a7w -RESZr

EVALUATION OF RECENT TREATMENT TECHNIQUES

FOR REMOVAL OF HEAVY METALS FROM
INDUSTRIAL WASTEWATERS
Robert W. Peters and Young Ku Environmental Engineering, School of Civil Engineering
H
Purdue University, West Lafayette, IN 47907
Dibakar Bhattacharyya Department of Chemical Engineering, University of Kentucky
Lexington, KY 40506

Removal of heavy metals from industrial wastewaters can be accomplished through various treatment options, including
such unit operations as chemical precipitation, coagulation, complexation, activated carbon adsorption, ion exchange,
solvent extraction, foam flotation, electrodeposition, cementation, and membrane operations. This paper describes these
various treatment strategies and methodologies employed for heavy metal removal. Comparison of their applications in
industry are addressed. Advantages and disadvantages are addressed for each treatment scheme.
INTRODUCTION bath. The spent process waters u s u a l l y con-
t a i n h i g h c o n c e n t r a t i o n s o f ammonia o r cyanide
Growing concern f o r t h e presence and con- which may i n t e r f e r e w i t h t h e removal o f the
t a m i n a t i o n o f heavy metals i n our water sup- heavy metals by hydroxide p r e c i p i t a t i o n .
p l i e s has s t e a d i l y increased over t h e l a s t few Generally, t h e waste problems are r e l a t e d t o
years. Elements such as mercury and cadmium t h e t r a n s f e r o f d i s s o l v e d metal from p l a t i n g
e x h i b i t human t o x i c i t y a t extremely low con- baths o r m e t a l surface c l e a n i n g baths by drag
c e n t r a t i o n s . The elements s i l v e r , chromium, out.
lead, copper, and z i n c a l s o e x h i b i t t o x i c pro-
p e r t i e s t o humans although t h e c o n c e n t r a t i o n s A number o f s p e c i a l i z e d processes have
a r e orders o f magnitude h i g h e r than t h a t r e - been developed f o r t h e removal o f metals from
q u i r e d f o r Cd o r Hg t o x i c i t y . The most pub- waste discharges. These u n i t operations i n -
l i c i z e d case o f i n d u s t r i a l heavy metal p o l l u - c l ude: chemical precipitation (18,67,85,87,111,124),
t i o n i n v o l v e d t h e discharge o f t h e c a t a l y s t coagulation/flocculation (38,431,ion exchange/
methylated mercury c h l o r i d e i n t o Minamato Bay, solvent extraction (36.44,76,93), cement-
Japan, from a p l a s t i c manufacturing f a c t o r y . a t i o n (41,681, complexation (66,99,1511,e l e c t r o -
Microorganisms converted t h e sedimented com- chemical operations (391, b i o l o g i c a l operations
pound t o monomethyl-mercury, which l e d t o an (27,301, a d s o r p t i o n (11,60,77,110), evaporation
enrichment o f t h i s t o x i c metal i n f i s h con- (1131,filtration (401, and membrane processes
sumed by l o c a l people, causing severe c h r o n i c (23,291.A number o f authors have presented
mercury p o i s o n i n g diseases . (31. Removal s o r summaries on various techniques a v a i l a b l e f o r
r e d u c t i o n s o f t o t a l heavy metal c o n c e n t r a t i o n s heavy metal removal from s o l u t i o n .
below 10 mg/l a r e u s u a l l y desirable p r i o r t o
any wastewater treatment o p e r a t i o n s i n c e many
heavy metals, adversely a f f e c t b i o l o g i c a l o x i - The purpose o f t h i s paper i s t o review
d a t i o n processes, (Z,27,113), such as trickling t h e processes c u r r e n t l y a v a i l able f o r waste-
f i l t e r s , a c t i v a t e d sludge, and anaerobic d i - waters laden w i t h heavy metals. The removal
ges t i on. e f f i c i e n c i e s and r e s i d u a l heavy metal con-
c e n t r a t i o n s r e p o r t e d i n t h e l i t e r a t u r e are
Metal processing, metal f i n i s h i n g , and summarized i n t h i s paper and w e l l as r e l a t e d
t h e p l a t i n g i n d u s t r i e s a r e obvious sources of c o s t i n f o r m a t i o n . This paper c o u l d n o t pos-
these heavy metals. The n a t u r e o f t h e waste s i b l y i n c l u d e a l l t h e research and a p p l i c a -
d i r e c t l y r e f l e c t s t h e p a r t i c u l a r combination t i o n s o f heavy metal removal from wastewaters;
o f metals and manufacturing processes used by r a t h e r t h i s paper seeks t o h i g h l i g h t many o f
a g i v e n p l a n t . For example, p l a t i n g i s com- the s i g n i f i c a n t contributions t o the f i e l d
monly done i n e i t h e r an ammonia o r a cyanide d u r i n g t h e p a s t twenty years.

165
 166 Separation of Heavy Metals
PRECIPITATION PROCESSES
I n i n d u s t r y , by f a r t h e most w i d e l y used
process f o r removal o f heavy metals from s o l -
u t i o n i s t h a t o f chemical p r e c i p i t a t i o n ; ap-
p r o x i m a t e l y 75% o f t h e e l e c t r o p l a t i n g f a c i l i -
t i e s employ p r e c i p i t a t i o n treatment ( i i 3 ) , u s i n g
e i t h e r hydroxide, carbonate, o r s u l f i d e t r e a t -
ment, o r some combination o f these treatments
t o t r e a t t h e i r wastewaters. The most commonly
used p r e c i p i t a t i o n technique i s hydroxide
treatment due t o i t s r e l a t i v e s i m p l i c i t y , low
c o s t o f p r e c i p i t a n t ( l i m e ) , and ease o f auto-
m a t i c pH c o n t r o l . The s o l u b i l i t i e s o f t h e
v a r i o u s metal hydroxides a r e minimized f o r
pH i n t h e range o f 8.0 t o 11.0. Peters and Ku
(124)have reviewed t h e c u r r e n t s t a t e - o f - t h e - a r t
'*for heavy metal p r e c i p i t a t i o n . Dean e t a1 .MI),
p o i n t o u t t h a t iron manganese, copper, zinc,
n i c k e l , and c o b a l t r e s u l t i n almost complete
removal by hydroxide p r e c i p i t a t i o n w i t h a l -
most no s p e c i a l m o d i f i c a t i o n r e q u i r e d .
However, p r e c i p i t a t i o n o f mercury, cadmium,
and l e a d may be slow and imcomplete. When
chromium i s present, r e d u c t i o n o f t h e s o l u t i o n
w i t h sodium m e t a b i s u l f i t e , f e r r o u s s u l f a t e ,
o r m e t a l l i c i r o n p r i o r t o l i m e treatment i s
necessary. To reduce hexavalent chromium t o
t h e t r i v a l e n t form, chrome b e a r i n g streams
are general l y s e g r e g a t e d and t r e a t e d s e p a r a t e l y .
C h l o r i n a t i o n i s sometimes r e q u i r e d t o break
down t h e con:,)l';xed organic metal 1i c compounds
p r i o r t o chemical p r e c i p i t a t i o n . Employing
hydroxide p r e c i p i t a t i o n a t e l e v a t e d pH p r o v i d e s
c o n d i t i o n s where t h e metal hydroxides have
1ow s o l u b i 1 it i e s and p r e c i p i t a t e o u t upon
s e t t l i n g , t y p i c a l l y over time p e r i o d s o f 2
t o 4 hours. L;uxxletk [ a ) , p o i n t s o u t t h a t when
two o r more heavy metals are found i n t h e
same waste stream, t h e optimum pH f o r p r e c - i p i -
, t a t i o n o f each c a t i o n may be d i f f e r e n t . The
q u e s t i o n then becomes whether i t i s p o s s i b l e
and p r a c t i c a l t o p r e c i p i t a t e one o r more o f
t h e metals s e p a r a t e l y a t t h e source a t one
pH and t r e a t t h e remaining stream(s) a t another
pH. I t must a l s o be determined i f one pH con-
d i t i o n e d can p r o v i d e s a t i s f a c t o r y , a1 though
n o t optimum, removal o f the metals p r e s e n t
i n t h e wastewater.
Chemical p r e c i p i t a t i o n o f heavy metals
may be accomplished by e i t h e r b a t c h o r con-
t i n u o u s systems. For small f l o w r a t e s ( l e s s
than 50,000 g a l l o n s p e r day), s i m p l e r and l e s s
expensive b a t c h systems are more f e a s i b l e .
Another a p p l i c a t i o n o f t h e b a t c h system i s
where t h e waste c h a r a c t e r i s t i c s may be v a r i a b l e
and r e q u i r e m o d i f i c a t i o n o f treatment from
time t o time. A c o n t i n u o u s treatment system
i s a p p l i c a b l e when wastewater c h a r a c t e r i s t i c s
a r e u n i f o r m o r when f l o w r a t e s are l a r g e .
AlChE SYMPOSIUM SERIES
Hydroxide P r e c i p i t a t i o n
Arumugam ( 5 ) s t u d i e d hydroxide p r e c i p i t-
a t i o n f o r recovery o f chromium from spent tan
l i q u o r . This p r e c i p i t a t i o n process was t h e
cheapest f o r t h e removal and recovery o f
chromium. The optimum pH f o r maximum removal
w i t h 1 ime i s 6.6; removal o f chromium exceed-
ed 98% a t t h a t pH. The p r e c i p i t a t e d chromium
hydroxide i s separated by s e t t l i n g , f i l t e r e d ,
and r e d i s s o l v e d i n s u l f u r i c a c i d t o form
chromium s u l f a t e which can be r e c y c l e d f o r
f u r t h e r tanning. The use o f l i m e was more
economical than t h e use o f o t h e r a l k a l i e s
(NaOH,Na2C03, and NH40H).
Rabosky and A1 tared131 1 presented a case
h i s t o r y o f wastewater treatment f o r a small
chrome p l a t i n g shop. Caustic soda was used
t o a d j u s t t h e wastewater pH t o 9.5 - 10.0
t o p r e c i p i t a t e t h e metals as metal hydroxides.
For t h e copper wastewaters, t h e p r e c i p i t a t i o n
was c a r r i e d o u t a t pH 10.5 u s i n g NaOH.
S h e f f i e l d (138) i n v e s t i g a t e d 1ime p r e c i p i -
t a t i o n f o r removal o f copper, i r o n , n i c k e l ,
chromium, and lead. These metals from these
e l e c t r o p l a t i n g shops c o u l d be s u c c e s s f u l l y
removed by p r e c i p i t a t i n g w i t h a hydroxide
(such as l i m e ) or soda ash w i t h a d d i t i o n o f
s u l f a t e o r s u l f i d e f o r t h e enhancement i n
removing t h e copper/i r o n complexes.
Peters and Ku (124) s t u d i e d batch precipi-
t a t i o n o f zinc, cadmium, and n i c k e l by both
hydroxide and s u l f i d e p r e c i p i t a t i o n f o r
v a r i o u s pH c o n d i t i o n s , r e a c t i o n times, and
type and c o n c e n t r a t i o n o f complexing agents.
The metal hydroxide p r e c i p i t a t e s tend t o be
c o l l o i d a l a n d amorphous i n nature, causing
t h e r e s u l t i n g sludqe t o be voluminous. The
presence o f complexing agents severely i n -
h i b i t e d metal hydroxide p r e c i p i t a t i o n . Gen-
e r a l l y h i g h e r pH c o n d i t i o n s enhance t h e
n u c l e a t i o n r a t e and enhances the r e s u l t i n g
p a r t i c l e s i z e d i s t r i b u t i o n . I n t h e absence
o f c h e l a t i n q agents, extremely low r e s i d u a l
z i n c and cadmium concentrations (Zn < 0 . 5
mg/l, Cd i 0.3 mq/l) c o u l d be obtained.
Hydroxide prec'ipi t a t i o n o f heavy metats
i s w e l l s u i t e d f o r automatic pH c o n t r o l and
has been shown t o be an e f f e c t i v e treatment
technique i n i n d u s t r y . As an example o f the
e f f e c t i v e n a t u r e o f hydroxide p r e c i p i t a t i o n
reTyyal e f f i c f p c i e s exceeded 98% f o r Cd++,
Cr , and Pb u s i n g spiked w e l l waters and
r i v e r waters ( 4 3 , 1 4 3 , 1 4 4 ) . L i m i t a t i o n s
associated w i t h t h e use o f hydroxide t r e a t -
ment(i2i) i n c l u d e :
No. 243,Vol. 81
Hydroxide p r e c i p i t a t e s tend t o r e s o l u b i 1 i z e
i f t h e s o l u t i o n pH i s changed.
Chromium ( V I ) i s n o t removed by hydroxide
precipitation.
Removal o f metals hydroxide p r e c i p i t a t i o n
o f mixed metal wastes may n o t be e f f e c t i v e
because t h e minimum s o l u b i l i t i e s f o r d i f -
f e r e n t metals occur a t d i f f e r e n t pH con-
ditions.
The presence o f complexing agents may have
an adverse e f f e c t on metal removal.
Cyanide i n t e r f e r e s w i t h heavy metal r e -
moval by hydroxide p r e c i p i t a t i o n .
Hydroxide sludge q u a n t i t i e s can be sub-
s t a n t i a l and are g e n e r a l l y d i f f i c u l t t o
dewater due t o the amorphous p a r t i c l e
structure.
Carbonate P r e c i p i t a t i o n
Patterson e t a1 . ( i l l )s t u d i e d t h e feasibility
o f carbonate p r e c i p i t a t i o n f o r heavy metals
removal. Carbonate p r e c i p i t a t i o n has several
advantages over t h a t o f conventional hydroxide
precipitation:
Optimum carbonate p r e c i p i t a t i o n treatment
occurs a t lower pH c o n d i t i o n s than those
f o r optimum hydroxide treatment.
Metal carbonate p r e c i p i t a t e s are r e p o r t e d
t o be denser than t h e hydroxide p r e c i p i t a t e
causing inproved s o l i d s separation.
Carbonate sludges have b e t t e r f i l t r a t i o n
c h a r a c t e r i s t i c s than hydroxide sludges.
For t h e case o f n i c k e l and z i n c , no b e n e f i t
i s d e r i v e d by u t i l i z i n g carbonate p r e c i p i t a t i o n
as opposed t o hydroxide p r e c i p i t a t i o n ; t h e
optimum pH f o r metal removal corresponds t o
t h e pH values p r e d i c t e d by the t h e o r e t i c a l
metal hydroxide s o l u b i l i t y diagram. No advan-
tage i n terms o f denser sludges o r b e t t e r
f i l t r a t i o n c h a r a c t e r i s t i c s were observed f o r
t h e z i n c carbonate and n i c k e l carbonate systems
over t h a t f o r t h e corresponding hydroxide
systems. B e n e f i c i a l r e s u l t s were observed
u s i n g carbonate p r e c i p i t a t i o n f o r cadmium and
l e a d removal. Comparable r e s i d u a l cadmium
c o n c e n t r a t i o n s were observed approximately
2 pH u n i t s lower f o r carbonate treatment versus
hydroxide treatment. The cadmium carbonate
system p r e c i p i t a t e had r e l a t i v e f i l t r a t i o n
r a t e s approximately t w i c e t h a t o f t h e cadmium
hydroxide system. Treatment e q u i v a l e n t t o
t h a t f o r l e a d hydroxide a t pH 10.5 was obtained
w i t h the lead, carbonate system a t pH {.? and
a t o t a l carbonate c o n c e n t r a t i o n o f 10- *
moles/l, o r a t pH 10 a d a t o t a l carbonate
c o n c e n t r a t i o n o f 10-2.9 m o l e s / l . The l e a d
carbonate system y i e l d e d a denser p r e c i p i t a t e
than t h e l e a d hydroxide system w i t h improved
167
f i l t e r a b i l i t y characteristics.
Sodium bicarbonate can a l s o be used t o
p r e c i p i t a t e t h e heavy metals o u t o f s o l u t i o n
(8). Such treatment has t h e dual advantage
o f p r e c i p i t a t i n g t h e metal carbonate h o l d i n g
pH w i t h i n a narrow range a t n e a r l y optimum
l e v e l s . Although sodium bicarbonate i s n o t
as e f f i c i e n t i n removing metal from s o l u t i o n
as o t h e r bases, i t has t h e advantage o f
n e u t r a l i z i n g excess a c i d i t y and t h i s helps
meet wastewater discharge standards. The
sodium bicarbonate a c t s as a b u f f e r t o main-
t a i n a l k a l i n i t y near t h e optimum pH l e v e l .
Some metals, such as zinc, do n o t r e a d i l y
p r e c i p i t a t e r e g a r d l e s s o f t h e amount o f c a r -
bonate added. However, by mixing soda ash,
sodium bicarbonate, and lime, i t i s p o s s i b l e
t o p r e c i p i t a t e z i n c as hydroxide w h i l e u s i n g
the carbonates t o s t a b i l i z e pH. Sodium b i -
carbonate treatment has the a d d i t i o n a l ad-
vantage o f easy handling, simple a p p l i c a t i o n ,
a b i l i t y t o f u n c t i o n i n continuous f l o w
operation, and moderate c o s t .
Sulfide Precipitation
S u l f i d e p r e c i p i t a t i o n has been demon-
s t r a t e d t o be an e f f e c t i v e a l t e r n a t i v e t o
hydracide precipitaticn ( 17,18,45,56,73,81,119,121,124,125 1
f o r removal o f heavy metals from i n d u s t r i a l
wastewaters. A t t r a c t i v e f e a t u r e s o f t h i s
process i n c l u d e :
Attainment o f a h i g h degree o f metal r e -
moval even a t low pH (pH - 2-3).
Low d e t e n t i o n time requirements i n t h e
r e a c t o r . because o f t h e h i g h r e a c t i v i t i e s
o f sulfides.
F e a s i b i l i t y o f s e l e c t i v e metal removal
and recovery.
Metal s u l f i d e sludge i s t h r e e times l e s s
s u b j e c t t o l e a c h i n g a t pH 5 as compared
t o metal hydroxi de sl udge(l5g)making f i n a l
disposal s a f e r and e a s i e r .
Metal s u l f i d e sludges e x h i b i t b e t t e r
t h i c k e n i n g and dewatering c h a r a c t e r i s t i c s
than t h e corresponding metal hydroxide
sludges.
L i m i t a t i o n s o f the process i n v o l v e the po-
t e n t i a l o f H S gas e v o l u t i o n and t h e concern
f o r s u l f i d e ?oxicity. Eliminating s u l f i d e
reagent overdose prevents formation o f t h e
odor causing H S. I n c u r r e n t l y operated
s o l u b l e s u l f i d g systems which do n o t match
demand, t h e process tanks must be enclosed
and vacuum evacuated t o minimize s u l f i d e odor
problems.
Two main processes e x i s t f o r s u l f i d e
168 Separation of Heavy Metals
precipitation of heavy metals (45) : soluble
sulfide precipitation (SSP) and insoluble s u l -
fide precipitation ( I S P ) , the difference being
on how the sulfide ion i s introduced i n t o the
wastewater. In the SSP process, sulfide i s
added in the form of a water soluble sulfide
reagent such as sodium sulfide (Na S ) or
sodium hydrosulfide. I n the ISP pfocess, a
slightly soluble ferrous sulfide (FeS) slurry
i s added t o the wastewater t o supply the
needed sulfide ions needed t o precipitate the
heavy metals. Since most of the heavy metals
have sulfides less soluble than ferrous sul-
fide, they will precipitate a s metal sulfides.
Advantages of the ISP process include the
absence of any6detect$gle H S gas and re-
duction of Cr t o Cr . D?sadvantages of
the process include considerably larger t h a n
stoichiometric reagent consumption and 1 arge
quantities of sludge being generated due t o
the ferrous hydroxide formation, In the SSP
process, the high sulfide concentration often
causes rapid precipitation of metal sulfides
(high nucleation rates) resulting in small
particulate fines and hydrated colloidal
particles. This causes poor s e t t l i n g and
f i l t e r i n g of the flocs. In the presence of
chelating agents, hydroxide precipitation of
heavy metals i s n o t possible even a t high pH.
With sulfide precipitation, heavy metal removal
i s possible even with chelants present, a l -
t h o u g h the heavy metal precipitation i s in-
fluenced by the presence of chelating agents.
In the absence of chelating agents, l i t t l e
metal hydroxide precipitation occurs f o r pH < 6.
An excellent description and review of the
sulfide precipitation processes has been pro-
vi ded by EPA (45).
Bhattacharyya e t a l . (17) found sulfide
precipitation using Na2S to be highly effective
for removal of Cd, Zn, Cu, Pb, As, and Se from
complex wastewaters. The separation character-
i s t i c s were evaluated using a dilute synthetic
wastewater and an actual copper smelting p l a n t
wastewater. Overall separation and precipi-
t a t e s e t t l i n g rates were optimum for under-
stoichiometric addition of sulfide (-0.60 x
theoretical stoichiometric sul fide requi rement)
and pH > 8.0. For the copper smelting plant
wastewater, removal of Cd, Zn, and Cu exceeded
99%, w i t h the removals of As and Se being 98%
and > 92%, respectively. The residual con-
centrations achieved f o r Cd, Cu, and Zn were
consistently in the range of 0.05-0.10 mg/l.
Using only hydroxide treatment, the s e t t l i n g
rates and metal separations were considerably
lower t h a n t h a t obtained by sulfide precipi-
t a t i o n . The Zn, Cd, and Se removals were much
poorer, even a t pH 10.5, using hydroxide t r e a t -
ment. A t pH 8.5, the residual metal concentra-
AlChE SYMPOSIUM SERIES
tions of Se, Cd, and Zn were 9,2, and 5 mg/l,
respectively. A t pH 10.5, the residual Cd
and Zn concentrations decreased t o 0.6 and
1.1 mg/l, respectively. The s e t t l i n g r a t e
of the sludges was a function of pH and the
suifide dose. Poor s e t t l i n g velocities re-
sulted from hydroxide precipitation and excess
sulfide precipitation. The s e t t l i n g rate
with 0 . 6 ~was twice t h a t obtained by hydroxide
precipitation. Bhattacharyya e t a l . (21) ob-
served essentially complete removal of zinc
using sulfide precipitation ( 1 . 0 ~ )for pH > 4.
Measurements taken on H2S loss (as gas) showed
H S loss was negligible due t o the preference
f$r the metal sulfide reaction over the
H -S- reaction. The f a c t t h a t nickel pre-
cipitation with sulfide was found to be a
s t r o n g function of reaction time for pH < 10
i n open systems was attributed to nickel
dissolution causing the formation of Ni(SOH)2
and NiSO i n the presence of oxygen. Using
sulfide ffrecipitation, residual concentrations
less t h a n 0.1 mg/l for Cu, Cd, Pb, and Zn
can be achieved(l8) for the pH range of 4-12.
The combined hydroxide-sulfide treatment a t
pH 8-9 was shown effective for removal of
As, Zn, Cd, Pb, Cu, Hg, and Fe in both
synthetic wastewaters and for full-scale
operation of wastewaters a t the Boliden Metal1
Corporation, Skelleftehamn, Sweden. Even
with sulfide overdoses a t low pH, no H2S gas
loss was observed.
Fender e t a l . (49) studied sulfide pre-
cipi tation for zinc-1 aden foundry wastewaters.
The wastewater pH was adjusted with 1 ime t o
pH's ranging from 8.5 t o 11.0. Ferrous sul-
fide (750 mg/l) was added t o each sample.
The residual lead and iron concentrations
were consistently less t h a n 0.1 mg/l for
i n i t i a l wastewater concentrations of 0.1 and
21.1 mg/l, respectively. The zinc concentra-
tion decreased from 775 mg/l t o 1.7-3.7 mg/l;
however t h i s removal was s t i l l inadequate.
Two stage hydroxi de/sul f i de prec i pi t a t i on
was investigated. The best treatment occurred
for lime treatment a t pH 9.6 t o which 20 mg/l
FeS was added t o the supernatant, resulting
i n a final f i l t e r e d effluent concentration
of 0.05 mg/l Zn.
A full scale SSP treatment plant(l33)was
constructed by the U.S. Army a t the Belvoir
Research and Development Center in Fort
Belvoir. Virainia. becomina oDerationa1 in
February 1985. Safety f e a h es of the plant
included: neutralization of the wastewater
pH prior t o sulfide a d d i t i o n automatic con-
t r o l of the sulfide feed via a specific ion
probe, ferrous sulfate addi t on t o remove
the excess sulfide, hydrogen peroxide oxidatioi
No. 243,Vol. 81
o f t h e r e s i d u a l e f f l u e n t s u l f i d e , and covering
and v e n t i 1a t i o n o f t h e process tanks. Removal s
exceeding 90% were observed f o r Cd, C r y Cu,
N i , and Zn, w i t h removal o f Pb exceeding 80%.
The sludge generated averaged 0.3 g a l l o n s o f
sludge/1000 g a l l o n s o f wastewater t r e a t e d ;
t h e s o l i d s c o n t e n t o f t h e f i l t e r cake averaged
23.4% w i t h o u t t h e use o f any sludge condi-
t i o n e r s . The sludge samples were found t o
be nonhazardous w i t h r e s p e c t t o t o x i c i t y using
t h e standard EPA t o x i c e x t r a c t i o n procedure
f o r hazardous waste determination. Chemical
c o s t s averaged $0.30/1000 gal 1ons - S1 udge
disposal c o s t s averaged $0.41/1000 g a l l o n s
o f wastewater t r e a t e d , causing t h e t o t a l
o p e r a t i o n a l c o s t t o be $0.71/1000 g a l l o n s
( e x c l u d i n g manpower and energy c o s t s ) .
Peters e t a l . (119,121,124) have s t u d i e d t h e
p a r t i c l e s i z e d i s t r i b u t i o n s o f ZnS, CdS, and
N i S p r e c i p i t a t i o n , because t h e removal e f -
f i c i e n c y and ease o f removing the sludge are
coupled. Both heavy metals removals and
p a r t i c l e s i z e d i s t r i b u t i o n s (PSD) were r e p o r t -
ed. Using s u l f i d e p r e c i p i t a t i o n v i r t u a l l y
a l l t h e z i n c was removed(l2l)at pH 8-10 ( r e s i -
dual Zn < 0.30 mg/l; removal e f f i c i e n c y >99.7%)
Few p a r t i c l e s l a r g e r than 20 pm i n s i z e were
observed; t h e dominant p a r t i c l e s i z e was o n l y
5-7 pm f o r t h e p r e c i p i t a t e s , causing a cloudy
appearance f o r t h e r e a c t o r suspension and
making sedimentation and f i l t r a t i o n operations
d i f f i c u l t . T h i s suggests a f l o c c u l a n t o r
coagulant a i d would be advantageous f o r t h i s
system. A1 though very h i g h s u p e r s a t u r a t i o n s
were achieved, t h e k i n e t i c o r d e r was low
(i< 1.02) f o r continuous ZnS p r e c i p i t a t i o n .
L i t t l e e f f e c t i s observed on t h e r e s u l t i n g
PSD by v a r y i n g t h e r e a c t o r d e t e n t i o n time,
T. I n c r e a s i n g t h e suspended s o l i d s concentra-
t i o n increases b o t h t h e p a r t i c l e growth r a t e
and t h e p r e c i p i t a t e dominant s i z e y i e l d i n g a
more f a v o r a b l e PSD. The presence o f c a l c i u m
improved t h e s e t t l i n g c h a r a c t e r i s t i c s o f both
t h e Cd-Ca-Na S and t h e Cd-Cas s l u r r y systems.
The metal s u g f i d e r e a c t i o n s are extremely
r a p i d ; chemical e q u i l i b r i a i s achieved w i t h i n
5 minutes r e a c t i o n time. A phase transform-
a t i o n from an i n i t i a l amorphous k i n e t i c a l l y
favored p r e c i p i t a t e t o a more c r y s t a l l i n e
thermodynamically favored p r e c i p i t a t e was i n -
d i c a t e d f o r t h e ZnS system as t h e p r e c i p i t a t e
.
ages. Patterson e t a1 (1ll)and Patterson and
Minear(ll3)have a l s o noted such phase t r a n s -
formations. P a r t i c l e s i z e r a t h e r than com-
pleteness o f t h e s o l i d phase f o r m a t i o n may
o f t e n times c o n t r o l t h e apparent removal e f -
f e c t i veness .
Peters and Ku (124) s t u d i e d batch p r e c i p i t-
a t i o n o f zinc, cadmium, and n i c k e l u s i n g both
169
hydroxide and s u l f i d e p r e c i p i t a t i o n a t v a r i o u s
pH c o n d i t i o n s w i t h and w i t h o u t t h e presence
and complexing agents. EDTA i n h i b i t e d z i n c
removal by b o t h hydroxide and s u l f i d e t r e a t -
ment due t o t h e f o r m a t i o n o f s t a b l e metal
chelates; t h e e f f e c t was more pronounced f o r
t h e Zn(0H) system. Extremely low r e s i d u a l
metal c o n c h t r a t i o n s can be achieved u s i n g
s u l f i d e p r e c i p i t a t i o n i n t h e absence o f c h e l a t -
i n g agents. Enhanced removals are achieved
u s i n g s u l f i d e p r e c i p i t a t i o n even i n t h e pre-
sence o f complexing agents, as compared t o
s i m i 1a r hydroxide p r e c i p i t a t i o n c o n d i t i o n s .
The presence o f phosphate enhances t h e PSD
due t o a flocculation/agglomeration mechanism.
The presence o f ammonia has a minimal e f f e c t
on metal s u l f i d e removal and t h e p r e c i p i t a t i o n
k i n e t i c s . The presence o f EDTA and crown
e t h e r s e v e r e l y i n h i b i t s CdS p r e c i p i t a t i o n .
E q u i l i b r i u m c o n d i t i o n s are q u i c k l y reached,
w i t h i n 5.0 minutes r e a c t i o n time, f o r the ZnS
and CdS systems, w h i l e e q u i l i b r i u m i s achieved
a f t e r 40 minutes r e a c t i o n time f o r t h e N i S
system, due t o o x i d a t i o n o f s u l f i d e i n t h e
open system.
1
The e f f e c t on c h e l a n t s on metal s u l f i d e
p r e c i p i t a t i o n s was addressed by Peters e t a1 .
(120)EDTA f o r m s s t r o n g metal c h e l a t e s which
i n t e r f e r e w i t h ZnS p r e c i p i t a t i o n . Weak c h e l -
a t i n g agents ( c i t r a t e , g l u c o n i c acid, t a r t r a t e ,
e t c . ) form weak metal chelates; f o r m a t i o n o f
t h e metal s u l f i d e p r e c i p i t a t e predominates.
Removal o f copper i s n e a r l y complete even i n
t h e presence o f EDTA.
Hohman(5)selectively p r e c i p i t a t e d Cd f r o m
a Cd-Fe wastewater a t pH 2 by employing a
s t o i c h i o m e t r i c + $ y l f i d e dose o n l y f o r t h e cad-
mium ions. Fe was s e l e c t i v e l y removed from
Cd a t pH 6 u s i n g hydroxide p r e c i p i t a t i o n .
The CdS p r e c i p i t a t i o n step goes t o completion
w i t h i n 1.0 minute r e a c t i o n time, w h i l e FeS
p r e c i p i t a t i o n i s much slower. A t h i g h s u l f i d e
l e v e l s , FeS r e s o l u b i l i z e s on formation o f
s o l u b l e species o r c o l l o i d s .
Peters and Ku (125) s t u d i e d the continuous
p r e c i p i t a t i o n o f zinc, n i c k e l , copper, and
chromium by both hydroxide and s u l f i d e t r e a t -
ment u s i n g s y n t h e t i c and a c t u a l i n d u s t r i a l
p l a t i n g wastewaters. For a z i n c - n i c k e l waste-
water, s l i g h t l y lower r e s i d u a l s and enhanced
f l o c s i z e were observed f o r s u l f i d e treatment
versus hydroxi de treatment . Low pH treatment
pH - 7.2-7.4) r e s u l t s i n incomplete removal
o f nickel; zinc p r e c i p i t a t i o n i s preferential
t o t h a t o f n i c k e l . A t h i g h e r pH l e v e l s (pH-lo),
removal o f both n i c k e l and z i n c exceeded 98%
u s i n g e i t h e r hydroxide o r s u l f i d e treatment.
Larger s u l f i d e doses and h i g h e r pH c o n d i t i o n s
 170 Separation of Heavy Metals
r e s u l t e d i n both g r e a t e r metal removals and
l a r g e r s e t t l i n g v e l o c i t i e s . Chromium was
n o t e f f e c t i v e l y removed from t h e Zn-Cu-Ni-Cr
wastewater u s i n g hydroxide treatment. In-
c r e a s i n g the s u l f i d e dose causes lower r e s i d u a l
heavy metal c o n c e n t r a t i o n s f o r Zn, Cu, and
C r , w h i l e t h e n i c k e l c o n c e n t r a t i o n increased
due t o t h e f o r m a t i o n o f f i n e f l o c s . A t pH
10.0 o p e r a t i o n u s i n g s u l f i d e treatment, r e -
movals exceeded 97%, 97%, 55%, and 83%, r e -
s p e c t i v e l y f o r Zn, Cu, C r , and N i . The under-
s t o i c h i o m e t r i c a d d i t i o n o f s u l f i d e appears
extremely promising as a treatment technique
t o achieve extremely low metal r e s i d u a l s w h i l e
m i n i m i z i n g t h e H2S e v o l u t i o n p o t e n t i a l and
s u l f i d e t o x i c i t y problems.
Kim(75) found t h a t calcium s u l f i d e s l u r r i e s ,
prepared by r e a c t i n g l i m e w i t h e i t h e r hydrogen
s u l f i d e o r sodium h y d r o s u l f i d e , a r e e f f e c t i v e
f o r metal s u l f i d e p r e c i p i t a t i o n . The a d d i t i o n
of Cas can be c o n t r o l l e d i n most cases by
measuring t h e pH. The use o f Cas enabled
wastewaters c o n t a i n i n g o i l emulsions and d i s -
solved copper t o be e f f e c t i v e l y t r e a t e d (73)
The a d d i t i o n o f Cas produces e a s i l y s e t t e a b l e
p r e c i p i t a t e s . The Cas p a r t i c l e s a c t as n u c l e i
s i t e s f o r t h e p r o d u c t i o n o f t h e metal s u l f i d e
p r e c i p i t a t e s . The d i s s o l v e d calcium a l s o
f u n c t i o n s as a coagulant. Since t h e c a l c i u m
added i n the form o f CaS i s d i s s o l v e d i n t h e
wastewater a f t e r r e a c t i o n , t h e increase i n
sludge volume i s minimal.
Coprecipi tation/Combined Chemical Treatment
McAnnally e t a l . (91) s t u d i e d t h e use o f
s o l u b l e s u l f i d e and carbonate f o r t h e i r e f -
f e c t i v e n e s s i n reducing n i c k e l i n a s y n t h e t i c
n i c k e l p l a t i n g wastewater. Employing j a r t e s t s ,
an optimum pH range f o r n i c k e l removal from
t h e s y n t h e t i c wastewater was found t o be 10.0-
11.0. Optimum removal occurred a t pH 11 where
a r e s i d u a l t o t a l n i c k e l c o n c e n t r a t i o n o f 0.1
mg/l was obtained w i t h a s u l f i d e : n i c k e l
weight r a t i o o f 2.0 and a carbonate: n i c k e l
weight r a t i o o f 20.0. A t pH 10, a s i m i l a r
degree o f removal (0.2 mg/l r e s i d u f l t o t a l
N i ) was obtained us?? a CO -: N i ratio
o f 10.0 and a S - : N i r a t i a o f 0.5. The
authors o f t h i s c u r r e n t paper speculate t h e
e x c e l l e n t N i removals observed are due t o a
c o p r e c i p i t a t i o n phenomena. TO t r e a t t h e
s y n t h e t i c n i c k e l wastewater, t h e pH was ad-
j u s t e d by dropwise a d d i t i o n o f 1N NaOH and
an e q u i v a l e n t amount o f 1N CaCl s o l u t i o n t o
simulate lime addition. The ca6bonate was
added i n t h e form o f NaHCO . Such c o n d i t i o n s
l i k e l y l e d t o the p r e c i p i t a t i o n o f calcium
carbonate, which has been shown t o be an ex-
cellent adsorbant for Cd,Ca,pb, and Zn(31,48,122,123).
AlChE SYMPOSIUM SERIES
Coprecipi t a t i o n and a d s o r p t i o n o f N i (OH)2,
and N i S onto t h e CaC03 surfaces may have
caused such excel l e n t N i removals. McAnnal l y
e t a1 .(91) however, d i d n o t r e p o r t t h e r e s i d u a l
c a l c i u m c o n c e n t r a t i o n s t o a s c e r t a i n whether
t h i s was t h e case o r n o t .
I n a study s i m i l a r t o t h a t o f McAnally
e t a l . (91) , McFadden e t a1 (74) i n v e s t i g a t e d
t h e e f f e c t o f i r o n as a c o p r e c i p i t a t o r o f
n i c k e l as w e l l as carbonate a d d i t i o n , pH
adjustment, and polymer a d d i t i o n . For pH
adjustment along w i t h carbonate a d d i t i o n ,
t h e optimum n i c k e l removal occurred f o r a
t o t a l carbonate c o n c e n t r a t i o n ( C ) o f 50 mg/l
a t pH 11. These c o n d i t i o n s resuTted i n t h e
s o l u b l e and t o t a l n i c k e l c o n c e n t r a t i o n s being
CO.10 and 0.10 mg/l, r e s p e c t i v e l y . A l l t h r e e
C c o n c e n t r a t i o n s employed (50, 100, and
260 mg/l) a t pH 10 and 11 achieved a t l e a s t
96% and 99% removal o f t h e t o t a l and s o l u b l e
n i c k e l , r e s p e c t i v e l y . McFadden e t a l . (94)
suggest t h e c a l c i u m may p r o v i d e a nucleus
f o r CaCO f o r m a t i o n thereby i n c r e a s i n g
s e t t l e a b j l ity, a1 though they do n o t r e p o r t
t h e f i n a l r e s i d u a l c a l c i u m c o n c e n t r a t i o n s ++
o f t h e t r e a t e d wastewater. The i n i t i a l Ca
c o n c e n t r a t i o n s were of t h e same manner as t h a t
o f McAnally e t a1 .(91). C o p r e c i p i t a t i o n o f
N i onto t h e CaCO surfaces may indeed be an
e x p l a n a t i o n f o r Zhe h i g h n i c k e l removals.
N i c k e l removal u s i n g hydroxide p r e c i p i -
t a t i o n was most e f f i c i e n t f o r t h e s y n t h e t i c
wastewater a t @I 10-11, depending on the Fe:
N i r a t i o and C (94). Both t h e s o l u b l e and
t o t a l n i c k e l a i pH 10, Fe:Ni = 2, and C = 0,
were reduced t o CO.10 mg/l. I d e n t i c a l $e-
s u l t s occurred a t pH ll,Fe:Ni = 2, and C -
100 mg/l as CaCO . A t pH 9 t h e b e s t o v e r a i l
removal was obta?ned f o r a Fe:Ni r a t i o of
1.0 and CT = 50 mg/l as CaCO , where t h e
t o t a l and s o l u b l e r e s i d u a l nqckel concentra-
t i o n s were 0.20 and 0.10 mg/l, r e s p e c t i v e l y .
For t h e a c t u a l wastewater, t h e most e f f i c i e n t
s o l u b l e n i c k e l removal occurred a t pH 10 w i t h
a Fe:Ni r a t i o o f 0.7 and C o f 0 mg/l as
CaC03. A t pH 9, the most z f f i c i e n t n i c k e l
removal f o r t h e a c t u a l wastewater occured
a t an Fe:Ni r a t i o o f 2.0 and C = 0 r e s u l t i n g
i n a t o t a l and s o l u b l e n i c k e l l o n c e n t r a t i o n
o f 0.30 and 0.25 m g / l , r e s p e c t i v e l y . The use
o f a n i o n i c and c a t i o n i c polymers d i d n o t
enhance t h e removal o f n i c k e l appreciably.
On t h e a c t u a l wastewater, the lowest c o s t
t o t r e a t t h e wastewater was $0.5349/1000
g a l l o n s f o r c o n d i t i o n s o f pH 10, Fe:Ni r a t i o
o f 0.7, and CT = 0.
Using f e r r o u s s u l f i d e as a c o p r e c i p i t a t o r
heavy metals (Cu, Cd, N i , Cr, and Zn) were
No. 243, Vol. 81
shown t o be s i g n i f i c a n t l y reduced i n concen-
t r a t i o n from t h e i n f l u e n t wastewater (136).FeS
treatment was found t o be s u p e r i o r t o con-
v e n t i o n a l hydroxide p r e c i p i t a t i o n employing
l i m e as t h e p r e c i p i t a n t .
P i l o t p l a n t s t u d i e s (%)employing t h e con-
d i t i o n s o f l i m e a d d i t i o n (260 mg/l g i v i n g r i s e
t o a pH o f 10.0) p l u s 20 mg/l f e r r o u s s u l f a t e
were used t o t r e a t a n i c k e l wastewater i n i t i a l -
l y c o n t a i n i n g 5 mg/l N i . The r e s i d u a l
n i c k e l c o n c e n t r a t i o n was reduced t o 0.35 mg/l
a f t e r sedimentation and f i l t r a t i o n . Hydroxide
p r e c i p i t a t i o n alone (pH 11.5, Ca(0H) dosage =
600 mg/l) r e s u l t e d i n a r e s i d u a l n i c a e l con-
c e n t r a t i o n o f 0.15 mg/l a f t e r sedimentation
and f i l t r a t i o n . Leckie e t a1 484). l i k e w i s e
observed t h a t t r a c e elements o f cadmium, zinc,
lead, arsenic, selenium, s i l v e r , chromium,
copper, and vanadium c o u l d be removed by ad-
s o r p t i o n / c o p r e c i p i t a t i o n w i t h amorphous i r o n
oxyhydroxide. For the case o f both anion and
c a t i o n adsorption, i r o n dose and s o l u t i o n pH
were t h e two adsorption c o n t r o l 1 i n g parameters.
Chang and Peters (31) observed t h a t cadmium
c o u l d be very e f f e c t i v e l y removed u s i n g conven-
t i o n a l l i m e s o f t e n i n g operations; t h e maximum
contaminant l e v e l o f 0.01 mg/l f o r Cd c o u l d
be met f o r t h e pH range o f 7.3-11.0. Calcite
was t h e o n l y morphological form observed f o r
the continuous CaCO p r e c i p i t a t i o n . The r e -
s i d u a l calcium c o n c s n t r a t i o n increased 1-30-40
mg/l i n t h e presence o f cadmium i n d i c a t i n g
an i n h i b i t o r y e f f e c t o f cadmium on CaCO pre-
c i p i t a t i o n . Removal o f cadmium was a t r j b u t e d
p r i m a r i l y t o p h y s i c a l a d s o r p t i o n onto t h e CaC03
s 1udges .
Tal b o t (153)descri bed a process u s i n g l e s s
than s t o i c h i o m e t r i c a d d i t i o n o f s u l f i d e g i v i n g
a combined h y d r o x i d e - s u l f i d e treatment. A t
pH 8.0, a s o l u t i o n i n i t i a l l y c o n t a i n i n g 15.0
mg/l Cd was lowered t o <O 05 mg/l u s i n g t h e
T a l b o t process, w h i l e hydroxide treatment p r o -
v i d e d a r e s i d u a l c o n c e n t r a t i o n o f 4.8 mg/l.
For a water c o n t a i n i n g 2.9 mg/l Hg, convention-
a l hydroxide treatment r e s u l t e d i n no mercury
removal , w h i l e t h e Tal b o t process lowered the
mercury l e v e l t o <0.001 mg/l a t pH 8.0. The
o p e r a t i n g c o s t o f t h e T a l b o t process i s com-
p a r a b l e t o t h a t o f conventional hydroxi de p r e -
c i p i t a t i o n . A s m a l l e r quani t i t y o f sludge
i s generated by t h e T a l b o t process (as compared
t o conventional hydroxide p r e c i p i t a t i o n ) t h e r e -
by l o w e r i n g t h e sludge disposal c o s t s . Peters
e t a1 .(118)likewise observed t h a t u n d e r s t o i c h -
i o m e t r i c a d d i t i o n o f s u l f i d e , even as low as
0.5 x s t o i c h i o m e t r i c requirement, l i k e w i s e
p r o v i d e d e x c e l l e n t removal o f z i n c and cadmium,
and decreased t h e r e s u l t i n g sludge volume.
171
They proposed t h e idea t h a t metals c o u l d be
s e l e c t i v e l y p r e c i p i t a t e d , removed, and r e -
covered from a mixed-metal wastewater, by
proper c o n t r o l o f the pH, s u l f i d e dose,
c h e l a n t dose, type o f chelant, and temperature,
i n a cascading s e r i e s o f r e a c t o r s . For ex-
ample, z i n c can be s e l e c t i v e l y p r e c i p i t a t e d
from n i c k e l a t pH 6.0, s t o i c h i o m e t r i c s u l f i d e
dose, and a d d i t i o n o f EDTA (118)Pugsley e t
a1 .(129) were t h e f i r s t i n v e s t i g a t o r s t o note
t h a t s e l e c t i v e removal o f a p a r t i c u l a r heavy
metal could be achieved i n a cascading r e a c t o r
system through proper c o n t r o l o f t h e dosage
r a t e s . P r e l i m i n a r y c o s t estimates show t h e
s u l f i d e treatment process t o be -$9.27/1000
g a l l o n s o f p l a t i n g wastewater, which f a v o r a b l y
compares w i t h t h e -$9.45/1000 g a l l o n s o f
p l a t i n g wastewater by conventional hydroxide
treatment (118)Considerable c o s t savings can
a l s o be r e a l i z e d through reuse, recycle, and
recovery o f t h e waste metals from t h e p l a t i n g
process.
Higgins and Slater(26) observed t h a t
treatment o f a m i x t u r e o f metals i s somewhat
more e f f e c t i v e than treatment o f metals i n -
dividually S u l f i d e treatment lowers the
s o l u b i l i t y o f n i c k e l and cadmium. F e r r i c
hydroxide p r e c i p i t a t e s reduce t h e metal sol -
u b i 1 it i e s by i n c o r p o r a t i o n o f o t h e r metals
i n an amorphous p r e c i p i t a t e and provides
surface s i t e s f o r adsorption. A d d i t i o n o f
f e r r o u s s u l f a t e t o an a l k a l i n e environment
(7spH(10) causes the i r o n t o p r e c i p i t a t e as
i r o n hydroxide and a i d s i n t h e f l o c c u l a t i o n
o f s o l i d s i n t h e process. Such treatment
was very e f f e c t i v e i n r e d u c t i n g hexavalent
chromium t o the t r i v a l e n t form. A combination
o f f e r r o u s s u l f a t e and sodium s u l f i d e produces
a sludge t h a t i s e a s i l y removed, y e t minimizes
sludge production.
Brantner and Cichon (26)studied and com-
pared the hydroxide, carbonate, and s u l f i d e
treatments f o r removal o f heavy metals (Zn,
C r , Cd, Cu, and Pb). E f f e c t i v e z i n c removal
was obtained by a l l t h r e e chemical p r e c j p i -
t a t i o n processes. For low s o l u b l e z i n c
l e v e l s i n the c l a r i f i e r overflow, i t appeared
z i n c removal was n o t l i m i t e d by s o l u b i l i t y
b u t r a t h e r by t h e e f f e c t i v e n e s s o f t h e s o l i d s -
l i q u i d separation. The i n a b i l i t y o f carbonate
p r e c i p i t a t i o n t o c o n s i s t e n t l y achieve low
r e s i d u a l z i n c concentrations was a t t r i b u t e d
t o t h e k i n e t i c s o f z i n c carbonate formation
causing the s o l u b i l i t y o f zinc hydroxide t o
govern t h e removal o f z i n c . E f f e c t i v e r e -
moval o f chromium was o n l y achieved by s u l -
f i d e p r e c i p i t a t i o n . P r e c i p i t a t i o n o f cadmium
and copper was very e f f e c t i v e l y achieved by
a l l t h r e e processes. Removal o f l e a d was
172 Separation of Heavy Metals
e f f e c t i v e l y achieved by carbonate and s u l f i d e
p r e c i p i t a t i o n causing a r e s i d u a l f i l t e r e d l e a d
c o n c e n t r a t i o n o f <0.1 mg/l; hydroxide p r e c i p i -
t a t i o n r e s u l t e d i n a mean e f f l u e n t l e v e l o f
0.2 mg/l. O f t h e t h r e e p r e c i p i t a t i o n pro-
cesses, carbonate p r e c i p i t a t i o n produced t h e
s m a l l e s t sludge volume. N e i t h e r t h e hydroxide
sludges o r t h e s u l f i d e sludges thickened w e l l
i n t h e c l a r i f i e r . When subjected t o a c i d i f i -
c a t i o n , t h e hydroxide sludge was the l e a s t
s t a b l e w h i l e t h e s u l f i d e sludge was t h e most
stable.
COAGULATION/FLOCCULATION
Coagul a t i o n / f l o c c u l a t i o n has been known
capable o f removing heavy metals from s o l u t i o n .
Coagulation r e f e r s t o t h e charge n e u t r a l i z a t i o n
o f t h e p a r t i c l e s . F l o c c u l a t i o n i n v o l v e s slow
m i x i n g t o promote the agglomeration o f t h e
d e s t a b i l i z e d p a r t i c l e s . EPA (43) i n v e s t i g a t e d
the use o f l i m e s o f t e n i n g and c o a g u l a t i o n
( u s i n g f e r r i c s u l f a t e o r a&m) f y i remyyal +6
o f such heavy metals as Pb , Cd , C r , C r ,
e t c . While l i m e s o f t e n i n g achieved removals
o f g r e a t e r than 98% i n t h e pH range o f 8.5-11.3
f o r cadmium, cadmium removals by f e r r i c s u l f a t e
and alum c o a g u l a t i o n were lower than t h a t of
l i m e s o f t e n i n g and were shown t o depend on
pH. Cadmium removals increased w i t h i n c r e a s i n g
pH. F e r r i c s u l f a t e c o a g u l a t i o n o f a r i v e r
water c o n t a i n i n g 0.3 mg/l Cd showed removal
t o increase from 20% a t pH 7.2 t o above 90%
a t pH 2 8. Alum c o a g u l a t i o n r e s u l t s a l s o i n -
creased w i t h i n c r e a s i n g pH; however above pH 8,
removals may depend on t h e raw water t u r b i d i t y .
Both f e r r i c s u l f a t e and alum c o a g u l a t i o n
achieved g r e a t e r than 97% removal o f l e a d from
a r i v e r water c o n t a i n i n g 0.15 mg/l Pb i n t h e
pH range o f 6-10. Experiments on w e l l waters
under s i m i l a r c o n d i t i o n s had removal r a t e s by
f e r r i c s u l f a t e and a1 um c o a g u l a t i o n o f >97%
and 80-90%, r e s p e c t i v e l y . When t h e l e a d con-
c e n t r a t i o n was increased t o 10 mg/l, f e r r i c
s u l f a t e c o a g u l a t i o n again achieved removals
i n excess o f 95% whereas alum coagulaJAon
achieved o n l y -80% removal. Using C r waters,
f e r r i c s u l f a t e achieved the b e s t r e s u l t s , r e -
moving -35% a t pQ65.5 on a r i v e r water c o n t a i n -
i n g 0.15 mg/l C r . Alum c o a g u l a t i o n c o u l d
do no b e t t e r than 10% removal throughout t h e
e n t i r e pH range.+3pH has o n l y a s l i g h t e f f e c t
qn removal o f C r by alum and i r o n coagula-
t i o n . F e r r i $ 3 s u l f a t e c o a g d l a t i o n achieved
Pycellent C r removals, i n excess of 98%,
Tnroughout t h e pH range o f 6.5-9.3. Alum
oagulation, although l e s s e f f e c t i v e , o b t a i n e d
rziiovals exceeding 90% f o r t h e pH range 6.7-
5 Above pH 8.5, removals began t o decrease;
3 t pH 9 . 2 t h e remyyal had decreased t o 78%.
F o r an i n i t i a l C r c o n c e n t r a t i o n o f 10 mg/l,
AIChE SYMPOSIUM SERIES
f e r r i c s u l f a t e and alum c o a g u l a t i o n b o t h
achieved removals i n excess o f 98% i n t h e
optimum pH range.
Daniel s(38) provided an e x c e l l e n t review
on t h e removal o f heavy metals by i r o n s a l t s
and p o l y e l e c t r o l y t e f l o c c u l a n t s . Removal o f
c e r t a i n 'heavy metals f r o m wastewaters can
occur simultaneously w i t h removal o f suspend-
ed s o l i d s , BOD, and t o t a l phosphorus when
chemical t r e a t m e n t i s employed. The i n s o l u b l e
f r a c t i o n s o f Fe, C r y Zn, Cu, and N i are
captured by sequential c o a g u l a t i o n and
flocculation.
.For treatment o f base metal mine drainage,
(64),use o f an a n i o n i c polymeric f l o c c u l a n t
provided greater c l a r i f i e r operational re-
1ia b i 1it y and reduced mean metal concentrations
i n t h e o v e r f l o w . Polymer a d d i t i o n s u b s t a n t i a l -
l y improved t h e sludge s e t t l i n g characteristics
Aulenbach e t a1 .(6) observed t h a t a d d i t i o n
o f alum o r sodium aluminate a t dosages t h a t
e f f e c t i v e l y remove phosphorus i s b e n e f i c i a l
i n t h e removal o f Cu, C r , and Pb from waste-
waters. Chromium removal i s enhanced by
sodium aluminate a d d i t i o n , b u t i s u n a f f e c t e d
by alum a d d i t i o n . Both aluminum s a l t s i n -
crease t h e removal o f 1ead. N i 1ssy$lOtj) itj-
veS.igaty$ the+remov$i o f &++, Cu Cr ,
Hg , Cd , Zn , N i ' , Co , and As'5 by
aluminum s u l f a t e and calcium hydroxide t r e a t -
ment. Orthophosphate had no i n f l u e n c e upon
t h e p r e c i p i t a t i o n . The concentrations of Pb,
Cu, Cr, Hg, Cd, and As were reduced t o low
l e v e l s by b o t h p r e c i p i t a n t s , w h i l e Zn, N i ,
and Co were p r e c i p i t a t e d o n l y f o r pH 9.5.
The p r e c i p i t a t i o n o f Cu and Pb were severely
i n h i b i t e d by t h e presence o f NTA a t pH 1 9 . 0 .
FLOTATION
Foam f l o t a t i o n depends on t h e use o f a
s u r f a c t a n t t h a t causes a nonsurface a c t i v e
m a t e r i a l t o become surface a c t i v e forming
a product t h a t i s removed by b u b b l i n g a gas
through the b u l k s o l u t i o n t o form a foam.
The use o f foam f l o t a t i o n techniques f o r r e -
moval o f heavy metals has been w e l l studied.
(32,52,142,155). With dilute wastewaters containing
heavy metals i n t h e p a r t s per b i l l i o n o r p a r t s
per m i l l i o n ranges, foam f l o t a t i o n o f f e r s
several d i s t i n c t advantages:
simplicity
f l e x i b i l i t y and e f f e c t i v e n e s s o f o p e r a t i o n .
l i m i t e d space requirements due t o r a p i d
reactions.
p r o d u c t i o n o f small, concentrated volumes
of sludge.
moderate c o s t s comparable t o t h a t o f l i m e
No. 243,Vol. 81
precipitation.
9 low c o s t s i n terms o f l a b o r , equipment,
energy, and chemical s .
capable o f a p p l i c a t i o n on small i n t e r m e d i a t e
and l a r g e scales.
capabi 1it y o f reducing t h e contaminant con-
c e n t r a t i o n s w e l l below t h e standards
e s t a b l i s h e d by r e g u l a t o r y agencies
To s i m u l a t e a lead-bearing waste, f e r r i c
c h l o r i d e was added t o form a p r e c i p i t a t e o f
f e r r i c hydroxide; t h e l e a d r a p i d l y adsorbed
o n t o t h e surface o f t h e Fe(0H) f l o c ( 1 5 5 ) .
F o l l o w i n g pH adjustment, a s u r f a c t a n t sodium
l a u r y l s u r f a t e (NLS) was added. P o s i t i v e l y
charged Fe(0H) f l o c p a r t i c l e s were a t t r a c t e d
t o t h e n e g a t i v h y charged bubbles formed by
b u b b l i n g a i r through t h e s o l u t i o n . The r i s i n g
bubbles o f NLS along w i t h t h e Fe(0H) f l o c
and adsorbed l e a d were removed as a foam and
then c o l l a p s e d forming a foamate o f about 2-3%
o f t h e i n f l u e n t volume.
Two p h y s i c a l models are used t o describe
t h e attachment o f f l o c p a r t i c f e s t o bubbles
i n t h e presence o f a s u r f a c t a n t (154,155). I n
t h e coulombic model, i o n i c s u r f a c t a n t i s ad-
sorbed on t h e a i r - w a t e r i n t e r f a c e o f t h e
bubble, r e s u l t i n g i n a surface charge d e n s i t y
on t h e bubbles. The charge d e n s i t y i s u s u a l l y
n e g a t i v e due t o t h e use o f a n i o n i c s u r f a c t a n t s .
The f l o c i s u s u a l l y given a surface charge
d e n s i t y opposite t o t h a t on t h e bubbles through
pH adjustment o r c o n c e n t r a t i o n o f o t h e r
p o t e n t i a l determining i o n s . The e l e c t r i c a l
a t t r a c t i o n between t h e f l o c p a r t i c l e and t h e
bubble i s reduced by t h e d i f f u s e e l e c t r i c a l
double l a y e r i n t h e v i c i n i t y o f t h e s u r f a c e .
Wilson (160) described methods t o c a l c u l a t e t h e
e l e c t r i c a l p o t e n t i a l i n solution, the p o t e n t i a l
energy o f i n t e r a c t i o n between t h e two i n t e r -
faces, and t h e a d s o r p t i o n isotherms.
I n t h e c o n t a c t angle model, s u r f a c t a n t
i o n s adsorb onto t h e primary l a y e r o f t h e f l o c
p a r t i c l e . They present t h e i r i o n i c o r p o l a r
ends t o t h e s o l i d and t h e i r hydrophobic hydro-
carbon t a i l s t o t h e s o l u t i o n . For s u f f i c i e n t l y
high concentrations o f surfactant, the s o l i d
surface i s o f a hydrocarbon c h a r a c t e r and i s
hydrophobi c. The s u r f ace tensions are such
t h a t t h e c o n t a c t angle o f t h e a i r - w a t e r i n t e r -
face on t h e s o l i d i s nonzero, thereby p e r m i t -
t i n g attachment o f the p a r t i c l e t o the bubble.
Using s t a t i s t i c a l mechanics, t h e b i n d i n g
energies and a d s o r p t i o n isotherms can be c a l -
c u l a t e d . Conclusions commoli t o both models
a r e summarized below (154):
1. I n c r e a s i n g i o n i c s t r e n g t h decreases the
flotation efficiency.
173
2. I n c r e a s i n g t h e l e n g t h o f the s u r f a c t a n t
hydrocarbon t a i l decreases t h e b u l k
l i q u i d concentration o f surfactant re-
q u i r e d t o produce f l o t a t i o n .
3. I n c r e a s i n g p a r t i c l e s i z e increases f l o t a -
tion efficiency.
4. I n c r e a s i n g temperature increases t h e r e -
q u i r e d s u r f a c t a n t concentration.
Plots o f F ( t h e r a t i o o f the f l u x of
metal o u t the bottom o f a column t o t h e f l u x
o f metal a t t h e t o p o f t h e column) as a
f u n c t i o n of t h e column, parameters shm (154,155):
F decreases ( b e t t e r performance) as speci-
f i c foam area increases.
F decreases as surface v e l o c i t y increases.
F i s roughly proportional t o l i q u i d
velocity.
F increases as the l i q u i d and foam t u r b u -
l e n t d i f f u s i o n c o e f f i c i e n t s increase .
F decreases as t h e mass t r a n s f e r c o e f f i c i e n t
increases approaching a f i n i t e e q u i l i b r i u m
- c o n t r o l l e d 1i m i t i ng value.
F decreases as t h e adsorption isotherm
rises.
F increases s l o w l y as t h e l o w feed con-
c e n t r a t i o n s increase.
P r e l i m i n a r y batch s t u d i e s o f Thackston e t a ] .
(154,155)showed t h e optimum pH f o r removal o f
l e a d was approximately 6.5 and t h a t i n c r e a s -
i n g i o n i c s t r e n g t h was d e t r i m e n t a l t o t h e
process; above 0.05M NaNO , t h e separation
e f f i c i e n c y d e c l i n e d markedly. F e r r i c hydro-
x i d e was much more e f f e c t i v e f o r adsorbing
l e a d than was aluminum hydroxide Sodium
carbonate was a more e f f e c t i v e n e u t r a l i z i n g
agent than was soda ash. High s u l f a t e con-
c e n t r a t i o n s reduced t h e optimum pH l e v e l
somewhat .
I n continuous f l o w studies4+l'ackstonet
a1 . (154,155) found t h e optimum Fe concen-
t r a t i o n was -150 mg/l and a s t a b l e foam c o u l d
be produced u s i n g -35 mg/l NLS. The i n f l u e n t
f l o w r a t e and h y d r a u l i c l o a d i n g r a t e d i d n o t
a l t e r t h e removal e f f i c i e n c y u n t i l i t became
so g r e a t as t o produce o v e r t u r n i n g o f she
fFam ( o c c u r r i n g a t a l o a d i n g o f -120 m /day-
m ) . E f f l u e n t l e a d concentrations l e s s than
0.15 mg/l c o u l d be maintained over a wide
pH range ( 5 . 0 t o 6 . 5 ) and i n f l u e n t f l o w r a t e
range. I f channeling and o v e r t u r n i n g occurred,
the r e s i d u a l l e a d averaged 0 . 5 - 1 . 5 mg/l.
I n c r e a s i n g t h e i o n i c s t r e n g t h t o 85011 a n d
17,000 mg/l Na NO3 increased the r e s i a u a l
lead t o 0.4 and 2 . 0 mg/l, respective:v
Experiments were performed by Mu.ai rt
a 1 . (98) i n v o l v i n g c o p r e c i p i t a t i o n of 9 f 11
174 Separation of Heavy Metals
i o n (Cd, Cu, Zn, o r Hg) w i t h f e r r i c hydroxide
f o l l o w e d by f l o t a t i o n u s i n g sodium o l e a t e as
a collector The t e s t s o l u t i o n s a l l con-
t i n u e d 1.0 mg/l o f the he$YY metal i n v o l v e d
and v a r y i n g amounts o f Fe . For t h e optimum
pH range f o r Cd removal (8<pH<10), t h e r e s i d u a l
cadmium c o n c e n t r a t i o n was l e s s than 0.05 mg/l.
Favorable Cu removal was maintained over a wide
pH range o f 6-10, w h i l e t h e optimum pH c o n d i t i o n
f o r Zn removal was pH 9-10. The Hg r e y y v a l
was -98% a t pH 8-9 w i t h t h e r e s i d u a l Hg con-
c e n t r a t i o n i n t h e t a i l i n g s o l u t i o n being 0.03
mg/l. Because Hg i s hard t o c o p r e c i p i t a t e ,
adoption o f a mu1 t i s t a g e + f l o t a t i o n o r a d d i t i o n
o f Na2S together w i t h Fe i n the coprecipit-
a t i o n stag$ i s r e q u i r e d t o minimize t h e r e -
s i d u a l Hg concentration. Flotations o f
c u p r i t e and c h r y s o c o l l a were performed w i t h
LIX65N reagent as a f u n c t i o n o f LIX concentra-
t i o n , pH, c o n d i t i o n i n g time, i o n i c s t r e n g t h ,
and s o l u t i o n copper concentration. Flotation
was a maximum around pH 5.5 and pH 10 i n
general agreement w i t h t h a t p r e d i c t e d on the
b a s i s o f t h e sol u b i 1 it y dependence w i t h pH.
F l o t a t i o n was low f o r the pH range o f 6.5-9.0.
Beitelshees e t a1 .(9) s t u d i e d p r e c i p i t a t e f l o -
t a t i o n as a method t o remove copper from
aqueous s o l u t i o n s c o n t a i n i n g 1-1000 mg/l d i s -
solved copper. S u l f i d e i o n was added i n a
s l i g h t excess t o p r e c i p i t a t e CuS, producing
a r e l a t i v e l y s t a b l e suspension o f submicron
(-0.1-0.5 Vm) c o l l o i d a l CuS p a r t i c l e s . Varying
amounts o f Hyamine 2389 and Amide 23 were em-
ployed i n t h e study. Hyamine was used t o serve
as t h e c o l l e c t o r s u r f a c t a n t . The primary use
o f Amide 23 was t h a t o f a foam s t a b i l i z e r .
The minimum a d d i t i o n s o f chemicals necessary
f o r good removal and steady column o p e r a t i o n
were 25 mg/7 Hyamine 2389 and 5 mg/l Amide 23.
I n 1976, t h e chemical c o s t s were estimated
t o be 37.6$/1000 g a l l o n s t r e a t e d o r 45.3Q/pound
o f copper removed. The CuS p a r t i c l e s were
r e a d i l y removed by f l o t a t i o n i n a bubble column.
Copper removals exceeding 90% f o r s o l u t i o n s
c o n t a i n i n g 10-1000 mg/l d i s s o l v e d copper were
achieved. A t 1 and 5 mg/l o f c a t i o n i c s u r -
f a c t a n t , t h e removal e f f i c i e n c y was 50% and
80%, r e s p e c t i v e l y . The p r e c i p i t a t e was con-
c e n t r a t e d i n a foamate f r a c t i o n , t h e volume
o f which was g e n e r a l l y l e s s than 5% o f t h e
i n i t i a l s o l u t i o n volume.
The comparative c o s t o f foam f l o t a t i o n
i s r e p o r t e d (95,140) t o be c o m p e t i t i v e w i t h t h a t
o f lime precipitation; i n t r e a t i n g a mixed
meigl waS$ewater c y y i a i n i n g 20 mg/l each of
Cu , Zn , and C r , t h e treatment c o s t s were
r e p o r t e d t o be $0.51/1000 l i t e r s f o r foam
f l o t a t i o n versus $0.60/1000 l i t e r s f o r l i m e
precipitation.
AlChE SYMPOSIUM SERIES
I O N EXCHANGE
I o n exchange i s an e f f e c t i v e means o f
removing heavy metals from wastewaters. I t
i s a r e v e r s i b l e chemical r e a c t i o n , where t h e
removal o f heavy metals i s accomplished by
t h e exchange o f i o n s on t h e r e s i n f o r those
i n wastewater. When t h e r e s i n s are saturated,
they must be regenerated w i t h an a c i d o r
a l k a l i n e medium t o remove t h e metal i o n s from
t h e r e s i n bed. The regenerant b r i n e i s
s m a l l e r i n volume and h i g h e r i n concentration
than t h e o r i g i n a l wastewater, b u t these metals
must then be adequately t r e a t e d o r recovered.
There are a v a r i e t y o f r e s i n s f o r
s p e c i f i c a p p l i c a t i o n s w i t h various metals.
S y n t h e t i c organic r e s i n s are mostly used
because o f t h e i r c a p a b i l i t i e s o f being manu-
f a c t u r e d f o r s p e c i f i c a p p l i c a t i o n s (44)
The use o f several i n o r g a n i c g e l s f o r the
removal o f heavy metals have a l s o been
studied(l47)due t o t h e i r s t a b i l i t y under more
d r a s t i c p h y s i c a l c o n d i t i o n s . L i q u i d - i o n ex-
change i s a e f f e c t i v e u n i t o p e r a t i o n used
t o p u r i f y and concentrate m i n e r a l s from
v a r i o u s s o l u t i o n s i n t h e hydrometallurgy
i n d u s t r y . There have been l i m i t e d a p p l i c a -
t i o n s i n in d u s t r i a1 wastewater treatment,
m o s t l y i n Europe. Removal o f heavy metals,
such a s Zn, C r , and Cd are e f f e c t v e l y handl-
ed by l i q u i d i o n exchange. Technically,
almost every metal i o n can be removed o r
recovered by some i o n exchange process
b u t economical concern p l a y s a very d e c i s i v e
r o l e i n t h e commerical a p p l i c a t i o n o f i o n
exchange. I o n exchange i s an i d e a l method
f o r t h e removal o f t r a c e amounts o f i m -
p u r i t i e s from d i l u t e wastewaters, w i t h t h e
h i g h q u a l i t y t r e a t e d water ready f o r reuse.
Due t o t h e f a c t t h a t i o n exchange i s
e f f i c i e n t i n removal o f d i s s o l v e d s o l i d s
from normally d i l u t e spent r i n s e waters, i t
i s w e l l s u i t e d f o r use i n water p u r i f i c a t i o n
and r e c y c l e . Many of t h e p l a t i n g chemicals,
acids, and bases used i n metal f i n i s h i n g are
i o n i z e d i n s o l u t i o n and can be removed by
i o n exchange. Factors making i o n exchange
e f f e c t i v e f o r such a p p l i c a t i o n s (44) i n c l u d e :
I o n exchange can economically separate
d i l u t e concentrations o f i o n i c species
from s o l u t i o n s .
The process can c o n s i s t e n t l y p r o v i d e high
p u r i t y water over a broad range o f con-
d i tions.
The r e s i n s used f o r separation are durable
under severe chemical environments.
I o n exchange i s a l s o a p p l i e d f o r end-of
No. 243, Vol. 81
p i p e " p o l l u t i o n c o n t r o l where t o x i c heavy
metals and metal cyanide complexes are s e l e c t -
i v e l y removed from combined waste streams be-
f o r e discharge. I o n exchange has been em-
p l o y e d as a p o l i s h i n g step f o l l o w i n g covention-
a1 hydroxide treatment t o lower t h e metal
c o n c e n t r a t i o n i n t h e discharge; i t has a l s o
been a p p l i e d as a means o f d i r e c t l y t r e a t i n g
wastewaters t o remove heavy metals and metal
cyanide complexes. I n comparison w i t h con-
v e n t i o n a l p r e c i p i t a t i o n treatment, i o n ex-
change o f f e r s t h e f o l l o w i n g advantages(53):
P r e c i p i t a t i o n and c l a r i f i c a t i o n equipment
r e q u i r e a l o t o f space w h i l e i o n exchange
equipment i s very compact.
Metal hydroxide sludges must be t r a n s p o r t e d
t o a l a n d f i l l l i c e n s e d t o handle them; i o n
exchange avoids t h e generation o f sludges.
No economical method i s c u r r e n t l y a v a i l a b l e
t o recover t h e metal values from metal
f i n i s h i n g sludges s o t h e metals cannot be
recycled. I o n exchange a l l o w s convenient
recovery o f t h e metal s .
I o n exchange i s a v e r s a t i l e process which
accommodates metal i o n c o n c e n t r a t i o n
v a r i a t i o n s and reasonable changes i n f l o w
r a t e w i t h o u t d e t e r i o r a t i o n i n performance.
I o n exchange has been used t o a l i m i t e d
e x t e n t t o remove t o x i c p o l l u t a n t s s e l e c t i v e l y
from an u n t r e a t e d wastewater w h i l e a l l o w i n g
most o f t h e n o n t o x i c i o n s t o pass through.
To f a c i l i t a t e t h i s a p p l i c a t i o n , approaches (44)
include:
Weak a c i d c a t i o n exchange r e s i n i n an ap-
p l i c a t i o n o f t h e wastewater s o f t e n i n g type
t o remove heavy metals and o t h e r d i v a l e n t
c a t i o n s from a wastewater laden w i t h sodium
ions.
Heavy-metal-selective weak a c i d o r c h e l a t i n g
c a t i o n exchange r e s i n f o r removal o n l y o f
the heavy metal i o n s w h i l e a l l o w i n g sodium,
calcium, and magnesium i o n s t o pass through.
A s t r a t i f i e d r e s i n bed c o n t a i n i n g s t r o n g
and weak a c i d c a t i o n and s t r o n g base anion
r e s i n s t o remove heavy metals and metal
cyanide complexes from s o l u t i o n w h i l e
a l l o w i n g t h e m a j o r i t y o f t h e wastewater
i o n i c c o n s t i t u e n t s t o pass through.
Each of these approaches i n v o l v e s pH a d j u s t -
ment ( t o ensure t h e pH i s w i t h i n t h e o p e r a t i n g
range o f t h e r e s i n ) and f i l t r a t i o n ( t o remove
suspended s o l i d s t h a t would otherwise f o u l
t h e r e s i n bed). The p o l l u t a n t s from t h e waste-
water are concentrated i n t h e i o n exchange
regenerant s o l u t i o n s . This regenerant b r i n e
i s much s m a l l e r i n volume and h i g h e r i n con-
c e n t r a t i o n than t h a t o f t h e o r i g i n a l waste-
water. Such processing serves as an e x c e l l e n t
175
pretreatment s t e p f o r subsequent p h y s i c a l -
chemical treatment o r as a p o l i s h i n g step.
Such a case h i s t o r y was o u t l i n e d where i o n
exchange treatment f o l l o w i n g hydroxide pre-
c i p i t a t i o n enabled HurdLock and Manufacturing
Company t o meet t h e s t a t e l i m i t s f o r Cd, Cr,
Cu, Fe, Pb, N i , and Zn. As a r u l e , i o n ex-
change systems are s u i t a b l e f o r chemical r e -
covery a p p l i c a t i o n s where t h e r i n s e water
feed has a low c o n c e n t r a t i o n o f p l a t i n g
chemicals and where a r e l a t i v e l y low degree
o f concentration i s required f o r recycle o f
t h e concentrate. I o n exchange has been
demonstrated commercially f o r recovery o f
p l a t i n g chemicals from acid-copper, acid-zinc,
n i c k e l , t i n , c o b a l t , and chromium p l a t i n g
baths (44). I t has a l s o been used t o recover
spent a c i d s o l u t i o n s and t o p u r i f y p l a t i n g
s o l u t i o n s f o r l o n g e r s e r v i c e l i f e . Typical
process condi ti ons, removal costs , and
o p e r a t i n g c o s t s are l i s t e d i n Reference(44).
Several i o n exchange systems have been
developed. The fixed-bed i o n exchanger system
i s a conventional w i d e l y used design which
r e q u i r e s m u l t i p l e columns and a l o t o f
operator a t t e n t i o n . Two approaches have been
used t o s i m p l i f y t h e o p e r a t i o n o f i o n ex-
change systems: t h e continuous i o n exchanger
and t h e r e c i p r o c a t i n g f l o w i o n exchanger.
The continuous i o n exchange system provides
simultaneous i o n exchange, regeneration, back
wash, and r i n s e c y c l e s i n separate sections.
However, t h e system's c a p i t a l c o s t i s h i g h e r
than t h a t o f fixed-bed systems. The r e c i p r o -
c a t i n g f l o w i o n exchanger operates on t h e
p r i n c i p l e t h a t f o r t h e s h o r t p e r i o d time,
t h e system goes o f f stream f o r regeneration.
C a p i t a l c o s t and l a b o r are minimized i n t h i s
system.
As an example o f recovery o f valuable
metals from i n d u s t r i O Q waste streams, hex-
a v a l e n t chromium (Cr ) can be s u c c e s s f u l l y
recovered u s i n g i o n exchange treatment (158).
The waste stream i s f i r s t passed through a
c a t i o n exchanger t o remove extraqT9us metals,
p r i m a r i l y Fe, Cu, Zn, N i , and C r . The -
hexavalent chromium passes through as Cr04-
and i s removed i n an anion exchanger; t h e
e f f l u e n t i s a demineralized wa+%r s u i t a b l e
f o r reuse. For recovery o f C r , t h e regener-
ated water w i t h NaOH and Na Cr04 i s released.
The Na C r O s o l u t i o n i s th6n passed through
anotheg c a t i o n exchanger which exchanges
sodium f o r hydrogen r e l e a s i n g chranic a c i d
(H2Cr04) i n the e f f l u e n t f o r recovery.
Semmens and M a r t i n (137)performed s t u d i e s
on the removal o f Pb, Ag, and Cd by c l i n o p t i -
l o l i t e i n t h e presence o f competing concen-
I 76 Separation of Heavy Metals
t r a t i o n s o f calcium, magnesium, and sodiyy.
Th$ obseryed s e l e c t i v i t y sequence was Pb > (composed o f an organic l i q u i d c o n t a i n i n g
Ag > Cd . The competing c a t i o n s s t r o n g l y
i n f l u e n c e d the metal exchange w i t h t h e z e o l i t e .
Metal removal was g r e a t e s t i n exchange y i t h
magnT-ium and decreased i n t h e o r d e r Mg > Na+
f o r l e a d $nd cadmium and i n the o r d e r
>
Mg " > Ca++ > Na f o r s i l v e r . The presence
o f any calcium i n s o l u t i o n had a profound
e f f e c t on the e x t e n t o f Cd removal. Both
batch and continuous f l o w s t u d i e s were performed
i n t h e i n v e s t i g a t i o n . Lead was found t o be
very e f f e c t i v e l y removed; l a r g e through p u t s
c o u l d be obtained b e f o r e breakthrough occurred
A1 k a l i n e pretreatment o f t h e z e o l i t e improved
t h e metal removal e f f i c i e n c y .
E t z e l and Tseng (&)recognized t h a t a
drawback i n t h e use o f i o n exchange i s t h e
f a c t t h a t t h e r e s i n must be regenerated a f t e r
exhaustion, thereby c o m p l i c a t i n g o p e r a t i o n
o f t h e system. Chemical c o s t s are h i g h p e r
u n i t o f metals removed; i t a l s o r e s u l t s i n
volumes o f regenerant s o l u t i o n which must be
t r e a t e d p r i o r t o discharge. Etzel and Tseng(46)
i n v e s t i g a t e d a new approach t o regeneration
o f a heavy metal exhausted c a t i o n exchange
r e s i n u s i n g a recoverable c h e l a t i n g agent,
whereby t h e regenerant s o l u t i o n c o u l d be reused
and t h e metal removed by t h e exchangeF r e -
covered. T h e i r s t u d i e s showed EDTA, NTA,
and c i t r a t e coul'd s u c c e s s f u l l y regenerate a
s t r o n g a c i d c a t i o n exchange r e s i n exhausted
by Cu, Zn, N i , o r a metal mixture, t o i t s
o r i g i n a l sodium form. The optimum pH range
f o r a l l t h e c h e l a t i n g agent s o l u t i o n s was be-
tween 8 a n d 9 f o r r e g e n e r a t i o n o f t h e r e s i n .
Regeneration e f f e c t i v e n e s s o f t h e c h e l a t i n g
agents was i n t h e o r d e r Cu>Zn>Ni; regeneration
e f f e c t i v e n e s s o f EDTA, NTA, and c i t r a t e was
i n t h e o r d e r EDTA = C i t > NTA.
Problems t y p i c a l l y i n v o l v e d w i t h i o n ex-
change treatment i n c l u d e :
M e t a l l i c f o u l i n g ( f r o m Fe, Mn, Cu, e t c . )
on t h e i o n exchange media.
* F o u l i n g due t o o i l , grease, s i l t , c l a y ,
c o l l o i d a l s i l i c a , organic m a t e r i a l s , and
microbes. The choice o f a proper c l e a n i n g
program can restoremuch o f t h e l o s t
e f f ic iency (115,116).
The presence o f f r e e a c i d reduces t h e
e f f i c i e n c y o f operation.
F a i r l y high operational costs.
LIQUID I O N EXCHANGE/LIQUID-LIQUID EXTRACTION
Recently research has been performed on
the use o f l i q u i d i o n exchange f o r removal of
heavy metals from p l a t i n g wastes(76,126).The
AlChE SYMPOSIUM SERIES
process b a s i c a l l y i n v o l v e s a two phase system
a dissolved, w a t e r - i n s o l u b l e a c t i v e compound
and t h e heavy metals i n t h e aqueous phase)
i n v o l v i n g l i q u i d - l i q u i d e x t r a c t i o n . The
l i q u i d extractant i s t y p i c a l l y present a t
a 10-40% a c t i v e l e v e l i n a s o l v e n t , such as
kerosene. The e x t r a c t a n t s o l u t i o n i s r u n
c o u n t e r c u r r e n t t o an aqueous feed c o n t a i n i n g
one o r more types o f metal ion, u s u a l l y a t
a temperature s l i g h t l y above ambient t o i m -
prove t h e exchange k i n e t i c s and t o f a c i l i t a t e
phase separation. A c i d - t r e a t i n g t h e organic
f r a c t i o n releases t h e metal i n a concentrated
w a t e r - s o l u b l e form.
Several advantages have been noted w i t h
a p p l i c a t i o n o f l i q u i d i o n exchange ( L I E )
technology (76,126):
LIE can s e l e c t i v e l y e x t r a c t a d e s i r e d
m e t a l l i c c a t i o n from a f e e d s o l u t i o n con-
t a i n i n g a s i g n i f i c a n t amount o f m e t a l l i c
. impurities.
LIE can concentrate t h e d e s i r e d c a t i o n
i n f i n a l aqueous s o l u t i o n so t h a t i t can
be t r e a t e d by methods i n a p p r o p r i a t e f o r
t h e i n i t i a l d i l u t e feed.
L I E i s w e l l s u i t e d f o r process automation
and e f f i c i e n t metal recovery from a mixed-
metal hydroxide s l u r r y .
One drawback w i t h l i q u i d - l i q u i d e x t r a c t i o n
i s i t s 1i m i t e d a b i l i t y t o concentrate t h e
metals d u r i n g t h e e x t r a c t i o n process; i n most
cases, e x t r a c t i o n produces no more than a
t e n - f o l d increase i n metal c o n c e n t r a t i o n .
This process has been s u c c e s s f u l l y adopt-
ed by t h e uranium and copper i n d u s t r i e s (39).
and o f f e r s promise i n t h e p l a t i n g and metal
f i n i s h i n g i n d u s t r i e s . Petersen e t a l . (126)
i n v e s t i g a t e d t h e use o f l i q u i d i o n exchange
i n removing cadmium and n i c k e l from both
segregated and composite wastestreams.
Langmuir and F r e u n d l i c h isotherm equations
adequately described t h e removal o f heavy
metals i n t h e i r system. They estimated the
c o s t o f a t y p i c a l moderate s i z e d p l a t i n g
f a c i i i t y employing r e d u c t i o n and l i m e pre-
c i p i t a t i o n was $4.71/1000 g a l l o n s . As a
comparison, u s i n g anion exchange t o remove
chromate and l i q u i d i o n exchange f o r removal
o f n i c k e l and cadmium, t h e treatment c o s t
w a s estimated t o be $2.45/1000 g a l l o n s .
Knocke e t a l . (76) i n v e s t i g a t e d t h e use o f
l i q u i d i o n exchange f o r treatment o f waste-
waters from T i n k e r A i r Force Base containing
N i , C r , Cu, Cd, and Ag. P r e l i m i n a r y extrac-
t i o n s t u d i e s were performed u t i l i z i n g a mixed
No. 243,Vol. 81
metal s o l u t i o n c o n t a i n i n g 100 mg/l each o f
C r y Cd, Cu, N i , and Zn. S i g n i f i c a n t r e s u l t s
o f t h e i r study are summarized below:
Thenoyl t r i f l u o r o a c e t o n e possesses h i g h
s e l e c t i v i t y f o r copper a t low pH c o n d i t i o n s .
8-Hydroxyquinoline was a b l e t o e x t r a c t
over 99% o f t h e n i c k e l i n t o t h e organic
l a y e r ; a t pH 2 over 95% o f t h e e x t r a c t e d
n i c k e l c o u l d be s t r i p p e d o f f i n t o t h e
aqueous phase u s i n g 2.4M HC1.
Using 0.5M 8-HydroxyquinolineY e x t r a c t i o n
a t pH 5.4 r e s u l t e d i n 99% o f t h e cadmium
being e x t r a c t e d i n t o the c h l o r o f o r m l a y e r ;
back e x t r a c t i o n r e s u l t e d i n a 79% recdvery
o f t h e cadmium i n t h e aqueous phase a t
pH 2.0.
A l l seven c h e l a t i n g compounds i n v e s t i g a t e d
performed p o o r l y f o r s e l e c t i v e chromium
extraction.
CEMENTATION
Cementation i s a metal-replacement p r o -
cess i n which a s o l u t i o n c o n t a i n i n g t h e d i s -
solved m e t a l l i c i o n ( s ) comes i n c o n t a c t w i t h
a more a c t i v e metal such as i r o n . Cementa-
t i o n i s thus t h e recovery o f an i o n i z e d metal
from s o l u t i o n by spontaneous electrochemical
r e d u c t i o n . t o t h e elemental m e t a l l i c s t a t e
w i t h subsequent o x i d a t i o n o f a s a c r i f i c i a l
metal (such as i r o n ) . The r e a c t i o n f o r copper
and i r o n ' i s :
Cu++ + Feo + Cuo + Fe++
The r e s u l t i s t o r e p l a c e copper w i t h i r o n i n
s o l u t i o n ; t h e copper p l a t i n g o n t o the s o l i d
i r o n surface. I f hexavalent chromium i s p r e -
s e n t i n a wastewater, i t can r e a c t w i t h e i t h e r
elemental o r f e r r o u s i r o n t o y i e l d t r i v a l e n t
chromium:
2 Cr+6 + 3 Feo + 2 Cr+3 + 3 Fe+2
Cr+3 + 3 Fet3
The cementation process can be p r e d i c t e d i n
terms o f e l e c t r o d e p o t e n t i a l s . Advantages
o f t h e process i n c l u d e :
Simple c o n t r o l requirements.
Low energy u t i l i z a t i o n .
Recovery o f v a l u a b l e h i g h p u r i t y metals,
such as copper.
Patterson and Jancuk(ll2)studied cementation
treatment o f copper i n wastewaters. They
found copper cementation i s a f i r s t - o r d e r
r e a c t i o n w i t h r e s p e c t t o removal o f copper
f r o m t h e wastewater. The r a t e o f cementation
was independent o f t h e presence o f oxygen.
Copper cementation was independent o f pH;
howeve, c.':t3ve ptl 3, f e r r i c hydroxide p r e -
177
c i p i t a t i o n masked and i n t e r f e r e d w i t h copper
recovery. The copper from t h e continuous
r e a c t o r s had a m o i s t u r e c o n t e n t o f -38%; t h e
d r i e d cement c o n t a i n e d -95.5% pure copper
on a d r y weight b a s i s .
A r e c e n t a p p l i c a t i o n o f t h i s technology
i n v o l v e d t h e suspension o f scrap i r o n i n a
p e r f o r a t e d r o t a t i n g drum through which t h e
wastewater f l o w s (69). Copper i s cemented
o n t o t h e i r o n and scraped o f f as p a r t i c u l a t e
copper as i t tumbles w i t h i n t h e drum.
COMPLEXATION/SEQUESTRATION
Complexation i n v o l v e s t h e f o r m a t i o n o f a
complex compound through a complexing o r
c h e l a t i n g agent. Sequestration i n v o l v e s t h e
removal o f a metal i o n from s o l u t i o n by
f o r m a t i o n o f a complex i o n t h a t does n o t have
t h e chemical r e a c t i o n s o f t h e i o n t h a t i s
removed, i n o t h e r words t h a t metal i o n i s
t i e d up o r complexed. Complex f o r m a t i o n
a1 t e r s t h e chemical c h a r a c t e r i s t i c s o f t h e
metal i o n s and a f f e c t s t h e removal mechanisms
i n v o l v e d (59). For example, t h e f o r m a t i o n o f
metal complexes increases t h e s o l u b i l i t y o f
metal p r e c i p i t a t e s as hydroxides, carbonates,
and s u l f i d e s . The e x t e n t o f complex f o r m a t i o n
i s a f f e c t e d by s o l u t i o n pH and t h e concentra-
t i o n o f p a r t i c i p a t i n g species. Mayenkar and
Lagvankar (%Found t h a t d i s s o l v e d chelated
n i c k e l c o u l d be e f f e c t i v e l y removed by con-
t a c t i n g t h e wastewater w i t h a bed o f i r o n
f i l i n g s ; t h e type o f c h e l a t i n g agent present
a f f e c t e d t h e r e a c t i o n r a t e . O;#)eilltpt ali$a)
inyQstigated+&he removal o f C y , Zn , Fe ,
C r , and C r by u l t r a f i l t r a t i o n by t y i n g
up t h e metal i o n s i n l a r g e molecularcomplexes
u s i n g EDTA. Although from s e l e c t i v i t y con-
s i d e r a t i o n s , i t appeared separation o f copper
and z i n c i n t h e pH range o f 5-6 was p o s s i b l e ,
such was n o t t h e case. For t h a t case,
s e p a r a t i o n o f metal c a t i o n s by c h e l a t i o n and
u l t r a f i l t r a t i o n d i d n o t appear promising.
Using s o l e l y camplexation f o r recovery o f
metals does n o t h o l d much promise i n the
p l a t i n g industry.
ELECTROCHEMICAL OPERATIONS
E l e c t r o l y t i c metal recovery i s one o f
a number o f technologies capable o f removing
metals from process wastewaters. The tech-
nology has been used f o r many years i n t h e
mining i n d u s t r y f o r e l e c t r o - w i n n i n g and
e l e c t r o r e f i n i n g o f ores, and has been used
t o recover copper from p i c k l e l i q u o r s .
Durinq t h e l a s t 25-30 years,
e l e c t r o l y t i c metal recovery
has been i n v e s t i g a t e d f o r recovery
178 Separation of Heavy Metals
o f meta ; i n dragout from p l a t i n g tanks. I n
e l e c t r o l y t i c recovery, a d i r e c t c u r r e n t i s
passed through an aqueous s o l u t i o n c o n t a i n i n g
metal i o n s between cathode p l a t e s and i n -
s o l u b l e anodes. The p o s i t i v e charged metal-
l i c ionsadhere t o t h e n e g a t i v e l y charged
cathodes l e a v i n g a metal d e p o s i t t h a t can be
s t r i p p e d o f f and recovered. The p r i n c i p l e s
and techniques o f electrochemical techniques
have been described i n t h e l i t e r a t u r e (2,117)
addressing such t o p i c s as e l e c t r o d e p o t e n t i a l s ;
e q u i l i b r i u m , o x i d a t i o n - r e d u c t i o n , and mixed
p o t e n t i a l s ; v o l tammetry, e l e c t r o c a p i l l a r i t y
capacity, s h o r t - c i r c u i t c u r r e n t measurements,
r e d u c t i o n by s u l f u r d i o x i d e and carbon mono-
xide, e t c . Pemsler and Rappas(ll7)point o u t
t h a t e l e c t r o - w i n n i n g i s a h i g h l y energy-
dependent and l a b o r i n t e n s i v e process. The
c a p i t a l c o s t o f an e l e c t r o w i n n i n g process
i s extremely h i g h and represents a s i g n i f i c a n t
p o r t i o n o f the t o t a l cost.
A graphical representation o f e l e c t r o -
chemical e q u i l i b r i a ( i n c l u d i n g chemical r e -
a c t i o n s such as h y d r o l y s i s and complex form-
a t i o n i s t h e Pourbaix diagram (128). These
diagrams p l o t the r e d u c t i o n p o t e n t i a l on t h e
hydrogen scale (E-HH) versus pH, showing t h e
domains o f predominance f o r t h e various species
i n t h e system. The l i n e s i n t h e diagrams
represent t h e locus o f equal a c t i v i t y o f two
species i n e q u i l i b r i u m ; h o r i z o n t a l l i n e s are
f o r oxidation o r reduction without hydrolysis
o r complex formation, w h i l e v e r t i c a l l i n e s
are f o r h y d r o l y s i s o r complex formation.
Areas between l i n e s represent f i e l d s o f s t a -
b i l i t y f o r a given a c t i v i t y level f o r the
chemical species considered.
D i l u t e r i n s e waters pose a s p e c i a l pro-
blem because cathode p o l a r i z a t i o n becomes
s i g n i f i c a n t a t low c o n c e n t r a t i o n s . As p l a t i n g
proceeds, t h e l a y e r o f s o l u t i o n adjacent t o
t h e cathode becomes depleted i n metal ions,
forming a p o l a r i z e d l a y e r . The r a t e o f d i f -
f u s i o n i n t o and across t h e p o l a r i z e d l a y e r
i s lower; the l a y e r becomes t h i c k e r and more
depleted. Cathode p o l a r i z a t i o n leads t o a
number o f o p e r a t i o n a l problems i n c l u d i n g a
low r a t e o f metal d e p o s i t i o n . A number o f
means e x i s t t o reduce cathode p o l a r i z a t i o n
i n c l u d i n g o p e r a t i o n a t lower c u r r e n t d e n s i t y ,
a d j u s t i n g t h e chemistry and s o l u t i o n tempera-
t u r e , a g i t a t i n g t h e s o l u t i o n , employing h i g h
cathode surface areas, and reducing t h e d i f -
f u s i o n l a y e r thickness.
The t h e o r y o f o p e r a t i o n b a s i c a l l y i n -
volves an o x i d a t i o n - r e d u c t i o n r e a c t i o n where-
by e l e c t r o n s are s u p p l i e d by an e x t e r n a l
e l e c t r i c a l source reducing t h e metal i o n s i n
AlChE SYMPOSIUM SERIES
t h e e l e c t r o l y 2 t o form elemental metal a t
t h e cathode surface. As an example, t h e
c a t h o d i c and anodic r e a c t i o n s f o r copper are
as f o l l o w s :
Cathode: Cu++ + 2 e- + Cuo
Anode: H20 + 2H+ + 30, + 2e-
Benni on and Newman (13) devel oped an
e l e c t r o l y t i c c e l l u s i n g porous, f i x e d , flow-
through e l e c t r o d e s as a means o f removing
metal i o n s from d i l u t e s o l u t i o n s . Using t h i s
c e l l , t h e copper c o n c e n t r a t i o n s were reduced
from 670 mg/l t o l e s s than 1 mg/l. The con-
t r o l l i n g f a c t o r f o r use o f t h e c e l l was i t s
c a p i t a l c o s t . E l e c t r o l y t i c recovery o f z i n c
from a p l a t i n g b a t h r i n s e stream ( c o n t a i n i n g
z i n c cyanide s o l u t i o n ) was accomplished using
a simple b a t c h e l e c t r o c h e m i c a l r e a c t o r w i t h
s t a i n l e s s s t e e l e l e c t r o d e s (157).Test s o l u t i o n s
rangPd i n c o n c e n t r a t i o n from 100-980 mg/l.
The h i g h e s t z i n c removal r a t e s were achieved
u s i n g h i g h a p p l i e d c u r r e n t s . The s i n g l e most
important f a c t o r i n achieving high deposition
r a t e s was a g i t a t i o n ; mechanical m i x i n g and
n i t r o g e n gas a e r a t i o n were b o t h e f f e c t i v e f o r
a g i t a t i o n . Zinc d e p o s i t i o n was h i g h e r f o r
h i g h e r n i t r o g e n gas feed r a t e s , due t o t h e
increased a g i t a t i o n reducing t h e concentration
p o l a r i z a t i o n . A g i t a t i o n promotes the r e -
plenishment o f z i n c i o n s a t t h e boundary l a y e r
as z i n c deposits on t h e e l e c t r o d e s . Higher
c u r r e n t d e n s i t i e s p r o v i d e moderately h i g h e r
d e p o s i t i o n r a t e s than low c u r r e n t d e n s i t i e s .
The NaCl dose had l i t t l e e f f e c t on t h e de-
p o s i t i o n r a t e s as l o n g as s u f f i c i e n t NaCl was
added t o achieve a c r i t i c a l minimum con-
d u c t i v i t y l e v e l . Bishop and Breton(24) studied
t h e e f f e c t o f cathode surface area on t h e
recovery o f copper from d i l u t e , chelated
copper r i n s e waters, by employing an e l e c t r o -
l y t i c c e l l c o n s i s t i n g o f a s e r i e s o f flow-
through cathodes and anodes i n an e l e c t r o d e
c e l l box. The copper removal e f f i c i e n c y
ranged from 80-851. I n f l u e n t pH had l i t t l e
e f f e c t on t h e c h e l a t e d copper removal over
t h e pH range o f 3 t o 11. I n f l u e n t copper
c o n c e n t r a t i o n and f l o w r a t e had t h e g r e a t e s t
i n f l u e n c e on t h e performance o f t h e e l e c t r o -
l y t i c u n i t w h i l e pH and r e c i r c u l a t i o n r a t e
had l i t t l e o r no e f f e c t on the o v e r a l l t r e a t -
ment e f f i c i e n c y . F i e l d data (146)indicated cop-
per c o u l d be removed t o l e v e l s o f l e s s than
1 mg/l from an i n i t i a l l e v e l o f 100 mg/l f r o m
s o l u t i o n s c o n t a i n i n g EDTA, Quadrol, t a r t r a t e ,
pyrophosphate, ammonium persul f a t e etch, and
peroxide s u l f u r i c copper etch.
Electrochemical processes p r o v i d e a means
o f i n t r o d u c i n g o x i d a n t w i t h o u t adding ex-
traneous chemicals o r i o n ~ ( l 2 7 ) ~ A y r eand s
No. 243, Vol. 81
Fedkiw(7) s t u d i e d t h e d e p o s i t i o n o f l e a d and
copper
.. on a r e t i c u l a t e d v i t r e o u s carbon surface
as+$ c a t $ l y t i c + $ g e n t f o r + $ l e c t r o d e p o s i t i o n o f
Cu , N i . Pb , and Zn from d i l u t e s o l u -
t i o n s (10 mg/l ) u s i n g a flow-through porous
e l e c t r o d e r e a c t o r + Lead d i d n o t c a t a l y z e t h e
d e p o s i t i o n o f Zn although i t d i d i n h i b i t
t h e H2 s i d e r e a c t i o n 2 ? t t h e h i g h e s t l o a d i n g
l e v e l used (50 Vg/cm ) . &pper shyred a s t r o n g
c a t a l y t i c a c t i v i t y f o r Zn and N i elytro-
d e p o s i t i o n a t l o a d i n g s from 2Oi30 pg/cm .
The presence o f 10-100 mg/l Cu acted as a
c a t a l y s t f o r CN- e l e c t r o o x i d a t i o n . A current
e f f i c i e n c y of+$!7% was measured as t h e concen-
t r a t i o n o f Cu was lowered from 95.6 mg/l
t o 0.05 mg/l. Ayres and Fedkiw (7)estimated
t h e e l e c t r i c a l o p e r a t i n g c o s t t o be 11B/lb
o f copper recovered (which compares w i t h 65.3C1
l b o f copper removed by hydroxide p r e c i p i t a -
t i o n ) . The sludge volume of t h e waste gen-
e r a t e d i s c o n s i d e r a b l y s m a l l e r by t h e e l e c t r o -
l y t i c recovery r o u t e than by t h e p r e c i p i t a t i o n
r o u t e (0.0279 g a l l o n s p e r l b copper e l e c t r o -
c h e m i c a l l y generated versus 4.45 g a l l o n s [ o f
4% s o l i d s ] p e r l b o f copper removed by hydro-
xide precipitation).
Farkas and M i t c h e l l (47) developed a p r o -
cess f o r electrochemical heavy metal recovery
from wastewaters. The equipment c o n s i s t s o f
a r e a c t o r module c o n t a i n i n g t h e anode and
cathode assemblies, two c o n t r o l l a b l e power
supplies, p l u s pumps, e l e c t r o l y t e tanks, e t c .
The cathode c o n s i s t s o f a bundle o f t h i n carbon
f i b e r s connected t o a feeder sheet. The
s u r f a c e area t o volume r a t i o i s extremely
high, -12,000~ h i g h e r than t h e apparent s u r f a c e
area t o volume r a t i o . The l a r g e s u r f a c e area
enhances t h e mass t r a n s f e r r a t e several o r d e r s
o f magnitude. Features o f t h e process i n c l u d e
no g e n e r a t i o n o f sludge, low o p e r a t i n g costs,
no consumable reagents r e q u i r e d f o r o p e r a t i o n ,
and metals are generated i n a s a l e a b l e form.
B I O LOG1CAL TREATMENT
Reid e t a l . (132)studied t h e e f f e c t s o f
m e t a l l i c i o n s on b i o l o g i c a l waste t r e a t m e n t
processes. Activateci sludge treatment p r o -
cesses can+&olerate up t o 10 mg/l o f heavy
metals (Cr , Cu, N i , and/or Zn) e i t h e r s i n g l y
o r i n combination w i t h o n l y a 5% r e d u c t i o n
i n e f f i c i e n c y . These same f o u r heavy metals
may be present, e i t h e r s i n g l y o r i n conibina-
t i o n , up t o c o n c e n t r a t i o n s o f 10 mg/l w i t h o u t
any adverse e f f e c t on anerobic sludge d i g e s t i o n .
B i o l o g i c a l t r e a t m e n t o f domestic sewage w i l l
n o t bf6adversely e f f e c t e d i f t h e c o n c e n t r a t i o n
of Cr does n o t exceed 2 mg/l. Biomass con-
c e n t r a t i o n s t r o n g l y a f f e c t e d t h e amount o f
copper t h a t c o u l d be removed from s o l u t i o n .
179
Removal of copper was more e f f i c i e n t w i t h
i n c r e a s i n g pH f o r a d s o r p t i o n by Zoogloea
ramigera. However, a t h i g h e r pH, o n l y p a r t
o f t h e copper removed i s due t o a d s o r p t i o n t o
bacterial biomass s i n c e copper hydroxide
p r e c i p i t a t i o n becomes appreciable above pH
5.0. The uptake o f copper i s r a p i d and
e f f i c i e n t ; about 0.17 grams o f copper are
adsorbed p e r gram o f biomass w i t h i n 10 minutes.
Several s t u d i e s have addressed t h e e f f e c t
o f metals on t h e a c t i v a t e d sludge process.
Moul t o n and Shumate(97)observed t h a t an ac-
c l i m a t e d a c t i v a t e d sludge system c o u l d g i v e
a r e d u c t i o n o f 80-85% f o r t h e copper concen-
t r a t i o n when t h e i n f l u e n t copper l e v e l was
50 mg/l. The a c t i v a t e d sludge process was
a b l e t o remove 50-79% o f t h e copper f o r an
i n f l u e n t c o n c e n t r a t i o n o f 0.4 t o 25.0 mg/l (104).
When t h e i n f l u e n t metal c o n c e n t r a t i o n was
v a r i e d from 2.1 t o 25.5 mg/l, a 7 4 4 6 % uptake
o f cadmium and a 8 1 4 2 % uptake o f copper
r e s u l t e d (33). Adsorption of cadmium (101)
increased from 15-20% a t pH 4 t o a d s o r p t i o n s
exceeding 90% a t pH 10; maximum a d s o r p t i o n
o f copper occurred i n t h e pH range 7<pH<8
Kodukula and P a t t e r s o n (78)observed t h e s o l u b l e
cadmium and n i c k e l c o n c e n t r a t i o n remained
c o n s t a n t a t low suspended s o l i d s c o n c e n t r a t i o n s
and was c o n t r o l l e d by p r e c i p i t a t e s o l u b i l i t y .
These c o n c e n t r a t i o n s decreased as t h e s o l i d s
l e v e l increased; s o l u b l e metal i s adsorbed
t o t h e s o l i d s . The p e r c e n t metal a d s o r p t i o n
increased by more than 70% over 1-2 pH u n i t s
change. For cadmium, s i g n i f i c a n t changes
i n t h e a d s o r p t i o n c a p a b i l i t y occur i n t h e
range 5.0<pH<7.0 whereas f o r n i c k e l t h i s
change i s observed f o r 6.0<pH<8.0. Removals
o f both n i c k e l and cadmium were about 90%,
a t pH 8, whereas a t pH 7, removal o f n i c k e l
and cadmium were approximately 60 and 90%
r e s p e c t i v e l y . Thus, i f t h e pH o f t h e a c t i v a t -
ed sludge mixed l i q u o r i s below 8.0, poor
n i c k e l removals are a n t i c i p a t e d . Kodukula
and Patterson(78)demonstrated t h e metals were
removed p r i m a r i l y by s o r p t i o n processes i n
a c t i v a t e d sludge treatment. F r i s t o e and
Nelson(51) developed a chemical s p e c i a t i o n -
d i s t r i b u t i o n model f o r heavy metals and
a p p l i e d i t t o cadmium i n a c t i v a t e d sludge
from a f u l l - s c a l e wastewater treatment p l a n t .
I n t h e model, cadmium a d s o r p t i o n t o b a c t e r i a l
s o l i d s was q u a n t i f i e d by t h e d e t e r m i n a t i o n
o f c o n d i t i o n a l a d s o r p t i o n constants; t h e
cadmium complexation by d i s s o l v e d organic
compounds was q u a n t i f i e d by t h e d e t e r m i n a t i o n
o f condi t i o n a l formation constants. Both t h e
a d s o r p t i o n by b a c t e r i a l s o l i d s and t h e cad-
mium complexation a r e s t r o n g l y pH dependent.
I n general, below pH 4, a d s o r p t i o n i s l e s s
than 20%; above pH 7, a d s o r p t i o n exceeds 80%.
180 Separation of Heavy Metals
A t pH 10 a d s o r p t i o n increases t o 90-99%.
Soluble cadmium s p e c i a t i o n i s dominated by
f r e e cadmium i o n below pH 6, by cadmium-organic
l i g a n d complexation i n t h e pH range o f 61pH17,
and by i n o r g a n i c species a t pH 8 and 9. The
cadmium adsorbed by b a c t e r i a l s o l i d s i n c r e a s e d
from -30% a t pH 4 t o near 90% a t pH 9. Organic
l i g a n d complexation o f cadmiumin a c t i v a t e d
sludge i s s i g n i f i c a n t i n t h e pH range o f 5
t o 8. Wu and Hilgev(163)observed t h a t mercury
contaminants e n t e r i n g an a c t i v a t e d sludge
wastewater treatment p l a n t may undergo several
a1 t e r n a t e b i o t r a n s f o r m a t i o n s d u r i n g t h e t r e a t -
ment process. Adsorption o f mercury by sludge
and v o l a t i l i z a t i o n o f m e t a l l i c mercury by
b a c t e r i a l r e d u c t i o n o f mercuric mercury were
observed t o be complementary processes d u r i n g
the transient period following the introduction
o f mercury. Adsorption was t h e major mechanism
f o r mercury removal a t steady s t a t e ; m e t h y l a t i o n
was i n s i g n i f i c a n t a t t h e dosages studied.
To date, most o f the research on heavy
metals removal i n b i o l o g i c a l systems has been
d i r e c t e d towards t h e suspended growth a c t i v a t -
ed sludge process. Chang e t a1 .(30)s t u d i e d
t h e removal o f heavy metals i n a f i x e d - f i l m
b i o l o g i c a l system f i n d i n g i t p r i m a r i l y a t t r i b u -
t a b l e t o t h e s o r p t i o n o f s o l u b l e and f i n e metal
p a r t i c u l a t e s by b i o l o g i c a l f l o c s ; t h e r a t e
o f uptake was g r e a t l y a f f e c t e d by pH. The
average removal o f s o l u b l e Cd was 95 and 85%
a t i n f l u e n t c o n c e n t r a t i o n s o f 5 and 20 mg/l,
respectively. Copper removals were g e n e r a l l y
lower than t h a t o f cadmium. The s o l u b l e Cu
removal increased from 40% a t 1 mg/l s p i k e
o f Cu t o 90% when t h e s p i k e was increased t o
5 mg/l. When t h e copper feed was increased
t o 10, 25, and 50 mg/l. the average s o l u b l e
Cu removal decreased t o 75, 40, and 30%, r e -
s p e c t i v e l y . Approximately 80-90% o f the heavy
metal r e d u c t i o n occurred i n t h e f i r s t stage
o f t h e three-stage r o t a t i n g b i o l o g i c a l con-
t a c t o r (RBC) system. L i m i t e d p a r a l l e l s t u d i e s
on t h e Cd and Cu removals between1 t h e RBC and
the a c t i v a t e d sludge systems i n d i c a t e d t h a t
a c t i v a t e d sludge was more e f f i c i e n t i n removing
metals a t low metal s p i k i n g c o n c e n t r a t i o n s
were used.
Pugsley e t a1 .(12g)showed t h a t w i t h sui t a b l e
n u t r i e n t s and a pH i n t h e range o f 5.5-9.0,
cultures o f Desulfovibrig desulfuricans w i l l
grow and w i l l reduce SO4- t o S- under anaerobic
c o n d i t i o n s . Given s u f f i c i e n t c o n c e n t r a t i o n s
o f SO4, n u t r i e n t s , D. desulfuricans, and a
l o n g growth p e r i o & sufflcien$+S- i s gerirated
t o p r e c i p i t a t e Cu , Fe , Zn , and Mn from
raw mine drainage wastewater.
AlChE SYMPOSIUM SERIES
EVAPORATION/DISTILLATION
The p r i m a r y use o f e v a p o r a t i o n and d i s t i l -
l a t i o n treatment has been f o r product recovery,
w i t h some l i m i t e d use t o t r e a t f i n a l concen-
t r a t e d wastewater residues t o dryness. These
techniques a r e b a s i c a l l y e n d - o f - t h e - l i n e pro-
cesses. G e n e r a l l y e v a p o r a t i v e processes are
economical o n l y f o r concentrated r i n s e s and
mu1t i s t a g e c o u n t e r c u r r e n t r i n s i n g ( 134) .This
technique r e q u i r e s segregation o f wastes by
compatible types and use o f v a r i o u s means f o r
e x c l u s i o n and/or removal o f i m p u r i t i e s .
Evaporative recovery concentrates t h e chemical
dragout i n t h e r i n s e water t o b a t h s t r e n g t h
r e t u r n i n g t h e concentrated s o l u t i o n t o t h e
process tanks. The evaporated water i s con-
densed and r e t u r n e d t o t h e r i n s i n g system,
thereby m i n i m i z i n g water consumption.
Two types o f evaporative recovery systems
are commonly used: t h e vacuum evaporator and
t h e atmospheric evaporator(ll3). The atmospheric
evaporator operates a t atmospheric pressure
and t h e normal b o i l i n g temperature o f t h e
s o l u t i o n b e i n g t r e a t e d . A vacuum evaporator
operates a t subatmospheric pressures enabling
evaporation t o occur a t temperatures i n t h e
range o f 130-190F. Both types o f evaporators
can be operated i n e i t h e r open o r closed l o o p
processing c y c l e s . I n t h e closed loop opera-
t i o n , t h e system i s designed t o recover 100%
o f t h e processing bath chemicals l o s t i n t h e
dragout f o r reuse i n t h e metal f i n i s h i n g cycle.
No e x t e r n a l r i n s e water i s added f o r makeup
except t h a t r e q u i r e d t o replace t h e l o s s due
t o atmospheric evaporation. The o n l y chemicals
r e q u i r e d are those r e q u i r e d t o replace what
has been deposited on p a r t s o r due t o any
s p i l l a g e and a c c i d e n t a l losses. The open loop
system i s o f t e n employed i n i n s t a l l a t i o n s where
t h e r e are an i n s u f f i c i e n t number o f r i n s e tanks
I t i s designed f o r p a r t i a l recovery o f t h e
processing bath.
Four d i s t i l l a t i o n processes are commonly
used t o t r e a t spent p i c k l e liquors(l48).These
d i s t i l l a t i o n processes have i n common t h e use
o f vacuum evaporation and a d d i t i o n o f s u l f u r i c
a c i d t o t h e spent p i c k l e l i q u o r a t some stage
i n t h e recovery scheme. Advantages o f work-
i n g under vacuum include:
The c o r r o s i v e a c t i o n o f t h e mixed a c i d i s
reduced due t o t h e lower d i s t i l l a t i o n
temperatures i n v o l v e d .
Lower c o s t m a t e r i a l s o f c o n s t r u c t i o n can
be used.
The i n t e r e c t e d reader i s r e f e r r e d t o reference
(148) f o r d e s c r i p t i o n s and d e t a i l s o f t h e
No. 243, Vol. 81
d i s t i l 1a t i o n processes.
P a t t e r s o n and M i n e a r ( l l 3 ) p o i n t o u t t h a t
e v a p o r a t i o n i s a w e l l - e s t a b l i s h e d technology
f o r r e c o v e r i n g p l a t i n g chemicals and water from
p l a t i n g waste e f f l u e n t s . Commericial u n i t s
have been b u i l t f o r h a n d l i n g zinc, copper,
n i c k e l , chromium, and o t h e r metal p l a t i n g baths.
Disadvantages o f e v a p o r a t i o n / d i s t i l l a t i o n
processes i n c l u d e :
Relatively high capital costs.
R e l a t i v e l y high operational costs ( p a r t i c u -
l a r l y f o r vacuum systems.)
D i s t i l l a t i o n processes are energy i n t e n s i v e .
The economics o f d i s t i l l a t i o n imposes a
c o n s t r a i n t on t h e s i z e range o f these systems.
These systems are complex, r e q u i r i n g t r a i n e d
personnel t o operate and m a i n t a i n them.
ADSORPTION
Due t o t h e h i s t o r i c a l development and use
o f a c t i v a t e d carbon i n water and wastewater
treatment, most o f t h e a p p l i c a t i o n s and research
e f f o r t on a c t i v a t e d carbon have been o r i e n t e d
towards o r g a n i c s removal (63). Research e f f o r t s
on i n o r g a n i c s removal by a c t i v a t e d carbon,
s p e c i f i c a l l y m e t a l l i c ions, have been markedly
1 i m i t e d . Huang(63) p r o v i d e s an excel l e n t r e v i e w
o f i n o r g a n i c s removal by a c t i v a t e d carbon by
c o n s i d e r i n g such f a c t o r s as s u r f a c e p r o p e r t i e s
(and t h e i r measurement) and a d s o r p t i o n charac-
t e r i s t i c s o f c a t i o n i c and a n i o n i c species o n t o
a c t i v a t e d carbon surfaces. I m p o r t a n t p h y s i c a l -
chemical p r o p e r t i e s a f f e c t i n g i n o r g a n i c e l e c t r o -
l y t e a d s o r p t i o n i n c l u d e : s p e c i f i c s u r f a c e area,
pore s t r u c t u r e , e l e c t r o p h o r e t i c p r o p e r t i e s ,
and s u r f a c e a c i d i t y .
Very l i t t l e has been r e p o r t e d on t h e use
o f a c t i v a t e d carbon f o r removal o f i n o r g a n i c s
f r o m wastewaters. A c t i v a t e d carbon was r e -
p o r t e d t o be a p o t e n t i a l adsorbent f o r heavy
metal removal (4,35). Salvaged automobile t i r e s
a r e capable o f removing t r a c e metals (A1 , Hg,
Ni, Cd, C r , Co, Cu, Fe, Pb, Mn, Ag, and Zn)
from s o l u t i o n due t o v a r i o u s m a t e r i a l s p r e s e n t
i n t h e t i r e s , such as s u l f u r , carbon black,
f i l l e r s , s y n t h e t i c rubber, a n t i o x i d a n t s , e t c .
(103-05).Saito(134)2sed a c t i v a t e d carbon and s u l -
f o n a t e d coal f o r removal o f Cu, Cd, and Fe f r m
wastewaters. Removals exceeding 98% were
achieved f o r c u p e r i c i o n s t r e a t e d w i t h s u l f o -
nated coal a f t e r a one-stage e x t r a c t i o n . For
an i n i t i a l copper c o n c e n t r a t i o n o f 312 mg/l,
t h e r e s i d u a l copper c o n c e n t r a t i o n was reduced
t o 0.08 mg/l a f t e r a two-stage e x t r a c t i o n .
S i g n i f i c a n t removals were achieved l i k e w i s e
w i t h a c t i v a t e d carbon. The e x t e n t of heavy
metal a d s o r p t i o n on a s p e c i f i c t y p e o f carbon
181
i s expected t o be a f u n c t i o n o f : m ? t d l - l i g a n d
c h a p f i + $ i s t r i b y t h o r ( f o r example ML ,
MH L -
' MOHL - ) ; f r e e metal and f r e e
l i g a n d charges; t h e pH o f t h e carbon s u r f a c e
and t h e p o l a r i t y o f l i g % % molecules. The
pH w i l l a f f e c t t h e charge d i s t r i b u t i o n o f
t h e v a r i o u s species as w e l l as t h e hydroxo
group d i s t r i b u t i o n a t t h e a c t i v a t e d carbon
surface. J e v t i t c h and Bhattacharyya (69)
e s t a b l i s h e d t h e a d s o r p t i o n c a p a c i t i e s o f com-
plexed heavy metal i o n s by a c t i v a t e d carbons
under e q u i l i b r i u m c o n d i t i o n s . An e x t e n s i v e
experimental i n v e s t i g a t i o n was conducted w i t h
a c t i v a t e d carbons t o establish2$he a$$or;;$p"
capaci5jes o f heavy metals (Cd , N i , Y
and Zn ) i n t h e presence o f complexing agents
(EDTA, t r i e t h y l e n e t e t r a m i n e (TRIEN), c i t r a t e ,
e t c ) . Adsorption e q u i l i b r i a a r e e x p l a i n e d
by species charges and carbon s u r f a c e charge
c h a r a c t e r i s t i c s . I n t h e pH range 7.5-8.0,
t h e a c t i v e s i t e s a r e p o s i t i y f l y charged. The
a d s o r p t i o n c a p a c i t i e s o f Cd (and o t h e r heavy
m e t a l s ) , f r e e ligands, and cadmium-ligands
were a l s o a f u n c t i o n o f feed metal concentra-
t i o n , t y p e s o f l i g a n d s , molar r a t i o o f l i g a n d /
metal, and pH. Complete m e t a l - l i g a n d species
d i s t r i b u t i o n s were c a l c u l a t e d by computer
solutions o f multiple reaction equilibria.
For an e q u i l i b r i u m cadmium c o n c e n t r a t i o n o f
0.1 mM (pH 7.5-8.0), t h e sequence i n adsorp-
t i o n c a p a c i t y f o r cadmium c h e l a t e s i s ,Q ,-c,
> QCD-citrate > QCd-TRIEN > QCd-tartrate.
Huang e t a1 . evaluated t h e a c t i v a t e d
carbon a d s o r p t i o n process f o r removal o f
Co(I1) from s o l u t i o n w i t h s p e c i a l emphasis
p l a c e d on t h e e f f e c t of v a r i o u s organic sub-
stances on Co(I1) removal. T h e i r r e s u l t s
showed Co( 11) was removed by a d s o r p t i o n r a t h e r
than be p r e c i p i t a t i o n alone. Fourteen types
o f a c t i v a t e d carbon were evaluated f o r t h e i r
Co(I1) removal c a p a b i l i t i e s . Two a c t i v a t e d
carbons, Nuclar SA and Nuchar SN, gave s i m i l a r
h i g h metal removal c a p a c i t i e s (removals
approached loo%, depending on t h e s o l u t i o n pH).
The Co(I1) removal percentage decreased w i t h
i n c r e a s i n g s u r f a c e l o a d i n g s . The authors
showed t h a t t h e presence o f o r g a n i c a c i d r e -
s u l t s i n f i v e d i f f e r e n t cases o f e f f e c t s i n
Co(I1) a d s o r p t i o n : 1. anion induced c a t i o n
adsorption, 2. complexes n o t adsorbable ( o r
c o m p e t i t i v e anion a d s o r p t i o n ) , 3. complexes
adsorbable ( o r non-competitive anion a d s o r p t i o n ) ,
4. anion-induced c a t i o n a d s o r p t i o n and com-
plexes n o t adsorbable, and 5 . anion-induced
c a t i o n a d s o r p t i o n and cumplexes adsorbable.
Depending on the extenL o f complex formation
and t h e a d s o r b a b i l i t y o f t h e complexed Co(I1)
and o f t h e l i g a n d , i t w a s p o s s i b l e t o d i f -
f e r e n t i a t e f o u r d i f f e r e n t e f f e c t groups:
182 Separation of Heavy Metals
a. enhancement over t h e mid-pH range, b.
i n h i b i t i o n as t h e pH increases, c. no
e f f e c t , and d. enhancement f o l l o w e d by i n -
h i b i t i o n as the pH increases. The regenera-
t i o n o f the exhausted a c t i v a t e d carbon by
s t r o n g a c i d was determined f e a s i b l e . The
a d s o r p t i v e c a p a c i t y o f the r e c y c l e d a c t i v a t e d
carbon was maintained a t t h e 92% l e v e l a f t e r
the 5th cycle.
Ku and Peters (80) i n v e s t i g a t e d t h e use
o f a c t i v a t e d carbon as a p o l i s h i n g s t e p f o r
treatment o f i n d u s t r i a1 p l a t i ng wastewaters.
When hydroxide p r e c i p i t a t i o n i s employed f o r
removal o f heavy metals, t h e use o f a c t i v a t e d
carbon a l l o w s s i g n i f i c a n t l y lower e f f l u e n t
metal concentrations t o be achieved. The
r e s i d u a l z i n c and cadmium c o n c e n t r a t i o n s were
reduced g r e a t e r than 70% through use of
a c t i v a t e d carbon f o l l o w i n g hydroxide p r $ $ i p i -
t a t i o n . The adsorption c a p a c i t y f o r Cd was
c a l c u l a t e d t o be between 5 and 20 Vmole/gm
o f powdered a c t i v a t e d carbon f o r 9 i p H i l l
which i s muchlower than t h e 40-50 vmoles/gm
o f powdered a c t i v a t e d carbon r e p o r t e d by
Huang and W i r t h (60). This i s l i k e l y due t o
t h e i n t e r f e r e n c e o f ammonia and cyanide on
t h e a c t i v a t e d carbon a d s o r p t i o n process(80).
Because o f t h e completeness and r a p i d i t y f o r
removal o f heavy metal s by s u l f i d e p r e c i p i t a -
t i o n , l i t t l e enhancement i n heavy metal removal
i s achieved u s i n g a c t i v a t e d carbon treatment
as a p o l i s h i n g step. The s i g n i f i c a n t r e s u l t
o f such a p o l i s h i n g step f o l l o w i n g s u l f i d e
p r e c i p i t a t i o n l i e s i n i t s a b i l i t y t o sub-
s t a n t i a l l y reduce t h e s u l f i d e concentration,
thereby lessening t h e p o t e n t i a l f o r H2S gas
evolution.
Algae has a l s o been used f o r removal of
heavy metals from wastewaters and f o r con-
c e n t r a t i o n o f valuable metals from d i l u t e
s o l u t i o n s (50,54). When algae grown i n a
sewage lagoon were mixed w i t h heavy metal
s o l u t i o n s and subsequently were dewatered by
an i n t e r m i t t e n t sand f i l t e r , 98% o f t h e Cu
and 100% o f the Cd were removed from s o l u t i o n
( 5 0 ) . Rapid uptake o f cadmium by algae was
observed i n the f i r s t stage o f a t e r t i a r y
treatment system ( 7 2 ) . Sloan e t a l . (141)
s t u d i e d the removal o f f o u r d i f f e r e n t metals
(Cd, Cu, Pb, and Zn) a t d i f f e r e n t concentra-
t i o n s u s i n g t h r e e d i f f e r e n t a l g a l species.
Cadmium, copper, and l e a d c o u l d be removed
i n a two stage process w i t h t h e f i r s t stage
b e i n g e i t h e r i o n exchange o r passive adsorp-
t i o n and t h e second stage being removal from
s o l u t i o n by passive d i f f u s i o n through t h e c e l l
membrane.
Swallow e t a l . (150) i n v e s t i g a t e d t h e
AlChE SYMPOSIUM SERIES
s o r p t i v e p r o p e r t i e s o f hydrous f e r r i c oxide
u s i n g copper and l e a d as sorbates. They noted
f r e s h hydrous f e r r i c oxide sorbed more l e a d
than aged and l e a d sorbed on t h e f r e s h oxide
was l e s s e f f i c i e n t l y recovered suggesting
o c c l u s i o n occurs i n the c o p r e c i p i t a t i o n pro-
cess. V a r i a t i o n s i n i o n i c s t r e n g t h and com-
p o s i t i o n o f t h e background e l f l t r o l y t e s o l -
u t i o n had no e f f e l i on t h e Cu sorption
isotherm. The Pb s o r p t i o n isotherm was
s i m i l a r l y u n a f f e c t e d by changes i n i o n i c
s t r e n g t h ; t h e presence o f C1 g r a m a t i c a l l y
decreased t h e percentage o f Pb sorbed a t
any given pH. Benjamin and Leckie (12) studied
the e f f e c t s o f complexation by C1, SO , and
S 0 on a d s o r p t i o n o f Cd o n t o f o u r d i f f e r e n t
oaide surfaces. I n t e r a c t i o n s between metal
i o n s and complexing l i g a n d s i n t h e presence
o f an adsorbent surface can be d i v i d e d i n t o
t h r e e groups based on t h e o r i g i n and s t r e n g t h
o f the interaction:
a. m e t a l - l i g a n d complexes may form i n s o l u t i o n
and adsorb o n l y weakly o r n o t a t a l l .
b. t h e species may i n t e r a c t i n d i r e c t l y a t
t h e surface a1 t e r i n g t h e surface e l e c t r i -
cal properties.
t h e m e t a l - l i g a n d complex can adsorb strong-
c.
l y enhancing t h e removal o f metal, l i g a n d ,
o r both from s o l u t i o n compared t o t h e
case when e i t h e r one i s present alone.
The c h l o r i d e and s u l f a t e complexes adsorb less
s t r o n g l y than t h e uncomplexed cadmium ions.
Adsorption o f t h i o s u l f a t e complexes i s more
l i k e t h a t o f free ligand.
The e f f e c t o f anions on the adsorption
o f heavy metals was addressed by Huang e t a l .
( 5 7 ) . The r o l e o f anions i n the adsorption
o f heavy metals i s d e l i n e a t e d by c o n s i d e r a t i o n
o f t h e f o l l o w i n g r e a c t i o n steps:
1. Anions accumulate i n t h e double l a y e r o f
a p o s i t i v e l y charged p a r t i c l e .
2. Approach o f metal i o n s t o the soil surface
being f a c i l i t a t e d .
3. Complexes form between t h e heavy metal
i o n s and t h e already adsorbed aqueous
anionic ligands.
For t h e s o i l - w a t e r environment, copper and
z i n c are more removable than l e a d and cadmium.
Various research s t u d i e s have been per-
formed t o i n v e s t i g a t e t h e removal o f a s i n g l e
heavy metal from s o l u t i o n s . These s t u d i e s
are summarized i n t h e f o l l o w i n g subsections.
Cadmium
Cedar wood f 1our cooked w i t h a1 k a l i (17.5%
NaOH) f o r 30 minutes t o convert p a r t of the
 No. 243,Vol. 81
way$ t o a l k a l i c e l l u l o s e was a b l e t o reduce
Cd from 8.7 t o 0.4 mg/l from a s o l y $ i o n (164).
The a d s o r p t i o n c h a r a c t e r i s t i c s o f Cd onto
t h r e e a c t i v a t e d carbons ( F i l t r a s o r b 400 Nuchar
722, and Nuchar C-190-N) were s t u d i e d by Huang
(63) i n v e s t i g a t i n g such f a c t o r s as pH, i n i t i a l
cadmium concentration, dose and type o f carbon,
and t h e presence o f c h e l a t i n g agents on cadmium
adsorption. Removal e f f i c i e n c y increased w i t h
i n c r e a s i n g pH f o r a l l t h r e e carbons. Since
t h e F i l t r a s o r b 400 and Nuchar 722 are both
H-type carbons, p r e c i p i t a t i o n o f CdCO occurs
a t h i g h pH and i s a s i g n i f i c a n t removh
megtanism. A t t h e pH , a f i n i t e amount of
Cd adsorbed on t h e keEhar 722 and s i g n i f i -
c a n t l y adsorbed on t h e Nuchar C-190-N. The
Nuchar C-190-N, a L-type carbon which adsorbs
o n l y a c i d i c m a t e r i a l s , i s an e x c e l l e n t ad-
sorbent f o r c a t i o n metal removal; t h e Nuchar
C-190-r+had t h e g r e a t e s t a d s o r p t i v e c a p a c i t y
f o r Cd a d s o r p t i o n o f t h e carbons tested.
I n c r e a s i n g t h e carbon tocadmium r a t i o lOOx,
a t h r e e - f o l d increase i n removal e f f i c i e n c y
r e s u l t e d ; however t h e time t o equi 1 ibrium
a d s o r p t i o n remains u n a f f e c t e d . Strong chel a t -
i n g agents were added i n an attempt t o improve
t h e cadmium removal c a p a c i t y o f t h e F i 1 t r a s o r b
400 ( F i 1t r a s o r b 400 adsorbs p r i m a r i l y a n i o n i c
species). An improvement i n terms o f t h i s
percentage metal removal, from 20% w i t h o u t
NTA t o 40% w i t h NTA a t 0 . 0 1 ~Cd. and 50% w i t h
NTA a t 0 . 1 ~Cdi r e s u l t e d a t n e u t r a l pH, w i t h
comparable r e s u l t s observed f o r Cd removal
performed i n t h e presence o f EDTA. Huang (63)
a t t r i b u t e d t h i s improvement t o t h e f o r m a t i o n
o f CdEDTA- o r CdNTA- complexes which c o u l d
be e l e c t r o s t a t i c a l l y a t t r a c t e d by F i l t r a s o r b
400 (whose surface charge i s p o s i t i v e f o r
pH < 7) f o l l o w e d by f u r t h e r a s s o c i a t i o n o f
Cdt+ i o n s w i t h t h e adsorbed anions.
Copper
Using a s y n t h e t i c seawater of h i g h i o n i c
s t r e n g t h (1.6!jy NaCl), Moore (96) s t u d i e d the
removal o f Cu by s i x d i f f e r e n t a c t i v a t e d
carbons, w i t h Barneby-Cheney PC-859$+being
t h e most e f f e c t i v e adsorbent f o r Cu removal.
The removal e f f i c i e n c y was extremely poor
.
however (6%) The a c t i v a t e d carbons t e s t e d
were a l l o f t h e H-type; a t pH 4-5, t h e carbon
surfaces a r e p o s i t i v e l y charqTd thereby
r e p e i l i n g t h e predominant Cu species (Cu",
CuCl , and CuOH ) from t h e c g b o n surface.
Although pH and t h e t o t a l Cu concentration
3r$+themost i m p o r t a n t f a c t o r s i n con1.olling
Cu adsorption, t h e magnitude o f Cu removal
by a c t i v a t e d carbon was i n s i q q i f i c a n t even
under t h e optimum pH and Cu concentration
c o n d i t i o n s . Huang (63) i n v e s t i g a t e d u s i n g
e i g h t d i f f e r e n t c h e l a t i n g agents t o improve
1
183
t h e Cu++ a d s o r p t i v e c a p a c i t y . Using 8-hydro-
xyquinol ine, t h e most e f f e c t i v e c h e l a t i p g
agent used, a s l i g h t improvement i n Cu ad-
s o r p t i o n from $+to 7% was adsorbed. The ad-
s o r p t i o n o f Cu onto a c t i v a t e d carbon (Aqua
Nuchar A) was found t o depend on t h e i o n i c
s t r e n g t h (102). For t h e c o n c e n t r a t i o n range
o f 0.001 t o 0.100 M NaCl adsorbabi 1it y o f CU+'
was h i g h w i t h a d i s t r i b u t i o n c o e f f i c i e n t D o f
-700. For h i g h e r NaCl concentrations, D i n -
creases w i t h i n c r e a s i n g NaCl concentrations;
D - 5+OtoO near 6M NaC1. The r a p i d increase
i n Cu adsorption w i t h i n c r e a s i n g NaCl con-
c e n t r a t i o n s was a t t r i b u t e d t o t h e a d s o r p t i o n
o f n e g a t i v e l y charged CuC12 complexes.
Mercury
The amount o f mercury removed i s known
t o increase w i t h decreasing pH. The e f f l u e n t
mercury c o n c e n t r a t i o n from a p r e c i p i t a t i o n /
f i l t r a t i o n / a d s o r p t i o n process was reduced from
30-50 ppb t o 3-5 ppb by l o w e r i n g t h e pH from
7 t o 2-4 (109). The mercury adsorption
c a p a c i t y increased s t e a d i l y by decreasing t h e
pH from 9 t o 2, as noted by Huang (@). Thiem
e t a1 . (56) noted t h e removal o f Hg by
a c t i v a t e d carbon was s e n s i t i v e t o pH; ap-
p r o x i m a t e l y t w i c e as much mercury was removed
a t pH 7 was compared t o pH 9. Research by
Humenick e t a l . (63) u s i n g column experiments
showed t h a t good mercury removal was a t t a i n e d
a t low pH. For a carbon column i n which t h e
i n f l u e n t was a c i d i f i e d t o pH 4 and employing
a c o n t a c t time o f 11 minutes, t h e e f f l u e n t
c o n c e n t r a t i o n averaged 1 ppb over a 5 day
period. The column mercury removal c a p a c i t y
increased from 0.3 t o 4.1 mg Hg removed p e r
gram o f carbon ( F i l t r a s o r b 400) by a d j u s t i n g
t h e pH from 10 t o 4. By adding a p r e c i p i t a t -
i n g c h e l a t i n g agent (ammonium 1 - p y r r o l i d i n e
dijQio-carbamate) t h e removal c a p a c i t y o f
Hg by a c t i v a t e d carbon was s i g n i f i c a n t l y
increased. Treatment o f t h e a c t i v a t e d carbon
surface by+$S was a l s o e f f e c t i v e i n increas-
i n g t h e Hg i d s o r p t i o n capacity. During a
study o f t h e c a t a l y t i c o x i d a t i o n o f H S over
carbon, Sinha and Walker (139) observgd t h a t
a l a r g e amount o f mercury from a mercury
d i f f u s i o n pump and mercury manometer was taken
up by t h e s u l f u r i z e d carbon c a t a l y s t a t 140C.
I n subsequent experiments, s i g n i f i c a n t mercury
adsorption was observed u s i n g t h e s u l f o n a t e d
a c t i v a t e d carbon.
Chromium
Chromates can be e f f e c t i v e l y removed from
wastewaters by passing t h e chromate 1aden waste-
water through a column packed w i t h p l a t i n u m
b l a c k catalyst-impregnated a c t i v a t e d carbon
184 Separation of Heavy Metals
A f t e r treatment, a wastewater i n i t i a l l y con-
t a i n i n g 100 mg/l chromate had a r e s i d u a l
c o n c e n t r a t i o n o f l e s s than 0.1 mg/l. By m i x i n g
200 m l K C r 0 s o l u t i o n w i t h 5.0 gms o f
powdered2c060t?ut she1 1 charcoal and h e a t i n g
i n an autoclave a t 200C f o r 30 minutes, t h e
c o n c e n t r a t i o n o f Cr( V I ) was reduced below
0.01 mg/l (152). Huang and Wu (61) found t h a t
t h e removal o f Cr(V1) by c a l c i n a t e d charcoal
was most s i g n i f i c a n t a t low pH and f o r low
i n i t i a l Cr(V1) concentrations. They specu-
l a t e d t h a t the HCrO - i o n s were t h e major
species being removgd. Landigan and Hal 1owe1 1
(82) demonstrated t h a t a c t i v a t e d carbon c o u l d
be used by small p l a t i n g f a c i l i t i e s f o r r e -
moval o f chromium.
I n a study on t h e a d s o r p t i o n o f C r ( I I 1 )
and Cr(V1) as a f u n c t i o n o f pH and t h e amount
o f t o t a l C r and Cr(V1) e l u t e d from a c t i v a t e d
carbon a t pH 4-6.5, Yoshida e t a l . (166)
found t h a t Cr(V1) was r e a d i l y adsorbed on
a c t i v a t e d carbo! as anioni$+species such as
HCr04- and C r O - w h i l e C r was m i n i m a l l y
adsorbed by ac?ivated carbon. I n a c i d i c
s o l u t i o n , Cr(V1) i s r e a d i l y reduced t o C r ( I I 1 )
i n t h e presence o f a c t i v a t e d carbon. Huang
and Wu (62) l i k e w i s e s t u d i e d t h e e f f e c t o f
pH on C r ( I I 1 ) and Cr(V1) adsorption by
F i l t r a s o r b 400 a c t i v a t e d carbon. Cr(V1) was
a t l e a s t t w i c e as adsorbable as C r ( I I 1 ) . The
optimum pH f o r a d s o r p t i v e removal was 5.5-6.0
and 5.0 f o r Cr(V1) and C r ( I I I ) , r e s p e c t i v e l y .
The removal o f Cr(V1) i n v o l v e d r e d u c t i o n and
adsorption steps o c c u r r i n g c o n s e c u t i v e l y (63) :
t 1/6
-d[ Cr( V I ) ] 4. 4 x m 3 [ Cr( V I ) ]3/4[ C][ H ]
- through an appropriate poms ne (cellulose acetate.
dt + 2 . 3 ~ 1 0 - ~C [r ( V I ) I[
C I 3 [H] a polyamide, polysulfone, etc.) and withdrawing the m
where t h e f i r s t term on t h e r i g h t hand s i d e
o f t h e equation denotes t h e r e d u c t i o n r a t e
o f Cr(V1) w h i l e t h e second term denotes t h e
r a t e o f Cr(V1) adsorption. The concentrations
are a l l expressed i n moles/l w i t h t h e excep-
t i o n o f C y r e p o r t e d i n gm/l. By p r e t r e a t i n g
the Cr(V1) wastewater w i t h C1, and h e a t i n g
the a c t i v a t e d carbon i n 1M HNO s o l u t i o n f o r
30 minutes, t h e r e s i d u a l C r ( I I ? ) was s i g n i f i -
c a n t l y reduced i n batch-mode o p e r a t i o n .
I n summary, a c t i v a t e d carbon w i l l adsorb
hexavalent chromium, mercury, and many metals
complexed i n organic form. The a d s o r p t i v e
c a p a c i t y depends on t h e carbon pore s i z e , t h e
s i z e o f t h e molecule, s o l u t i o n pH, and t h e
i n i t i a l and f i n a l c o n c e n t r a t i o n o f t h e m e t a l ( s ) .
Adsorptive c a p a c i t y increases as t h e pH de-
creases; a d s o r p t i o n e f f i c i e n c y increases as
t h e c o n c e n t r a t i o n increases. Most e f f e c t i v e
treatment r e s u l t s w i t h d i 1Ute wastes. A c t i -
vated carbon treatment shows considerable
promise f o r removing t h e l a s t t r a c e o f metal
AlChE SYMPOSIUM SERIES
( i n t h e range o f 1-2 ppm) f o l l o w i n g o t h e r
treatments (such as hydroxide p r e c i p i t a t i o n ,
e l e c t r o d e p o s i t i o n , cementation, e t c . ) . A c t i -
vated carbon treatment has been s u c c e s s f u l l y
used f o r e x t r a c t i n g g o l d f r o m cyanide s o l u t i o n s .
To determine t h e e f f e c t i v e n e s s o f a c t i -
vated carbon f o r a p a r t i c u l a r metal bearing
wastewater, a d s o r p t i o n isotherms a r e developed
i n d i c a t i n g t h e amount o f m a t e r i a l adsorbed
a t a p a r t i c u l a r c o n c e n t r a t i o n . The t e s t s are
r u n on several d i f f e r e n t carbons t o determine
which one p r o v i d e s t h e most e f f e c t i v e t r e a t -
ment. Granular a c t i v a t e d carbon (GAC) i s
u s u a l l y p r e f e r r e d s i n c e i t can be chemically
regenerated and reused. Powdered a c t i v a t e d
carbon (PAC) i s l e s s expensive, b u t i t can
o n l y be used on a once-through b a s i s . PAC
i s d i f f i c u l t to handle due t o a tendency t o
dust and i t must be removed from t h e waste-
stream by c o a g u l a t i o n and/or f i l t r a t i o n .
A c t i v a t e d carbon treatment has n o t been widely
employed f o r removal o f heavy metals : ( 2 9 ) .
MEMBRANE OPERATIONS
The use o f msrbrane processes for water reuse,
wastewater v o l m &tion, and byproducts (such as,
valuable m t a l s recovery) i s gaining considerable atten-
tion i n many industries. W r a n e pmesses can be divi-
ded i n thwe cakqories: high pressure reverse o m s i s
(500-1500 psi), lm pressure reverse o m s i s (200-500
psi), and ultrafiltration (20-100 psi). The pnxess
consists i n letting the solution flw under pressure
brane permeate product water at atmospheric pressure. For
reverse o m s i s (Ro), the applied pressure nust be cm-
siderably greater than the o m t i c pressure of the re-
jected solutes i n order to obtain adequate water flux.
Ultrafiltration with neutral n e s i s normally used
to m v e large mlecular w i g h t (W > 1ooO) solutes.
Recently Bel f o r t (10) provided an ex-
t e n s i v e overview o f s y n t h e t i c membrane pro-
cesses and v a r i o u s wastewater treatment a p p l i -
c a i t o n s . An e x c e l l e n t review o f membrane
m a t e r i a l s p r e p a r a t i o n and c h a r a c t e r i z a t i o n
was r e p o r t e d by Lloyd ( 8 6 ) . Reverse osmosis
membrane f l u x and s o l u t e t r a n s p o r t have been
commonly described by two models: t h e s o l u t i o
d i f f u s i o n model (88) and t h e p r e f e r e n t i a l
s o r p t i on-capi 11a r y f 1ow model : ( 145).
The development o f s y n t h e t i c t h i n - f i l m
composi t e membranes has r e s u l t e d i n sol u t e
removals a t lower pressures over a broad pH
range (pH 2-12). The new generation membranes
No. 243,Vol. 81
a1 low simultaneous separation o f metal s a l t s
and o r g a n i c s from aqueous systems. These low
pressure processes w i t h composite membranes
have d e f i n i t e advantages i n terms o f energy
savings and c a p i t a l cost. T h i n - f i l m membranes
r e s y l t i n a h i g h e r water f l u x (25-35 g a l l o n s /
( f t ) ( d a y ) ) and 95-99% removal o f various chem-
i c a l s (14,16).
Much o f t h e development work and commer-
c i a l u t i l i z a t i o n o f t h e RO process has occurred
w i t h i n t h e l a s t 15 years, w i t h p a r t i c u l a r em-
phasis devoted t o d e s a l i n a t i o n and water t r e a t -
ment and recovery. The power requirements
amount t o 4 t o f hp/1000 g a l l o n s wastewater
t r e a t e d . T h i s technique has shown promise f o r
removal and recovery o f metal i o n s from waste
s o l u t i o n s . Reverse osmosis has been used t o
dewater mixed p l a t i n g r i n s e streams p r i o r t o
chemical p r e c i p i t a t i o n / c l a r i f i c a t i o n t o reduce
t h e h y d r a u l i c l o a d i n g t o t h e c l a r i f i e r ( 28).
T y p i c a l o p e r a t i n g c o n d i t i o n s are summarized
below:
feed stream t o t a l d i s s o l v e d s o l i d s 1000-10000
PPm
t o x i c metals c o n c e n t r a t i o n 1-100 ppm
feed r a t e s 5-100 gpm
C a r t w r i g h t (28) estimated ghe e x i s t i n g market
p o t e n t i a l t o be $5-10 x 10 p e r year along w i t h a
p r o j e c t e d growth r a t e o f 10-15%/year. Reverse
osmosis has a1 so been used f o r e l e c t r o p l a t i n g
s o l u t e recovery ( p l a t i n g s a l t s ) from r i n s e -
waters. The concentrate i s r e t u r n e d t o t h e
p l a t i n g p a t h and t h e permeate i s r e t u r n e d t o
t h e l a s t r i n s e . Over 170 baths a r e c u r r e n t l y
t r e a t e d w i t h RO; t y p i c a l feed r a t e s are 2-10
gal/min. The e x i s t i n g magket p o t e n t i a l was
e s t i m a t e d t o be $5-10 x 10 /year w i t h a p r o j e c t e d
growth r a t e o f lO%/year ( 2 8 ) . Continuous s i d e -
stream u l t r a f i l t r a t i o n has a l s o been employed
f o r e l e c t r o d e p o s i t i o n p a i n t baths f o r removal
o f water and contaminants. The concentrate
i s r e t u r n e d t o t h e baths; permeate i s used as
t h e f i r s t rinse o r i s discharged.
I n another membrane process, e l e c t r o -
d i a l y s i s i n v o l v e s t h e t r a n s p o r t o f i o n i c species
through membranes by a p p l i c a t i o n o f a d.c.
p o t e n t i a l . The membrane c o n t a i n s c a t i o n o r
anion exchange r e s i n s , s e l e c t i v e f o r o n l y
c a t i o n s o r anions i n t h e waste s o l u t i o n . The
c a t i o n exchange membrane p e r m i t s t h e passage
o f c a t i o n s w h i l e r e j e c t i n g anions w h i l e t h e
anion exchange membrane a l l o w s anions t o pass
and r e j e c t s c a t i o n s .
These membrane s e p a r a t i o n processes have
become standard procedures f o r s e p a r a t i o n o f
m o l e c u l a r s o l u t i o n s . I n UF, t h e d i f f e r e n t
chemical components a r e separated e x c l u s i v e l y
185
by molecular s i z e . I n RO, p a r t i c l e s i z e and
t h e chemical n a t u r e b o t h are important f o r
t h e separation o f m a t e r i a l s . F o r multicom-
ponent m i x t u r e s where h i g h l y t o x i c o r v a l u a b l e
m a t e r i a l s (heavy m e t a l s ) have t o be removed
from i n d u s t r i a l wastewaters c o n t a i n i n g these
i o n s i n low c o n c e n t r a t i o n s i n a d d i t i o n t o a
m i x t u r e o f o t h e r s a l t s , Strathman and Kock (149)
p o i n t o u t t h a t RO i s n o t w e l l s u i t e d f o r t h i s
s o r t o f separation problem. I n t h e i r study,
p o l y e t h y l e n i m i n e showed a good s e l e c t i v i t y
for+Cu ag$ was somzwhat l e s s s e l e c t i v e f o r
Zn , N i , and Ag i o n s . Quaternized p o l y -
ethylenimine had a good s e l e c t i v i t y f o r Pd,
P t , Hg, and Au. P o l y t h i o u r i e a was w e l l
s u i t e d t o b i n d Hg.
The r e j e c t i o n c h a r a c t e r i s t i c s o f low-
pressure u l t r a f i l t r a t i o n mebranes (800 mM
charge c a p a c i t y ) have been s t u d i e d f o r several
a l k a l i n e - e a r t h , heavy metal ions, and
oxyanions: (23). For many closed-loop process
i n v o l v i n g water reuse, adequate r e j e c t i o n s
o f up t o 97% w i t h charged UF membranes prevent
t h e b u i l d u p o f low molecular weight i o n i c
s o l u t e s i n t h e r e c y c l e d water : (15,19,20) .
Low-flux, t i g h t uncharged membranes (such as
c e l l u l o s e acetate) are commonly used f o r r e -
moval o f i n o r g a n i c e l e c t r o l y t e s . The s a l t
r e j e c t i o n s o f t e n exceed 98%; however t h e h i g h
e f f e c t i v e osmotic pressures and the membrane
t i g h t n e s s o f t e n n e c e s s i t a t e h i g h pressure
operation, which causes membrane compaction
problems and a r e d u c t i o n i n t h e water f l u x ( 2 3 ) .
Bhattacharyya and Grieves (23) a l s o p o i n t o u t
t h a t s e l e c t i v e separation o f s p e c i f i c i o n i c
s o l u t e s from mixed metal mixtures i s n o t
g e n e r a l l y p o s s i b l e . Membrane s w e l l i n g i s un-
d e s i r a b l e s i n c e i t would produce a loss i n
r e j e c t i o n o f monovalentanions g r e a t e r than
t h a t o f d i v a l e n t anions. Bhattacharyya and
Grieves (23) provided t h e f o l 1owing resu]i$s
foy+the c h l o y j d e and s u l f a t e s a l t s of Cu ,
N i , and Zn r e l a t i n g the u l t r a f i l t r a t e
stream c o n c e n t r a t i o n t o the i n l e t stream con-
cen t r a t i on : 1.36
Cf = 0.093 Ci
R
* = 1-0.093 C 1.
0.36
Th$+reje$$ion depeggence on concentration f o r
Cu , N i , and Zn s u l f a t e s a l t s was l i k e -
wise described bv:
1.21
Cf = 0.082 Ci
0.21
R* = 1-0.082 C
i
P o t e n t i a l a p p l i c a t i o n s o f t h i s technology
include u l t r a f i l t r a t i o n o f plating rinse
waters, u l t r a f i l t r a t i o n o f t o x i c metal con -
186 Separation of Heavy Metals
s t i t u e n t s from metal manufacturing wastewaters,
d i s s o l v e d s o l i d s reduction, and u l t r a f i l t r a t i o n
o f photographic processing water c o n s t i t u e n t s .
As an example, a s e r i e s o f UF experiments(23)
were performed w i t h a c t u a l rinsewaters by
d i 1u t i n g a Watts-type b r i g h t n i c k e l - p l a t i n g
s o l u t i o n . The unadjusted pH ranged from 5.2
t o 6.8; t h e i n l e t n i c k e l c o n c e n t r a t i o n ranged
from 35 mg/l 8 0 949 mg/l. The r e j e c t i o n s ( a t
hp = 2.8 x 10 N/m ) of t o t a l organic carbon,
c o n d u c t i v i t y , and o p t i c a l d e n s i t y ( a t 400 nm)
were 0.67, 0.73, and 0.90+, r e s p e c t i v e l y .
Bhattacharyya and Grieves (23) a1 so observed
t h a t cadmium s u l f a t e r e j e c t i o n (88%) was some-
what greater+than t h a t of++the o t h e r s u l f a t e
s a l t s o f Ca , N i , and Zn i n a metal manu-
f a c t u r i n g wastewater. Using a n e g a t i y T l y
charged UF mgybrane, r e j e c t i o n s o f Cu , Ni",
Zn , and Cd were 0.88, 0.88, 0.88, and 0.90,
respectively .
Pusch and Walch (130) p o i n t o u t t h a t
membrane separation processes r e q u i r e o n l y
about 1/10 o f t h e energy c o s t s o f a correspond-
i n g d i s t i l l a t i o n process i f small t o medium
wastewater treatment p l angs are considered
( p l a n t s i z e s o f 100-1000 m /day). Restrictions
associated w i t h t h e use o f membrane processing
i n v o l v e membrane l i f e t i m e and s e l e c t i v i t y s i n c e
s t r o n g a c i d i c , a l k a l i n e , and/or o x i d i z i n g
s o l u t i o n s o f t e n have t o be concentrated r a t h e r
than n e u t r a l o r p H - c o n t r o l l e d r i n s e water.
Conventional membranes r a p i d l y d e t e r i o r a t e
i n such chemically a c t i v e b r i n e s . Recycling
i s l e s s e f f e c t i v e i f v a l u a b l e m a t e r i a l s must
be i s o l a t e d i n t h e presence o f l a r g e amounts
o f low value by-products. I t thus becomes
necessary f o r development o f processes f o r
separation o f d i f f e r e n t s a l t s i n a d d i t i o n t o
t h e p u r i f i c a t i o n o f t h e r i n s e water. These
goals can be approached through several d i f l
f e r e n t means (130):
1. Use o f complexing agents t o complex
s p e c i f i c i o n s . The f i l t r a t e s o l u t i o n
c o n t a i n i n g o t h e r contaminants c o u l d be
f u r t h e r processed by h y p e r f i l t r a t i o n t o
y i e l d a good q u a l i t y r i n s e water f o r reuse.
2 . Use o f " A c t i v e t r a n s p o r t membranes" con-
s i s t i n g of a water-immiscible l i q u i d
organic complexing agent immobilized w i t h -
i n t h e pores o f a microporous membrane.
3. A d d i t i o n o f chemicals (chelate, p o l y e l e c -
t r o l y t e s , e t c . ) f o r eventual separation
o f t h e valuable i o n from t h e complexing
agent. Pusch and Walch (130) found t h e
separation of two s o l u t e s was more e f f e c t i v e
a t 40 atm than a t 100 atm due t o t h e l e s s
r a p i d increase i n t h e contaminant r e j e c t i o n
AlChE SYMPOSIUM SERIES
w i t h i n c r e a s i n g pressure. By adapting t h e
p r o p e r t i e s o f t h e membrane polymer t o t h e
p r o p e r t i e s o f t h e s o l u t e s and by v a r i a t i o n
o f t h e process parameters ( a p p l i e d pressure,
s o l u t e concentration, pH, e t c . ) , separation
numbers g r e a t e r than 1000 f o r low molecular
weight s o l u t e s can be achieved by h y p e r f i l t r a -
t i o n . Separation i s most e f f e c t i v e i f one
o f t h e species y i e l d s a r e j e c t i o n g r e a t e r than
99% a t a h i g h water recovery r a t e .
Charged, n o n c e l l u l o s i c u l t r a f i l t r a t i o n
membranes p r o v i d e t h e advantages o f good water
f l y x a t !ow t r a smem rane pressures (5.0 x
10 t o 7.0 x 10! N/m 3 P ) and t h e s e l e c t i v e
separation o f simple and complexed i o n s from
aqueous s o l u t i o n s . The s e p a r a t i o n o f heavy
metals i n t h e presence o f complexing agents
i s p a r t i c u l a r l y d i f f i c u l t w i t h conventional
processes. An e x t e n s i v e experimental i n v e s t i -
g a t i o n (22) was conducted w i t h n e g a t i v e l y -
charged, n o n - c e l l u l o s i c u l t r a f i l t r a t i o n mem-
branes t o e s t a b l i s h t h e r e l a t i v e r e j e c t i o n
behaviors o f complexed heavy metals under
i n s i g n i f i c a n t c o n c e n t r a t i o n p o l a r i z a t i o n con-
d i t i o n . Three types of complexing agents were
u t i l i z e d : cyanide (CN), ethylenediamine t e t r a -
a c e t i c a c i d (EDTA), and o x a l a t e ( O X ) . The
w g a t i v e l y - c h a r g e d ( s u l f o n i c a c i d groups) mem-
brages used had a t y p i c a l water flux o[ 1.32x
10- cm/sec a t a pressure o f 5.6 x 10 N/m .
The r 9 J e c t i g g deptrrdence ofl$.he heavy
metals (Zn , Cd , Cu , and Cu ) and f r e e
complexing agents (CN-, EDTA, and o x a l a t e ) was
found t o be a f u n c t i o n o f feed r a t i o (L/M) o f
complexing agent to metal P H , ~i o n i c strength,
and pressure (below 5.0 x 10 n/M ) . For EDTA
and o x a l a t e systems, t h e r e j e c t i o n s o f metal
were independent o f i n i t i a l metal concentration
whereas f o r t h e cyanide system t h e r e j e c t i o n s
o f both metal and cyanide decreased w i t h feed
c o n c e n t r a t i o n . The c o n c e n t r a t i o n e f f e c t was
f u r t h e r v e r i f i e d by t h e h i g h water recovery
experimegts. A t a transmembrane pressure o f
5.6 x 10 n/M2, metal r e j e c t i o n s ranged be-
tween 77% and 96%. The r e j e c t i o n behavior i s
e x p l a i n e d i n terms o f metal complex species
d i s t r i b u t i o o and Donnan Exclusion model. The
r e j e c t i o n s o f a l l complexed metal i o n s are
s t r o n g f u n c t i o n s o f average species charge.
Because negatively-charged membranes r e j e c t
d i v a l e n t anions b e t t e r than monovalent anions,
t h e r e j e c t i o n o f ML- > ML would be expected.
The complexed metal i o n charge i s a f u n c t i o n
o f the L/M r a t i o and pH.
The membranes used i n the study had a
t y e l c a l CuC12 r e j e c g i o n $ R ) o f 34% a t 1.6 x
10 M and 5.6 x 10 N/m pressure. Typical
r e j e c t i o n s obtained w i t h complexed copper
No. 243,Vol. 81
species were 94%, 96%, and 80% f o r Cu)CN)-
Cu(EDTA)-, and Cu(0X)-, r e s p e c t i v e l y . The r e -
j e c t i o n s o f f r e e CN-, EDTA-, and OX- were 30%,
85%, and 93%, r e s p e c t i v e l y . For a l l cases,
t h e metal r e j e c t i o n s show t h e f o l l o w i n g t r e n d :
High metal r e j e c t i o n s
%-EDTA > R ~ > R- ~ -~ o ~ ~.
were o b t a i n e d a t L/M = 1.0, pH 4-10 w i t h EDTA;
a t L/M = 4-6, pH 9-10 w i t h cyanide; and L/M
= 10-12, pH 6-7 w i t h o x a l a t e . The r e j e c t i o n s
of v a r i o u s s p e c i e s - f o l l o w t h e order: Cu(CN1-
> Zn(CN)i > Cd(CN)- ; ZN(EDTA)- > Cd(EDTA)-
Removals a t h i g h wa?er r e c o v e r i e s were a l s o
computed from t h e c o n c e n t r a t i o n dependence
c o r r e l a t i o n and f u r t h e r v e r i f i e d by e x p e r i -
ments. S e l e c t i v e separation o f metals c o u l d
be o b t a i n e d by a d j u s t i n g t h e pH and complex-
i n g agent t o metal feed r a t i o .
C a r t w r i g h t (29) describes t h e present
a p p l i c a t i o n s and p o t e n t i a l uses o f membrane
processes i n t h e p l a t i n g shop. More than
100 RO systems a r e used t o t r e a t n i c k e l
p l a t i n g rinsewaters. T y p i c a l o p e r a t i n g c o s t s
( i n c l u d i n g l a b o r and maintenance, e l e c t r i c a l
expenditures f o r t h e h i g h pressure pump and
t r a n s f e r pump and rep1 acement o f t h e c a r t r i d g e
f i l t e r and RO membrane element) range from
$0.75 t o $2.00/1000 g a l l o n s o f feedwater pro-
cessed. The economic value o f recovered
nickel-plating salts usually results i n a
c a p i t a l payback p e r i o d of l e s s than 18 months.
C a r t w r i g h t (29) p o i n t s art that few RO i n s t a l -
l a t i o n s a r e used t o t r e a t wastewaters such
as a c i d copper o r t i n - l e a d f l u o r o b o r a t e due
to low evaporation r a t e s and low value o f t h e
plating salts.
For membrane e x t r a c t i o n o f heavy metals,
the netals a r e removed through membranes which
separates these two phases ( 7 4 ) . No m i x i n g
i s i n v o l v e d and no w i n g p a r t s are used,
thereby e l i m i n a t i n g many problems a s s o c i a t e d
w i t h d i m t mixing necessary i n conventional
s o l v e n t e x t r a c t i o n processes. This new
technology o f t h e membrane e x t r a c t i o n process
employes two h o l l o w f i b e r modules, one f o r
e x t r a c t i o n and theother f o r s t r i p p i n g . The
o r g a n i c s o l v e n t s c i r c u l a t e between t h e two
modules p i c k i n g up metal i o n s i n t h e e x t r a c -
t i o n module. The metals are removed from
t h e o r g a n i c s o l v e n t i n t h e s t r i p p i n g module.
The regenerated s o l v e n t i s r e c y c l e d back t o
t h e e x t r a c t i o n module. Water d r o p l e t s i n
t h e o r g a n i c phase s i g n i f i c a n t l y d e t e r i o r a t e
t h e performance o f t h e system. The water
d r o p l e t s i n t h e o r g a n i c phase w i l l c a r r y
s t r i p p i n g s o l u t i o n t o t h e aqueous stream,
thereby s h i f t i n g t h e e q u i l i b r i u m r e l a t i o n s h i p
and causing a r e d u c t i o n i n t h e removal e f -
f i c i e n c y . However, s i n c e o r g a n i c l o s s i s
l e s s than t h a t w i t h conventional s o l v e n t
e x t r a c t i o n , i t i s p o s s i b l e t o use more ex-
187
pensive s o l v e n t m a t e r i a l s . Membrane e x t r a c -
t i o n can be used f o r separation and concen-
t r a t i o n o f copper, n i c k e l , zinc, chromium,
c o b a l t , uranium, and o t h e r heavy metals.
Major advantages o f t h i s technology o v e r o t h e r
c o m p e t i t i v e processes are h i g h s e l e c t i v i t i y
f o r a s p e c i f i c metal , s i m p l i c i t y o f operation,
and h i g h chemical and p h y s i c a l s t a b i l i t i e s .
I n summary, membrane processes a r e be-
coming more and more accepted w i t h i n t h e i n -
d u s t r y . To d a t e however, t h i s system i s
e s s e n t i a l l y a c o n c e n t r a t i o n technique. Major
l i m i t a t i o n s associated w i t h t h e use o f mem-
brane processes i n c l u d e membrane f o u l i n g ,
l i m i t e d l i f e o f t h e membranes, d i s s o l u t i o n
o f t h e membrane by s t r o n g o x i d i z i n g agents,
solvents, and o t h e r organic compounds. New
generation composite membranes o f f e r broad
pH (pH 2-12) and temperature (up t o 50C)
o p e r a t i n g 1i m i t s .
EMERGING TECHNOLOGIES
Several i n n o v a t i v e technologies have
emerged over t h e l a s t few years. Kamperman
and Lancy ( 7 1 ) s t u d i e d t h e basic f a c t o r s
causing erratic r e a c t i o n r a t e s i n s u l f i d e p r e -
c i p i t a t i o n o f heavy metals i n a secondary
t r e a t m e n t s t e p a f t e r n e u t r a l i z a t i o n and s e t -
t l i n g . Since EDTA forms t h e t i g h t e s t complex
encountered among t h e usual organic a d d i t i o n s
i n metal f i n i s h i n g process s o l u t i o n s , syn-
t h e t i c s o l u t i o n s were prepared by adding a
s l i g h t excess o f metal s a l t s above t h e
s t o i c h i o m e t r i c amount t o an EDTA s o l u t i o n a t
pH 4. The s o l u t i o n pH was r a i s e d t o 9.0,
s t i r r e d f o r several hours , and f i1t e r e d
through a 0.45 filter, The r e a c t i o n r a t e s
were s l u g g i s h and e r r a t i c . The i n i t i a l
r e a c t i o n r a t e was a c c e l e r a t e d through a d d i t i o n
o f unchelated metal s a l t s t o p r o v i d e seeds
t o hasten t h e r e a c t i o n . Residual suspended
s o l i d s from a p r e v i o u s l y c l a r i f i e d e f f l u e n t
a l s o served as a seed f o r t h e r e a c t i o n . I n -
c r e a s i n g t h e pH reduced t h e t i g h t n e s s o f t h e
EDTA complex a l l o w i n g a more complete r e a c t i o n
t o occur. Kamperman and Lancy ( 7 1 ) developed
a f i l t e r f o r which t h e r e s u l t a n t media i s
e f f e c t i v e i n adsorbing s o l u b l e heavy metals
and r e t a i n s a c t i v e s u l f i d e s i n i t s body
allowing f u r t h e r reduction i n the soluble
heavy metal residues. That f e a t u r e n e a r l y
e l i m i n a t e s t h e s l i p p a g e o f excess s u l f i d e
p r e v e n t i n g t h e contamination o f t h e e f f l e u n t
by s u l f i d e .
I t o e t a1 . (65) developed a continuous
treatment system f o r t h e magnetic separation
o f heavy metal i o n s u s i n g e i t h e r f e r r i t e o r
magnetite. Advantages o f t h e process include:
188 Separation of Heavy Metals
Various heavy metal i o n s can be t r e a t e d
together .
The sludge formed i s s t a b l e t o pH and
temperature changes.
The f e r r i t e sludge can be separated by
a p p l y i n g a magnetic f i e l d .
The sludge formed i s a p p l i c a b l e t o t h e
o x i d e magnetic m a t e r i a l .
Water i n s o l u b l e s t a r c h xanthate (ISX)
has been shown t o be an e f f e c t i v e a l t e r n a t i v e
t o heavy metal m v a l and recovery (161,162).
Using t h i s l w c o s t product, I S X i n e f f e c t i v e
i n removing metal i o n s a t d i f f e r e n t concen-
t r a t i o n l e v e l s . Wing and Rayford (161) p o i n t
o u t t h a t i f t h e i n i t i a l metal concentrations
exceed 100 mg/l, i t i s n o t economical t o use
I S X treatment, and removal by chemical pre-
c i p i t a t i o n or sane other process should be used.
I S X i s a h i g h l y c o s t c o m p e t i t i v e method com-
pared t o o t h e r treatment processes f o r f i n a l
p o l i s h o f process o r e f f l e u n t discharge water
c o n t a i n i n g l e s s than 10 mg/l o f heavy metal
contaminants i n s i n g u l a r o r complexed f o r m
(162). The I S X process was originally Qveloped
a t t h e U.S. Department o f A g r i c u l t u r e . ISX
i s a c e r e a l grain-based product c h e m i c a l l y
c r o s s - l i n k e d t o make i t i n s o l u b l e i n water,
and t h e n i s xanthated t o form an a n i o n i c polymer.
When added t o wastewater c o n t a i n i n g heavy
metals, I S X exchanges sodium and magnesium
i o n s f o r t h e heavy metal c a t i o n s Wing (162)
presented several case h i s t o r i e s demonstrat-
i n g t h a t very low r e s i d u a l metal c o n c e n t r a t i o n s
can be achieved i n the t r e a t e d e f l u e n t s .
Advantages and c h a r a c t e r i s t cs o f t h e
I S X process i n c l u d e :
1. The average c a p a c i t y i s i n t h e range o f
1.1-1.5 meq o f metal i o n s /gm I S X .
2. The I S X process i s e f f e c t i v e over t h e pH
range o f 3-11 w i t h maximum e f f e c t i v e n e s s
shown f o r pH > 7.
3. S a l t c o n c e n t r a t i o n s up t o 10% have 1it t l e
e f f e c t on t h e removal o f heavy metals by
t h e I S X process.
4. I S X r a p i d l y removes heavy metal i o n s from
solution.
5. Treatment i s a p p l i c a b l e t o batch o r c o n t i n -
uous f l o w systems.
6. Metals can be recovered from t h e ISX-metal
sludge by n i t r i c a c i d treatment o r i n -
cineration.
7. ISX-metal sludge s e t t l e s r a p i d l y and de-
waters t o 30-90% s o l i d s c o n t e n t a f t e r
f i l teration or centrifugation.
8. P r e l i m i n a r y estimates t o manufacture I S X
amount t o $0.30/1 b .
Johannesmeyer and Ghosh (70) i n v e s t i g a t e d
AlChE SYMPOSIUM SERIES
two techniques f o r f i x a t i o n o f heavy metals
i n e l e c t r o p l a t i n g wastes. Waste f i x a t i o n i n -
volves s t a b i l i z a t i o n / s o l i d i f i c a t i o n t h a t
immobilizes, isolates,. o r c o n t a i n s i n d u s t r i a l
waste products. The Silicate and cement based
and l i m e based techniques were evaluated i n
t h e i r study. The in i t i a1 c o n c e n t r a t i o n o f
chromium and cadmium were 0.490 and 0.102 mgll,
r e s p e c t i v e l y . I t i s p o s s i b l e f o r t r a c e amounts
of m t a l s t o escape f i x a t i o n due t o improper
f i x a t i o n i n g r e d i e n t t o sludge r a t i o , i n s u f -
f i c i e n t m i x i n g of f i x a t i v e and sludge, improper
m o i s t u r e c o n t e n t o f t h e sludge, e t c . Both
f i x a t i o n techniques were capable o f reducing
t h e l e a c h i n g o f chromium and cadmium from the
t r e a t e d product. Sodium s i l i c a t e and cement
was more e f f e c t i v e than f l y ash and l i m e i n
i m m o b i l i z i n g chromium and cadmium d u r i n g t h e
EP t o x i c i t y and column leach t e s t s . Both
methods showed a l o s s o f chromium and cadmium
over t h e study period; t h e s i l i c a t e method
re1 eased c o n s i d e r a b l y lower amounts than t h e
l i m e based method. The l a r g e r t h e s i l i c a t e
content, t h e more e f f e c t i v e t h e method was
a t i m m o b i l i z i n g cadmium and chromium.
SUMMARY
The v a r i o u s treatment techniques a v a i l -
a b l e f o r removal o f heavy metals from waste-
waters have been addressed. By f a r , t h e most
commonly used technique i s t h a t o f chemical
p r e c i p i t a t i o n . The advantages and 1 i m i t a t i o n s
associated w i t h each process have been d i s-
cussed. Table 1 summarized t h e treatment
conditions, i n f l u e n t conditions, residual
metal concentrations, and removal e f f i c i e n c i e s
r e p o r t e d i n the 1it e r a t u r e .
ACKNOWLEDGEMENTS
The authors wish t o acknowledge the
support o f t h e School o f C i v i l Engineering
a t Purdue U n i v e r s i t y and t h e Department of
Chemical Engineering a t t h e U n i v e r s i t y of
Kentucky i n performing t h e review and conduct-
i n t h e heavy metal removal research.
No. 243,Vol. 81 189

Table 1. S m m r y o f heavy metal removals by various treatment techniwies.

Technology Metal(s) pH I n i t i a l Metal, Residual Metal Removal Conrilents Ref e rence
Em1oyed Concent r a t i o n Concentration E f f ic iency ,%
Hydroxide 0a 10-11 7.0-8.5 -- >go __ 43
Predpita- 9.2 10.0-12.0 -- 84 P i l o t plant tests 43
tion 10.5 10.0-12.0 -- 93
11.6 10.0-12 .o -- 82
10.5 7.5 -- 88 F u l l scale t e s t s 43
10.3 17.4 __ 95
Cd 8.5-11.3 0.3 __ >98 ___ 43
11.2-11.3 10 -- > 98 ---
6.0-10.0 100 e0.3 >99.7 Synthetic p l a t i n g w a s t w a t e r 124
10.0 100 <0.3 .99.7 Synthetic p l a t i n g wastewater 124
100 2.0 98
100 5.0 95
8.0 -- 2350 __ 10 mg/l CO= 111
8.6 _- 126 __ OI mg/l co3
9.4 __ 5 _- OI nig/l CO:
10.4 -- 0.2 -- 55 mgll CO -
__
Cr
11.9
6.6 Crt3.i;25
0.3
Crt3.26.0 >98
100 mg/l
_ _ d;
_ 5
9.5-10.0 c~+
.40~ I I Crt3:0.3 78.6 Nickellctyonte r i n s e
Cr+6:2 .23 Cr+6 :<0.01 939.5
9.5-1 0.5 ~ r:4.0+ ~ C:;r ; O .03 99.3 F u l l scale p l a n t 5
~r+~:4.5 C r .<0.01 >99.7
Cr+3 10.6-11.3 0.15 -- >98 --- 43
9.21 0.15 __ >70 _--
Cr+6 9.5-11.6 0.15 __ <lo --- 43
cu 10.5 0.45 0.08 02.2 Copper r i n s e 131
9.5-10.5 5.7 0.89 84.4 F u l l scale p l a n t
Pb 8.5-11.3 0.15 -- >98 ___ 43
6.0 -- 1700 __ 15mg/l CO= 111
7.4 -- 25.6 __ 15mgil C03
8.8 -_ 6.0 __ 15mg/1 C03
10.5 -- 0.6 __ 40nig11 co3
11.9 -- 280 __ 12311gll ca
12.3 __ 1050 __ 275mg/1 cni
Hq 10.7-11.4 9 . 3 u9/1 -- 60-00 --- 43
(inorganic) 9.4 9.3 P9/1 -- 30 ___
9.3-11.3 9.3 u9/1 __ e5 ___ , 43
tlg
9.0 0.15 _- 70 ___ 43
Ag
11.5 0.15 __ 90 __-
20 10.0 100 0.3 99.7 124
100 32.0 68
6.2 -- 1900 -_ 111
7.5 -_ 27.5 __
8.3 _- 0.55 _--_
9.5 -- 0.25
11.0 -- 0.68 __
11.8 -- 0.95 -- 25 my11 COJ
N1 6.8 -_ 1450 _- 19 mg/l co3 111
7.4 _- 930 -_ 30 mgll C03
8.3 -- 15 __ 38 mg/l co3
9.4 __ 0.5 _- 38 mg/l co3
11.0 -- 0.3 __ 90 mg/l co3
12.3 -- 0.5 __ 225 mg/l Cc!
Mixed Metal : >8.5 Electroplat?rig p l a n t da 1 138
cu 60.0 0.9 98.5
Ni 1.9 0.3 84.2
Pb 1.2 0.4 66.7
Mixed Eletals: 8.5-9.1 E l e c t r o p l a t i n g p l a n t data 138
Fe 20-60 0.3-2.4 >96
Pb 0.1 0.5 --
Sn 1 .o 0.5 >50
Mixed k t a l s : 8-10 P r i n t e d c i r c u i t board 138
cu 20-150 0.5-2.0 >97.5 manufacturer
Pb 0.5-1.0 <0.05 90-95
Si 0.1-0.5 0.1 <EO
Mixed Metals: 9.7-10.2 26
Cd 1.66 0.04 97.6
Cr 1.11 0.97 12.6
cu 0.29 0.03 89.7
Pb 1.7 0.2 88.2
Zn 31 0.28 99.1

Carbonate Cd 7.2 _- 440 __ 5 IIKJ/l co= 111

Predplta- 8.4 -- 7.5 -- 5 niqll co3
tion 9.5 -- 0.6 -- 10 mg/l ca
10.7 -- 0.35 -- 50 m q / l C03
11.9 __ 0.5 -- 225 mg/l ca
Cd 8.1 __ 5 -- 1200 mg/l cd 111
8.4 -- 1.2 -- 2800 mg/l co3
8.7 -- 1.7 __ 3350 mg/l C03
10.0 -- 0.25 __ 4200 mg/l C03
10.8 -- 0.25 __ 4400 mg/l C03
11.7 -- 0.35 __ 4300 mg/l C03
Ni 7.2 -_ 8M) __ 1500 mg/l C03 111
8.2 -- 60 _- 3000 nig/l C03
9.0 -_ 3.8 __ 3500 mg/l co3
10.5
11.5
--
--
2.7
I .4
__-- 5500 n q l l C03
5500 mg/l C03
12.5 -- 1.4 __ 5500 nq/1 CO;
 Separation of Heavy Metals AlChE SYMPOSIUM SERIES
Table 1. (cont. 1
Technology Metal(s) pH I n i t i a l Metal, Residual Metal Reinoval Comnents Reference
EtiiplDyed Concentration Concentr a t ion Efficiency%,
Carbonate Pb 5.6 --
-- 4.6 __
-- 10 mg/l co= 111
Preci p i t a - 6.1 43.6 15 m g / ~ co3
tion 6.8 -- 17.4 -- 20 w/~ co3
10.1 -- 0.6 -- 55 ~1 co3
11.6 -- 10.0 __ co3
55 mg/l
12.3 -- 1260 -- 55 ~1 co3
Pb 7.5 -- 1 .o -- 1200 mg/l 20 111
8.4 -- 2.0 -- 4000 w / ~co3
9.2 -- 3.6 _- 4650 mg/l C03
10.5 -- 8.0 __ 5500 mg/l C03
11.4 -- 6.0 -- 5500 mg/l C03
12.4 -- 150 -- 5500 mg/l C03
Zn 6.6 -- 260 __ Sample nt: adalyzed f o r CO; 111
8.3 -- 0.95 _-
9.1 -- 0.75 --
10.0 -- 0.60 -- 5500 mg/l CO=
10.8 -- 0.85 _- 6500 ng/l C03
11.9 -- 1.60 __ 5500 s g / l C03
12.5
Mixed Metals: 7.8-8.5
-- 49.6 -- 3500 m g i i ro:
-- 26
Cd 1.37 0.04 97.1
Cr 0.67 0.60 10.4
cu 0.18 <O .03 .83.3
Pb 1.4 <0.1 >92.9
Zn 26 1.18 95.4

Sulfide cu 4.0 100 0.08 99.92 No chelants present, S==l.O5x 119

P r e c i p it a - 6.0 100 0.08 99.92
tion 8.0 100 0.05 99.95
10.0 100 0.05 99.95
cu 4.0 100 1.3 98.7 100 mg/l EDTA, S==l.Ox 21
4.0 100 0.6 99.4 100 mg/l Gluconic Afid. S==l.Ox
4.0 100 0.3 99.7 100 Citrate, 5 ~ 1 . 0 ~
t g / l
4.0 100 0.2 99.8 100 mg/l Tartrate. S-=I .Ox
cu 3.0 100 0.9 99.1 100 mg/l EDTA. 5 =I.O5x 119
4.0 100 0.8 99.2
6.0 100 0.6 99.4
8.0 100 0.6 99.4
10.0 100 1 .o 99.0
cu 4.0 100 0.08 99.92 No chelants present, S==l.O5x 81
100 0.85 99.15 100 mg/l EDTA, S'= 1 . 0 5 ~
100 0.65 99.35 100 W g / l C i t r a t e , S'=1.05x
100 0.25 99.75 100 iwg/l tiluconic Acid. S - = 1 . 0 5 ~
100 0. I 5 99.85 100 mg/l T a r t r a t e , S =-l.O5x
cu 8.0 100 0.05 99.95 No chelants present. S==1.05x 81
100 0.7 99.3 100 mg/l OTA, S-=1,05x
100 0.4 99.6 100 mg/l C i t r a t e , S ~ 1 . 0 5 ~
100 0.1 99.9 100 mq/l Tartrate, S-=l.O5x
cu 8.0 100 0.5-1.0 >99.0 100 m q / l EDTA. S =1.05x 120
Cd 4.0-10.0 500 0.01 .99.99 s==1.bx 119
4.0 100 1.2 98.8 100 mall EDTA. S==I.OX 21
9.0 100 0.16 99.84 No cheiauts present, CaS 75
precipitation
Zn 3.0 100 12.0 88.0 No chelants present. S==l.O5x 119
4.0 100 0.3 99.1
8.0 100 0.2 99.8
10.0 100 0.15 99.85
Zn 4.0 100 16.5 83.5 100 nig/l ,,EDTA. S==l.O5x 119
6.0 100 15.0 85.0
8.0 100 17.8 87.2
10.0 100 12.0 88.0
Zn 4.0 100 8.0 92.0 100 mq/l EDTA, Sz71.Ox 21
8.0 100 12.0 88.0 100 mg/l EUTA, S - 1 . 0 5 ~ 120
Mixed Metals: 8.0 Wastewater froin e l e c t r o p l a t ing 133
Cd 2.06 0.10 95.1 and metal f i n i s h i n g operation a t
Cr 2.61 0.32 87.7 F o r t B e l v o i r . VA
cu 1 .a2 0.04 97.8
Ni 3.50 0.07 98.0
Zn 5.8 0.41 92.9
Mixed Metals:
Zn 10.8 81 3 6.66 99.2 Pure hydroxide treatment 49
Fe <O.l <o. 1 ._
Pb 23.5 0.09 99.6
Zn 11.1 813 6.74 95.2 50 mg/l 7s 49
Fe <o. 1 <o. 1 ._
Pb 23.5 g0.03 >9Y.8
Zn 10.6 813 3.90 99.5 100 mg/l,,FeS 49
Fe <O.l 4.1 __
Pb 23.5 0.03 99.8
Zn 10.4 813 4.59 99.4 500 mg/l ,,FeS 49
Fe go.1 <0.1 __
Pb 23.5 0.10 99.6
Zn 10.85 81 3 4.40 99.45 1000 mg/;, FeS 49
Fe co.1 co.1 __
Pb 23.5 0.03 99.8
Zn
Fe
10.7 81 3
<0.1
4.64
<O.l __
99.4 2000 m/l FeS 49

Ph 23.5 0.04 99.8

No.243,Vol. 81 191
Table 1. (cant.)
Techology Metal(s) pH I n i t i a l Metal. Residual Metal Removal Conmnts Reference
Fmployed Concentration Concentration Efficiency ,%
Sulfide Mixed Metals: 8.0 S-=0.6x, f u l l scale p l a n t 18
Preciplta- Zn 30-60 -- 51-75
tion Pb 20-40 -- 97-99
Cd 3-16 -- 99
cu 3-5 -- 90
H9 2 -4 -- 99
Fe 5-20 _- 2 -26
Mixed Metals: Copper smelting p l a n t scrubber 17
Cd 8.5 10.5 0.6 94.3 wastewater; Hydroxide treatment
cu 297 0.5 99.8 only
Zn 85.5 3.1 96.4
Pb 39 0.7 98.2
Fe 149 ~0.5 >99.7
se 3.0 <1 .o >66.7
As 100 6.8 93.2
Cd 8.0-8.5 10.5 <o.os ~19.5 s== 5 mM 17
cu 297 0.2 99.9
Zn 85.5 0.9 98.9
Pb 39 0.4 99.0
Fe 149 <0.5 >99.7
se 3.0 <1 .o >66.7
As 100 2.0 98.0
Cd 8.0-8.5 10.5 <O .05 >99.5 S== 8 nt4 17
cu 297 0.1 >99.9
Zn 85.5 0.05 99.4
Pb 39 0.4 99.0
Fe 149 <0.5 >9Y. 7
se 3.0 1.2 60.0
As 100 11.0 89.0
Cd 8.0-8.5 10.5 <0.05 >99.5 s== 12 mM 17
cu 297 <0.05 P99.9
Zn 85.5 ~0.05 >99.5
Pb 39 0.3 99.2
Fe 149 <0.5 >99.7
se 3.0 1 .0 66.7
AS 100 21 .o 79.0
Mixed Metals:
cu 8.0 100 0.4 99.6 No EDTA. S== 1 . 0 5 ~ 120
Zn 100 0.3 99.7
cu 8.0 100 0.3 99.7 100 mg/l EDTA, S'=l.O5x 120
zn 100 15.0 85.0
cu 8.0 100 0.4 99.6 200 mg/l EDTA, S==l.OSx 120
zn 100 27.0 73.0
cu 8.0 100 0.5 99.5 200 mg/l EDTA. S==0.8x 120
zn 100 74.0 26.0
Mixed Metals: 9.0 CaS p r e c i p i t a t i o n process 75
Cd 7.95 <0.05 >99.4
cu 18.6 <0.05 >99.7
Cr 1.34 <O .05 >96.2
Pb 3.5 <0.5 ~85.7
zn 47.0 ~0.05 >98.9
Mixed Metals: I n d u s t r i a l p l a t i n g wastewater
Zn 8.0 24.5 2.4 90.2 Hydroxide treatment only 125
cu 62.4 1.45 97.7
Cr 28.0 13.6 51.4
Ni 1.04 0.36 65.4
zn 8.0 24.5 1.70 93.0 S== 0 . 8 3 ~ 125
cu 62.4 1.325 97.9
Cr 28.0 8.8 68.6
Ni 1.04 0.30 71.1
zn 8.0 24.5 0.40 98.4 s== 1.ox 125
cu 62.4 1.40 97.75
Cr 28.0 9.6 65.7
Ni 1.04 0.30 71.1
Zn 8.0 24.5 0.39 98.4 s== l.lx 125
cu 62.4 1.475 97.6
Cr 28.0 8.0 71.4
Ni 1.04 0.20 80.8
Zn 10.0 24.5 0.5 97.9 Hydroxide treatment only 125
cu 62.4 14.4 76.9
Cr 28.0 2.35 91.6
Ni 1.04 0.15 85.5
Zn 10.0 24.5 0.53 97.8 S== 0 . 8 3 ~ 125
cu 62.4 12.2 80.4
Cr 28.0 2.05 92.7
Ni 1.04 0.175 83.1
zn 10.0 24.5 0.605 97.5 s== 1.ox 125
cu 62.4 12.4 80.1
Cr 28.0 1.75 93.8
Ni 1.04 0.175 83.1
zn 10.0 24.5 1.2 95.1 s== l.lx 125
cu 62.4 10.8 82.7
Cr 28.0 1 .so 94.6
Ni 1.04 0.20 80.8
 Separation of Heavy Metals AlChE SYMPOSIUM SERIES
Table 1. (cont.)
Technology Metal ( 5 ) pH I n i t i a l Metal, Residual Metal Rewval Comnent s Reference
Employed Loncentr a t ion Concent r a t i o n Efficiency ,%
Sulfide Mixed Metals: 8.0-8.4 FeS dose = 1 . 5 ~ 26
Precipita- Cd 3.3 0.06 98.2
tion Cr 0.52 <O .05 >90.4
cu 0.35 e0.03 >91.4
Pb 4.5 eo. 1 >97.7
Zn 93 0.68 99.3

Combined Ni 6 10 8.2 18 Hydmxide treatnlent only 91

Precipitation 7 10 9.5 5
Treatment 8 10 6.8 32
q 10 4.0 60
10 10 0.2 98
11 10 0.1 99
Ni 6 10 7.3 27 Hydroxide treatment. CT= 5Onq/l 91
7 10 7.8 22
8 10 8.3 17
9 10 1.6 84
10 10 0.05 99.5
11 10 0.1 99
Ni 6 10 9.8 2 Hydroxide treatment. CT= 100 mg/l 91
7 10 8.8 12
8 10 8.9 11
9 10 2.3 77
10 10 0.12 98.8
11 10 0.05 99.5
Ni 6 10 9.7 3 Hydroxide treatment, CT= 200 mg/l 91
7 10 9.6 4
8 10 8.7 13
9 10 6.4 36
10 10 0.1 99
11 10 0.05 99.5
Ni 6 10 7.0 30 5 T= 5 mg/l. cT= 0 91
7 10 9.4 6
8 10 7.8 22
9 10 1.5 85
10 10 0.1 99
11 10 0.05 99.5
Ni 6 10 8.7 13 ST= 5 mg/l. CT= 50 ing/l 91
7 10 8.4 16
8 10 8.8 12
9 10 3.2 68
10 10 0.3 97
11 10 0.05 99.5
Ni 6 10 10.0 0 ST= 5 mg/l, CT= 100 mg/l 91
7 10 9.5 5
8 10 9.2 8
9 10 4.8 52
10 10 0.1 99
11 10 0.05 99.5
Ni 6 10 9.2 8 ST= 5 mg/l. CT= 200 mg/l 91
7 10 9.4 6
8 10 9.1 9
9 10 4.8 52
10 10 0.15 98.5
11 10 0.05 99.5
Ni 6 10 9.1 9 ST= 10 mg/1. CT= 0 91
7 10 7.6 24
8 10 7.7 23
9 10 4.6 54
10 10 0.1 99
11 10 0.05 99.5
Ni 6 10 8.9 11 ST= 10 w/l. CT= 50 nq/1 91
7 10 7.8 22
8 10 8.1 19
9 10 4.5 55
10 10 0.1 99
11 10 0.05 '99.5
Ni 6 10 9.1 9 sT= 10 mg/l. cT= 100 mg/l 91
7 10 9.2 8
8 10 8.6 14
9 10 6.8 37
10 10 0.9 91
11 10 0.05 99.5
Ni 6 10 9.2 8 ST= 10 mg/l, CT= 200 mg/l 91
7 10 8.8 12
8 10 8.5 15
9 10 6.6 34
10 10 0.1 99
11 10 0.05 99.5
Ni 6 10 9.7 3 sT= 20 mg/l, cT= 0 91
7 10 8.2 18
8 10 1 .o 90
9 10 3.1 69
10 10 0.1 99
11 10 0.05 99.5
, 7

Table 1. (cant.) 193

Technology Metal(s) pH I n i t i a l Metal,, Residual Metal Reinoval Cmnents Reference
Employed Concentration Concentrat i o n E f f i c i e n c y ,%
Conbined Ni 6 10 9.3 7 ST= 20 n g / l . CT= 50 mg/l 91
Precipitation 7 10 6.1 39
Treatment 8 10 5.2 48
9 10 2.8 72
10 10 0.15 98.5
11 10 0.1 99
Ni 6 10 9.5 5 ST= 20 mg/l. CT= 100 mg/l 91
7 10 9.2 8
8 10 9.1 9
9 10 3.4 66
10 10 0.15 98.5
11 10 0.05 99.5
Ni 6
7
10
10
8.5
9.0
15
10
sT= 20 mg/l . cT= 200 mg/l 91
8 10 8.8 12
9 10 5.4 46
10 10 0.3 97
11 10 0.05 99.5
Ni 6 10 8.2 18 C = 0, Fe/Ni = 0 94
10 8.2 18 CT= 0 . Fe/Ni = 0.5
10 4.9 51 CT= 0. Fe/Ni = 1.0
10 6.7 33 CT= 0, Fe/Ni = 2.0
6 10 7.6 24 CT= 50 mg/l. Fe/Ni = 0 94
10 9.2 8 CT= 50 mg/l, Fe/Ni = 0.5
10 9.5 5 CT= 50 mg/l, Fe/Ni = 1 .O
10 8.8 12 CT= 50 mgll. Fe/Ni = 2.0
6 10 9.9 1 CT= 100 mg/l. Fe/Ni = 0 94
10 9.6 4 CT= 100 w/l, Fe/Ni = 0.5
10 9.3 7 CT= 100 mg/l, Fe/Ni = 1 .O
10 6.9 11 CT= 100 n g / l . Fe/Ni = 2.0
6 10 9.5 5 CT= 200 m g / l . Fe/Ni = 0 94
10 9.0 10 CT= 200 mg/l, Fe/Ni = 0.5
10 8.8 12 CT= 200 mg/l, Fe/ni = 1.0
10 8.8 12 CT= 200 mg/l, Fe/Ni = 2.0
Ni 9 10 7.7 23 CT= 0, Fe/Ni = 0 94
10 0.5 95 CT= 0, Fe/Ni = 0.5
10 0.35 96.5 CT= 0, Fe/Ni = 1.0
10 0.35 96.5 CT= 0, Fe/Ni = 2.0
9 10 2.0 80 =C! 50 m/l. Fe/Ni = 0 94
10 1.7 83 C'= 50 m g / l - Fe/Ni = 0.5
10 0.2 98 CT= 50 mg/l: Fe/Ni = 1 .O
10 0.3 97 C+ 50 mg/l, Fe/Ni = 2.0
Ni 9 10
10
10
2.8
1.9
0.3
72
81
97
<-
C = 100

C
100
100
mg/l. Fe/Ni = 0
nig/l. Fe/Ni = 0.5
mg/l, Fe/Ni = 1.0
94

10 0.22 97.8 CT= 100 mg/l. Fe/Ni = 2.0

9 10 6.8 32 <= 200 mg/l. Fe/Ni = 0 94
10 2.0 80 C = 200 mg/l. Fe/Ni = 0.5
10 0.12 98.8 CT= 200 ng/l. Fe/Ni = 1 .O
Ni 10
10
10
10
0.20
0.20
0.10
98
98
99
CT=
CT-
CT=
0. Fe/Ni -
200 mg/l, Fe/Ni = 2.0
0
0, Fe/Ni = 0.5
94
10 co.10 >99 CT= 0. Fe/Ni = 1.0
10 co.10 >99 CT= 0. Fe/Ni = 2.0
10 10 co.10 >99 CT= 50 mg/l. Fe/Ni = 0 94
10 co.10 >99 CT= 50 mgll. Fe/Ni = 0.5
10 <0.10 >99 CT= 50 mg/l, Fe/Ni = 1 .O
10 co.10 >99 CT= 50 w/l, Fe/Ni = 2.0
10 10 0.14 98.6 CT= 100 mg/l. Fe/Ni = 0 94
10 0.10 99 C:
= 100 mg/l. Fe/Ni = 0.5
10 co.10 >99 CTz 100 mg/l. Fe/Ni = 1.0
10
10
10
co.10 >99 5- 100 mg/l. Fe/Ni = 2.0
co.10 >99 Cf 200 mg/l, Fe/Ni = 0 94
10 co.10 >99 C = 200 mg/l. Fe/Ni = 0.5
10 co.10 >99 CT= 200 mg/l , Fe/Ni = 1.0
10 co.10 >99 CT= 200 mg/l. Fe/Ni = 2.0
Ni 10.0 5.0 0.35 93 FTSO = 20 mg/l 89
Cd 6.90 1.o Cd=0.08:Ca=147.5 92 Cai 9 1511 mg/l as CaCO3 31
7.32 1 .o Cd4.01 ;Ca=129.5 299
7.60 1.o CdcO.01 ;Ca=ll9.4 ;99
7.76 1 .o Cd<O .01 ;Ca=75 .O >99
8.04 1 .o Cd:ND; Ca r39.0 >99
9.44 1.o Cd:NO; Ca = 4.6 >99
10.38 1.o Cd:ND; Ca = 3.0 ? 99
10.84 1 .o Cd:NO; Ca = 3.1 >99
Cd 7.42 1.o CdcO.01 ;Ca=152.3 >99 Cai = 2 5 i mg/l as CaC03 31
7.45 1 .o Cdc0.01 ;Ca=125.9 > 99
7.66 1 .o Cdc0.01 ;Ca=92.5 >99
7.96 1 .o Cd:NO; Ca =51.7 > 99
8.66 1 .o Cd:NO; Ca =11.5 >99
9.74 1.0 Cd:ND; Ca = 4.2 >99
10.62 1 .o Cd:ND; Ca = 3.7 >99
11.01 1 .o Cd:ND; Ca = 3.7 >99
cd 7.36 1.o Cdq.01 :Ca -191.6 >99 Cai = 35: mg/l as CaC03 31
7.41 1.o Cd:NO: Ca=156.7 >99
7.57 1.0 Cd:NOi Ca-117.0 >99
7.62 1.0 Cd:NO; Ca= 92.1 >99
7.64 1.0 Cd:ND; Ca-106.5 >99
8.03 1.0 Cd:NO; Ca- 37.1 >99
9.58 1.0 Cd:ND; Cam 10.3 '99
10.81 1.0 Cd:ND; Ca= 2.7 >99
 Separation of Heavy Metals AlChE SYMPOSIUM SERIES

Table 1. (cont.)
Technology Hetal(s) pH I n i t i a l Metal, Residual Etetal Removal Coiinlents Reference
Einploved Concentration Concentration E f f i c i e n c y .%

Combined Cd 7.79 5.0 Cd=O.O2, Ca=148.9 98 Cai= 150 mg/l as CaC03 31

Precipitation 8.05 5.0 Cd-0.01. Ca=llO.O 99
Treatment 9.42 5.0 Cd<O.Ol, Ca138.7 >99
10.96 5.0 Cd:ND, Ca=52.2 >99
11.30 5.0 Cd<0.01, Ca-32.2 >99
Cd 7.82 5.0 Cd=0.02, Ca=l15.8 98 Cai= 250 mg/l as CaC03 31
8.21 5.0 Cd=0.02. Ca=75.0 98
8.82 5.0 Cd<0.01, Ca=40.5 >99
10.47 5.0 Cd:NO, Ca.11.2 .99
11.07 5.0 Cd:ND. Ca=14.4 $99
11.39 5.0 Cd-0.02, Ca=10.6 98
Cd 7.67 5.0 Cd=O.03. Ca.208.1 97 Cai= 350 mg/l as CaC03 31
7.97 5.0 Cd<0.01, Ca=119.4 >99
8.38 5.0 Cd:NO, Ca.67.2 > 99
10.09 5.0 Cd<O.Ol, Ca=22.8 299
10.66 5.0 Cd-0.01, Ca.14.8 99
10.95 5.0 Cd<O.Ol, Ca=15.3 >99
11.30 5.0 Cd:NO. Ca110.8 > 99
Mixed Metals:
Zn 8.0 50 0.57 98.9 153
Ni 15 1.8 88.0
Pb 15 ~0.05 >99.7
Cd 15 ~0.05 >99.7
cu 15 <O .03 >99.8
Hg 2.9 <0.001 >99.9

Zn 9.5 50 0.04 99.9 153

Eli 15 e0.05 .99.7
Pb 15 <0.05 >99.7
Cd 15 <O .05 >99.7
cu 15 <0.03 >99.8
Hq 2.9 <0.001 >99.9

Coagulation/ Cd 7.2 0.3 --- 20 FeS04 coagulation o f r i v e r water 43

Floccu 1a t i o n 8.0 0.3 _-- 90
Pb 6-10 0.15 --- >97 FeSO coagulation o f r i v e r water 43
6-10 0.15 --- >97 A l ~ m ~ c o a g u l a t i oonf r i v e r water
6-10 0.15 --- >97 FeSO coagulation o f w e l l water 43
6-10 0.15 --- 80-90 A l ~ m ~ c o a g u l a t i oonf w e l l water
6-10 10 --- > 95 FeSO coagulation o f w e l l water 43
6-10 10 --- 80 A l ~ m ~ c o a g u l a t i oonf w e l l water
CrC6 5.5 0.15 --- -35 FeSO coagulation of r i v e r water 43
6-10 0.15 --- <10 Alum4coagulation of r i v e r water
Cr+3 6.5-9.3 0.15 --- '98 FeSO coagulation 43
6.7-8.5 0.15 __- >90 A1uotcoagul a t ion
9.2 0.15 __- 78 Alum coagulation
optimum 10 _-- >98 FeSO coaqulation 43
optimum 10 --- >98 A1um4coagulati o n
Mixed Metals: -- 38
Cr 1.2 0.3 75 Primary treatment w i t h 18.3 mg/l
cu 0.8 0.4 50 f e r r i c i r o n + 0.32 mg/l
Fe 2.2 1.9 14 P u r i f l o r A23 f l o c c u l a n t
Ni 1.3 0.9 31
Zn 2.8 0.9 68
Mixed Metals: --
Cr 1.2 0.2 83 Secondary treatment w i t h 150 mg/l 38
cu 0.4 0.2 50 f e r r i c i r o n + 0.20 mg/l P u r i f l o c
Fe 3.6 1.1 69 A23 f l o c c u l a n t
Ni 0.8 0.4 50
2n 3.7 1.3 65
Mixed Metals: 6.5-7.0 Alum Sulfate treatment 106
Pb 3.4 0.5 85.3
cu 3.0 0.2 93.3
Cd 3.1 1.2-1.7 .45.1
cr+3 3.2 0.2-0.4 s37.5
Cr+6 3.0 0.9-2.3 ~23.3
Zn 2.6 1.7 34.6
Mixed Metals5.5-7.0 Alum S u l f a t e treatment 106
Pb 17 0.7 95.9
cu 15 1.8 88.0
Mo 11 12 0
~ r + ~ 15 0.3 98.0
Zn 17 2.6 84.7
Ni 16 11 .o 26.3
co 12 12.5 0
Mixed Metals: --- A1um coagulation 6
Cd 5.86 0.57 90.3
Cr 158.8 17.3 89.1
cu 528:9 42.3 92 .O
Pb 767.3 78.2 89.8
Hg 0.29 0.20 > 31.0
Ni 1000 2.0 > 93.1
Aa 28.79 __ --
Zi 550 300 M5.5
No. 243. Vol. 81 195
' 0

Table 1 (cont.)
Technology Metal(s) pH I n i t i a l Metal Residual Metal Reilloval Comnennts Reference
Employed Concent r a t i o n * Concentration* E f f i c i e n c y ,%

Coagula- Mixed Metals: -- Sodium Aluminate Coagulation 6

tionl Cd 17.29 4.10 76.3
-
F1occu 1
ation
Cr
cu
48.1
536.1
3.8
57.9
92.1
89.2
Pb 72.3 5.9 91 .E
0.64 0.23 64.1
H9
Ni 1000 --- -_-
A9 20.86 2.0 90.4
Zn 990 300 '69.7
Flotation Pb 6.0 50 1.4 97.2 100 mg/l Feftt, 30 mg/l NLS, 155
6.5 50 0.0 100 A i r f l o r r a t e = 1.4 ml.sec,
7.0 50 - 0.1 99.8 0 M NaN03
7.5 50 0.0 100
8.0 50 0.1 99.8
Pb 6.0 50 1.4 97.2 0.025 M NaN03 155
6.5 50 0.0 100
7.0 50 0.14 99.7
7.5 50 0.20 99.6
0.0 50 1 .I 97.8
Pb 6.0 50 1.5 97.0 0.050 M NaN03 155
6.5 50 0.10 99.8
7 .O 50 0.42 99.2
7.5 50 0.56 98.9
R.0 50 7.8 94.4
Pb 6.0 50 1.3 97.4 0.075 M NaN03 155
6.5 50 1 .0 98.0
7.0 50 0.7 98.6
7.5 50 2.2 95.6
8.0 50 6.3
Pb 6.0 50 2.1 155
6.5 50 1.1
7.0 50 5.8
7.5 50 2.6
8.0 50 19.0 62.0
Pb 5.6 20 7.0 70.0 100 mg/l Fettt, 40-50 nig/l NLS, 155
6.4 20 1.5 92.5 Influent flow rate = 2 galhiin,
6.6 20 0.9 95.5 A i r f l o w r a t e = 84 m3/hr
6.7 20 0.5 97.5
6.9 20 0.6 97.0
7.0 20 0.8 96.0
7.2 20 0.9 95.5
Cd 8-10 1 .o ~0.05 295 Fe(0H) copreci p i t a t i o n 98
Hg 8-10 1 .o <0.03 .97 followsd bv f l o t a t i o n w i t h sodium

Ion Mixed Metals: 8.4 Ion exchange p o l i s h i n g system 44

Exchange Ni 8.9 0.16 98.2
cu 0.3 0.02 93.3
Mixed Metals: -- Metal cyanide wastewater 44
Cd 0.4 0.0001 >99.9
Ca 28.8 1.637 94.3
Cr 0.52 0.356 31.5
cu 0.28 0.41 0
Ni 2.92 0.425 85.4
Fe 3.3 0.195 94.1
Zn 23.0 2.62 88.6
CN 31.4 3.0 90.4
Mixed Metals: 11.0 Chrome f l o o r sump 165
Cd 0.55 q0.005 >99.1
Cr 688 <0.02 >9Y. 99
cu 33.6 <0.05 >99.85
Fe 64.0 ~0.05 ~99.92
Pb 1.6 (0.05 >96.87
Ni 64.2 <0.05 >99.92
2n 1050 co.02 >99.99
Mixed Metals: 11.0 Chrome r i v e r sump 165
Cd <0.02 <0.005 >75.0
Cr 450 <0.02 >99.99
cu 3.2 <0.05 >98.43
Fe 5.65 < O . 05 .99.11
Pb 0.20 ~0.05 >75.0
Ni 0.45 <0,G? >88.88
Zn 245 cC.G; .9Y.99
Mixed Metals: 6.9 Nickel r i n s e sump 165
Cd <0.02
Cr 0.33
__
CU 2.1
Fe 0.8 .0.05 >93.75
Pb 2.0 ~0.05 >97.50
Ni 133.75 <0.05 >99.96
Zn 30.0 <0.02 >99.93
 Separation of Heavy Metals AlChE SYMPOSIUM SERIES
Table 1 (cont.)

Technology Metal(s) pH I n i t i a l Metal Residual Metal Removal Comnents Reference

Employed Concentration* Concentration* Efficiency,%

Ion Mixed Metals: 11.6 Zinc sump 165

Exchange Cd <0.01 <0.005 >50.0
Cr 0.10 <0.02 >80.0
cu 3.24 <0.05 >98.46
Fe 0.08 <0.05 >37.5
Pb ~0.05 <0.05 ---
Ni 1.08 <0.05 >95.37
Zn 19.0 <0.02 >99.89
L i q u i d Ion Ni 2;0 100 <1 > 99 Mixed nletal wastewater 76
Exchange cu 3.1 100 C1 > 99 containing 100 mg/l each of
Cd 5.4 100 <I > 99 Cd, C r . Ni, and Zn
Cenlentation Cu 2.1 100 89.3 11.7 7.25 mg/l Fe.27.9 min. reaction time 112
100 79.6 20.4 13.55 mg/l Fe.25.7 min. reaction tinie
100 56.3 43.7 36.75 mg/l Fe.25.8 min. reaction time
100 63.0 37.0 7.25 mg/l Fe.52.0 min. reaction time
100 12.9 87.1 36.75 mq/1 Fe.46.0 niin. reaction tinie
Electrochemical C r 4.0 195 0.1 99.94 30 min., c u r r e n t density-0.0085 Alcm2 127
Operations 6.8 180 0.04 99.97 50 min., c u r r e n t density=0.007 A/"
7.7 150 0.0 -100.0 30 min., c u r r e n t density=0.011 A/"
8.8 185 0.06 99.96 40 min., current density=0.012 A / c d
7.6 175 0.1 99.94 60 min., current density=0.0085 A / c d
8.9 188 0.18 99.90 50 niin., c u r r e n t density=0.011 A/"
---
cu 100 <l.O >99.0
.
F i e l d data f o r solutions containing 146
EDTA. Quadrol t a r t r a t e pyrophosphate,
amnoniuni p e r s u l f a t e etch, and peroxide
s u l f u r i c copper etch
cu --- 670 c 1 .o >99.85 --- 13
cu ___ 95.6 0.05 99.95 87 % c u r r e n t e f f i c i e n c y 7
cu -9 -230 -0 -100 -3.2 hours 47
Cu 3.0.9.0 >50 --- >80 P r i n t e d c i r c u i t board wastewater 24
Zn _-- 180-300 --- >60 Zinc p l a t i n g l i n e 157
Mixed Metals:
Cir.Pb -9 -150 -0 -1 00 -2.6 hours treatment 47
~~~

Biological Cu --- 50 80-85 Acclimated a c t i v a t e d sludge 97

Operations Cu --- 0.4-25.0 50-79 Activated sludge 104
Cd 7 .O-8.0 __- - 90 Suspended s o l i d s = 2.6 gm/l 78
Cd e4 5.16-10.4 < 20 Activate! sludge 51
5-6 5.16-10.4 50
'7 5.16-10.4 > 80
10 5.16-10.4 90-99
Ni 7.0 __- -60 Suspende! s o l i d s = 4.4 gm/l 70
8.0 --- --- -90
Cd 7.2-7.4 1.9-2.3 <0.1 -95 5 mg/l Cd spike i n R8C operation 30
2 .O-2.4 0.2-0.5 -85 20 mg/l Cd spike i n RBC operation
cu 7.2-7.4 0.18 0.10-0.14 40- 1 mg/l Cu spike i n RBC operation 30
0.45 0.05 -90 5 mg/l Cu spike i n RBC operation
1 .u 0.25 75 10 mg/l Cu spike i n R8C operation
1.1 0.63 43 25 mg/l Cu spike i n RBC operation
1.2 0.84 30 50 mg/l Cu spike i n RBC operation
cu 7.2-7.4 0.18-0.45 Reniovals were 60-90% i n the 1 s t 30
1.0-1.2 stage, 15% i n the 2nd stage, and
10% i n the 3rd staqe.
Adsorption Co >9 _-_ --- >80 1 gui/l F i l t r a s o r b a c t i v a t e d carbon 58
>9 --- --- >8U 1 gm/l Nuchar a c t i v a t e d carbon
>8 __- r-- 2 ?80 7 1 gm/l Oarco a c t i v a t e d carbon
Zn 8.5 2.1 0.25,,0.9 88.1,,57.1, Carbon adsorption p o l i s h i n g EO
9.0 0.7 0.15,,0.25, 78.61~64.3, f o l 1owing hydroxide prec ip i t a t ion
9.5 0.6 0.10,,0.15, 83.3,,75.02 treatnlent using 1.0 qm/l o f :
10.0 0.4 0.101,0.057 75.0, ,87.57 1.Darco 5-51 and 2.Calgon F300
10.5 0.45 0.10, ,0.052 77.71.88.8,
11 .o 0.55 0.12 ,0.05 78.2 .90.9
Cd 9.0 1.55 0.50 67.7 Carbon adsorption p o l i s h i n g 80
9.5 0.5 0.05 90.0 f o l l o w i n g hydroxide p r e c i p i t a t i o n
10.0 0.25 0.05 80.0 treatment using 1.0 sm/l Oarco
10.5 0.2 0.05 75.0 S-51 a c t i v a t e d carbon
Cd 9.5 1.3 0.45 65.4 Carbon adsorption p o l i s h i n g 80
10.0 0.9 0.10 88.9 f o l 1owing hydroxide prec ip i t a t ion
10.5 0.8 0.10 87.5 treatment using 1.0 gm/l Oarco S-51
0.35 0.05 85.7 a c t i v a t e d carbon i n the presence o f
100 mg/l CN-
Cd 8.7 0.4 95.4 Cedar wood f l o u r cooked w i t h 164
a l k a l i f o r 30 min. t o convert
the wood t o a l k a l i c e l l u l o s e
rr( -_- --- -100 Alaae used t o adsorb heavy 50
--- 98 iisials
--- >80 Adsorption onto 0.5 gm/l y-FeOOH 12
--- >80 Adsorption onto 1.0 gm/l y-A1 0
-_- >80 Adsorption onto Fe 0 ( 0 . W l k ?e)
-- --- >80 Adsomtion
hydroxi de onto hv&rdus f e r r i c

Membrane Ni --- _-- --- 90-97 Cellulose acetate membranes 29

Operations used i n reverse osmosis operation
cu --- -0.6 0.17-0.03 >71 --- 74

* A l l concentrations are reported i n mg/l unless otherwise noted.

No.243, Vol. 81
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