one forchromic acid recovery and necessary auxiliaries and de- is returned t o the rinse system.
and one for metal salt recovery. scribes the operating cycle. The The RFlE unit regenerates itself auto-
Another unit is designed to deionize segregated rinse water after a matically based either on a cycle
mixed-metal rinse solutions to timer or on the conductivity of
the treated water. With the conduc-

39
~~~

tivity controller, the conductivity of Table 19.


the treated water is compared
with that of the unit feed. When the Performance of RFlE Chromic Acid Recovery U n i r
unit is no longer achieving sufficient
conductivity reduction, regenera-
tion is initiated. Regeneration
Regensrant SOIUtlonS:
frequency is based on the quantityof NaOH ........................................... 3.7 Ib
chromic acid in the rinse and the ......... 12.2 Ib
unit’s resin volume. The unit is 80 gat
off stream for regeneration for ap- 1.2W gallcycle: 200 ppm CrO,
proximately 20 min. The chromate
Purified rinse .......... 1,200 gallcycle
Product.C r03. ................................ 2 Ib each at 10%CIO,
ions removed from the rinse are Purge to waste treatment.. ............................. 80 gal
concentrated in the anion resin bed.
They are eluted in the form of a Chemical savings
sodium chromate solution when this ............................
C a 3 , 2 Ib a t $2.501lb.. 5.00
NaOH at 50.15llb ................................. -0.56
bed is regenerated with sodium n+o, st $o.o511b.. ............................... -0.61
hvdroxide. The sodium chromate so-
lution is passed through a second Total saving per cycle.. .......................... 3.83
strong acid cation resin bed to
convert the sodium chromate to v.35 n3 anion resin.
chromic acid. The recovered chromic b1g8o dollars.
acid solution is stored and used for
chemical makeup in the chromium
plating bath. The product concentra-
tion is approximately 1 0 percent
chromic acid. After the resin beds
are washed with water, the unit goes
back on stream.

The RFlE units come in several


sizes; higher chromic acid loading
rates require larger resin bed
volume. Ideally, the unit performs
two cycles per hour. Each cycle
reclaims a certain amount ofchromic
acid and consumes a set amount
of regenerant chemicals. Table 19
shows the chemical savings,
reagent cost, and amount of chro-
mium recovered per cycle.

Figure 24a presents the purchase


cost of RFlE units for chromic
acid recovery as a function of the
amount of chromic acid the unit can
recover. Including reagent and
product storage, piping and utility
connections, startup, and shipping
expenses, the total installed cost
for a system should be approximately
120 percent of the unit cost.
...
-Metal Salts. RFlE units are recover-
ing plating drag-out from nickel,
copper, zinc, tin, and cobalt plating
rinses. The major area of application
is for nickel plating baths. Two
basic units are used for metal
Three-column parallel-flow ion exchange package unit ready for installation

40
recovery. One employs a cation bed
to reclaim the metal ions and an
anion bed to remove the counter-
ions; the deionized water is recycled
to the rinse station. For applications
40 - where only recovery of the metal
is desired, the anion bed is elim-
inated and the metal-free water is
discharged.

tw-- 30 - Figure 25 presents RFlE system


hardware and the necessary auxil-
+
Y)
iaries for metal salt and rinse
water recovely and describes the
8 operating cycle. The segregated
t
f 20 - rinse water after the plating bath (or
baths) is pumped to the ion ex-
change unit and passed, in series.
Minimum
unit size through a prefilter, a strong acid
cation resin bed, and a strong

lo t base anion bed. The demineralized


water is returned to the rinse

n- 7
0 2 4 6
DRAG-OUT RATE (Ib CrOJh)
8 10
system. The metal ions concentrate
on the cation resin and are eluted
with either sulfuric or hydrochloric
acid. The concentrated salt solution
(either the metal sulfate or chlo-
ride) is stored and used for chemical
makeup in the plating bath. The
(b) 50
regenerantfrom the anion bed is sent
to waste treatment.

Metal salt recovery units also come


40 in various sizes, with unit size
determined by the amount of metal
salts in the rinse water. Each
cycle will reclaim a set amount of
$
4
metal salts and consume a set

- 30
amount of regenerant chemical.
w- Table 20 shows chemical savings,
+
Y)
reagent consumption, and the
8 amount of metal recovered per cycle
5 20
for nickel plating recovery.
a
The purchase cost for an RFlE metal
Minimum salt recovery unit is presented in
unit size .Based on 2 cycles per hour. Figure 24b as a function of the
10 amount of metal salts the unit can
bOual-bed (cation snd anion).
recover. The price is for a unit
%sed on 7.5 cycles per hour. with both a cation and an anion bed:
the price is approximately one-
third less for a unit with a single cat-
0 ion bed. Including the basic RFlE
0 10 20 30 40 50
unit, reagent and product storage,
DRAG-OUT RATE (Ib NiSO, 6H,O/h) piping and utility connections, stert-
up, and shipping, the total installed
Figure 24.
Equipment Cost of RFlE Units: (a) Chromic Acid Recovery and
(b) Metal Salt Recovery

41
,

+9 3+
Reagent measuring I
tanks
L-----------------------
PACKAGE UNIT COMPONENTS I
Note.-Automated control included with package unit.
.
Utilities
water
Air
J’
(b) +REGENERATION =- . - 1 WASHING -1
1O
-N STREAM (LOADING)--(
Recovered
Rinse water
nickel
Purified water slectrolyte Waste water waste
Filter

catton Anion cstion Anion Cation Anion

Caustic water

I Acid Acid

Figure 25.
Metal Salt Recovery RFlE System: (a) Hardware Components and (b) Operating Cycle

cost for a recovery system should been contaminated by metal salts. be desorbed with water. This
be 120 percent of the unit cost. The process, called acid retardation, technique has been commercialized
brings an acid solution in contact using reciprocating flow methods
with a strong base anion resin. The similar to those described for
Acid Recovery Systems resin will sorb the strong acid chemical recovery.
but not the metal salts. The acid can
Ion exchange is used to purify The two process steps are
concentrated acids (such as sulfuric, -
shown in Figure 26. In the on-
hydrochloric, and nitric) that have stream step (upstroke), the metal-

42
Table 20. salt-contaminated acid is metered
into the bottom of the resin bed.
Performance of RFlE Metal Salt Recovely U n i r The free acid is sorbed by the resin
and the metal salt byproduct
Item Value (per cycle) solution flows out the top of the bed.
Regenerant Solutions:
In the regeneration step (down-
NaOH ...................................... 0.63 Ib stroke), water elutes the acid
H,SO, ..................................... 1.2 ib from the resin, yielding an acid con-
water ..................................... 58 gal centration equal to that of the
Spent rinse.. ................................... 250gal/cycle;600ppmNiSO,. 6H20, feed solution and a lowerconcentra-
150 ppm NiCl .BH,O
Purified rinse ................................... 2 5 0 gallcycle
tion of metal contaminants.
.
Product. NiSO, 6 H 2 0 . . .........................
Purge to waste treatment.. .......................
.
1.7 Ib each at 17% NiSOl BH,O
58 gal Two applications are seen for this
system:
Chemical savings
Anhydrous N i S O , 1 Ib at $ 1 , 5 3 / l b . , ........... 1.53 e Purification of strongly acidic
NaOH at $0.15/lb ........................... -0.09 process baths
H,SO, at $0.05/lb.. ......................... -0.06
e Recovery of excess acid from cat-
Total savings per cycle ..................... 1.38 ion exchange regenerantsolutions

'0.35 ft3 cation resin. Demonstrated uses of ion exchange


bl
9 8 0 dollars.
acid purification include removing
aluminum salts from sulfuric
acid anodizing solutions, removing
I I -
metals from nitric acid rack-stripping
solutions, and removing metals
Metal salt solution
from sulfuric and hydrochloric acid
Compressed
I .warn air to w a s * pickling solutions. The major
area of application is for aluminum

A
6
anodizing solutions.

I 1 Water
metering
tank
Spent
acid
metering
Resin bed
Investment in an acid purification
system is justified by the savings in
purchases of replacement acid
and of neutralizing reagentsfortreat-
ing the spent acid. The amount
saved depends on the type of acid
to be recovered, the volume and
concentration of the spent acid dis-
carded yearly, and the cost of

B
treating the spent acid.

Acid purification systems are


I Comorsssed air Spent acid
available in a range of sizes. Size is

1 a function of the volume of acid


that can Be purified per unit of time:
size requirement is determined
spent by the rate a t which metal salt
water
metering
acid
Resin bed
accumulates in the acid bath.
metering Table 21 shows the feed, product,
and waste stream concentration of a
purification system for sulfuric acid

P t
Purified acid (product)

Figure 26.
Acid Recovely System Operation: (a) Upstroke and (b) Downstroke

43
PP

6051 Z0E 1VO


........................ p 9 1 / 8 0 0 $ 1 B 'HOeN
ZE'11 9Z'Z 1E'O
......................... 9119OO$ 10 '*OSzH
&I/$] SBU!AnS
6L 1 8'5E 6'P
......................... .l~/ClO BlBJ I P O W W UOll
OOP 08 11
........................... (q/leB) elel pee4 P!3V
000'95 CmO'OZ
OOool ................................. pl$l 1603 I!un
Bibliography Abrams, I. M. "Selective Removal of Dow Chemical Company. "Chemical
Heavy Metals from Wastewaters Processing by Ion Exchange."
by Ion Exchange and Absorb- Midland MI, Dow Chemical
ent Resins." Paper read at South Company. undated.
Central Regional Meeting of National
Association of Corrosion Engineers, Dow Chemical Company. "Dower
1974. WGR-2 Weakly Basic Anion
Exchange Resin." T.D. Index 330.1.
Anderson, R. E. "Some Examples Midland MI. Dow Chemical Com-
of the Concentration of Trace pany, undated.
Heavy Metals with Ion Exchange
Resins." In Proceedings: Trace Dow Chemical Company. "Weak
Heavy Metals in Water, Removal Acid Cation Resins." Idea Exchange,
Process and Monitoring. Nov. 15-16, 2(3). undated.
1973. Princeton NJ, Princeton Uni-
versity Press, 1973. Kunin. R., and R . J. Myers. Ion
Exchange Resins. John Wiley and
Brown, C. J., D. Davy, and P. J. Sim- Sons, 1950.
mons. "Nickel Salt Recovery by
Reciprocating Flow Ion Exchange." Kunin, R. "Ion Exchange for the
Paper read a t 62nd Annual Tech- Metal Products Finishers." Products
nical Conference of American Finishing, Apr.-May-June 1969.
Electroplaters' Society, 1975. (3 pt. article)

Brown, C. J., D. Davy, and P. J. Sim- Rohm and Haas Company. "Helpful
mons. "Purification of Sulfuric Hints in Ion Exchange Tech-
Acid Anodizing Solutions.'' Plating nology." Philadelphia PA, Rohm
and Surface Finishing, 66(1):54-57. and Haas Company, May 1972.
Jan. 1979.
Rohm and Haas Company. "Am-
Brown, C. J., and C. R. McCormick. beditem200.'' Philadelphia PA,
"Pollution Abatement via Re- Rohm and Haas Company,
source Recoveryfora Plastics Plating Nov. 1976.
Shop.'' Paper read at American
Society of Electroplated Plastics Rohm and Haas Company. "Ion
12th Annual Meeting, 1979. Exchange in Heavy Metals Removal
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Calmon, C., and H. Gold. Ion 162. Philadelphia PA, Rohm
Exchange for Pollution Control. and Haas Company. 1979.
Vol. 1. West Palm Beach FL. CRC
Press, 1979. Rohm and Haas Company. "Porous
Polymers and Absorbents-A
Crampton. P. "Application of Review of Current Practices.'' Amber
Separation Processes in the Metal Hilite No. 163. Philadelphia PA,
Finishing Industry." Paper read Rohm and Haas Company, 1980.
atThird Annual EPA/AESConference
on Advanced Pollution Control in Schweitzer. P. A. Handbook o f
the Metal Finishing Industry, 1980. Separation Techniques for Chemical
Engineers. New York NY, McGraw-
Dorfner, K. Ion Exchangers; Proper- Hill, 1979.
ties and Applications. Ann Arbor
MI, Ann Arbor Science, 1977.

Dow Chemical Company. "Anion


Resins: Selection Criteria for Water
Treatment ADplications." Idea
Exchange, 5(2), undated.

45
U S . Environmental Protection Wing, R. E. "Processes for Heavy Yeats. A. R . "Ion Exchange Selec-
Agency. Environmental Pollution Metal Removal from Plating Waste- tively Removes Heavy Metals
Control Alternatives: Economics of water." Paper read at First Annual from Mixed Plating Wastes." Paper
Wastewater Treatment Alternatives EPA/AES Conference on Advanced read a t 32nd Purdue Industrial
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EPA 625/5-79-016, 1979. Finishing Industry, 1978.

46