ELSEVIER

Desalination 180 (2005) 163-172

DESALINATION
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Devel opment of an ion exchange system
for plating wastewater treatment
Tae- Hyoung Eom a, Chang- Hwan Lee a, Jun-Ho Ki m b, Choul - Ho Lee a*
aDepartment of Chemical Engineering, Kong j u National University, Kong ju, 314-701 South Korea
Tel. +82 (41) 8528638; Fax +82 (41) 8582575; e-mail: chlee@kongju.ae.kr
bRR C/NMR, Kong j u National University, Kong ju, 314- 701 South Korea
Received 13 July 2004; accepted 29 November 2004
Abs t ract
Ion exchange technology was applied to this study to treat nickel ion from plating wastewater which
contains heavy metal, bringing environmental problems such as chromium, zinc, copper, and lead. To separate
nickel ion from wastewater, the nickel recovery unit (NRU) used a column packed with strongly acidic cation
resin. The leak of the ion appeared when rinse water that has a concentration of 1.8 g-Ni/L-distilled water
flowed into the NRU as much as 20 times the bed volume. At this time, the capacity of resin packed in the
column was 1.7 meq/ml and over 99% nickel ion was removed. Sulfuric acid was employed with a reagent in
order to regenerate nickel ion from the resin adsorbed. Nickel ion recovered by sulfimc acid was obtainable up
to 120 g-Ni/L. The concentration of sulfuric acid was 2N and space velocity was 2/h. Acid retardation unit
(ARU) experiment could be accomplished by deacidification to control the pH of the solution to recycle in the
plating process. The composition was 30 g-Ni/L and the pH maintained was over 3.0.
Keywords: Ion exchange technology; Plating waste water; Nickel recovery unit; Acid retardation unit; Ion ex-
change system
1. I n t r o d u c t i o n
Was t ewat er di schar ged f r om i ndust ri es like
pl at i ng pr ocesses cont ai ns many heavy metals.
They, such as copper, lead, chr omi um, ni ckel ,
iron, and zi nc etc., have a fat al ef f ect on t he
human body as wel l as causi ng envi r onment al
pollution. Especially, nickel that has been used
in pl at i ng processes, ni ckel batteries, alloys, and
steels. To be pr oduced f r om ri nse wat er t o el ec-
*Corresponding author
t r ol yt e aft er pl at i ng is a maj or sour ce that ex-
hausts ni ckel i on in t he mi ddl e o f t hem [1-5].
The ni ckel concent r at i on cont ai ned in ri nse
wat er is about f r om 500 ppm t o 2000 ppm.
In envi r onment al pol l ut i on, pl at i ng com-
p a n e s f ocussed on t he r emoval of t oxi c ma-
terials in t he past, but r ecent l y researchers have
been st udyi ng a t echnol ogy t o hol d back
pol l ut ant s at least and r ecycl e t hem [4].
In or der to choose t he met hod t o r ecycl e t he
met al s in t he pl at i ng process, t here are some
0011-9164/05/$- See from matter 2005 Elsevier B.V. All rights reserved
doi: 10.1016/j.desal.2004.11.088
164
T.-I-L. Eom et al. / Desalination 180 (2005) 163-172
points to consider like using the solution con-
centrated from the process, treatment for by-
product sludge, regeneration and recycling of
process water and recycling for treated waste-
water [3,4].
Technologies to separate ions from waste-
water have been physical adsorption using an
adsorbent such as silica gel, activated carbon
and activated alumina, etc. These physical
methods, however, are limited in selective re-
moval of organic materials and other metals
containing high concentration in the rinse water
from the plating line. To overcome the problem
of physical methods and to efficiently separate
pollutant ions, many methods have been used
such as oxidation/reduction, precipitation, ion
exchange, reverse osmosis, adsorption, electro-
winning, electrodialysis and so on. Of the above
methods, the performance of electro-dialysis
and reverse osmosis has some advantages over
the others. But even though both methods have
an advantage in efficiency, they have some
problems such as installation charges and
operation costs. Also, there is the need to
secondarily treat the recovered solution and
there are difficulties in treating large volumes
and high concentration due to the pressure drop
[4-6,8].
Comparing the technology of ion exchange
with others, ion exchange technology has the
advantage that it can treat a large volume at
once and directly recycle the metals in a plating
bath. It can recover over 97% [6,7].
Ion exchange is a phenomenon that is re-
versibly exchanged between counter ion on
bead surface and ion in the solution by the dif-
ference of electrostatic force. In the process, ca-
tion, such as nickel, copper, sodium etc., is ex-
changed with hydrogen ion. Also, anion, as
sulfates, chromates and chlorides etc., is ex-
changed with hydroxyl ion [ 10-13].
This technology has been mainly applied to
pharmaceutical purification, water softening pro-
cesses, separation and purification in the food
industry, catalyst and manufacture of ultra-pure
water used in semiconductor processes etc.
Technology recovering nickel ion-by-ion ex-
change uses a column that packed beads. At the
present, to separate nickel ion, ion exchange
resins use cation resins that are able to selec-
tively exchange the nickel ion with hydrogen
ion in wastewater. While the solution flows into
the column until its capacity is reached to break-
through point, the resin separates nickel ion
from the solution. After adsorbing nickel ion,
the resin is regenerated by acid [11-13]. Be-
cause the pH of the solution recovered through
the column packed with cation is too low to re-
cycle directly in the plating bath, it requires
other treatment to be able to use the solution in
it. To accomplish this requirement, acid retard-
ation also was used in this study. That is the
technology that high concentration acid is ad-
sorbed on the anion resin and metal salts are
excluded by passing through the resin. This is a
reversible process and acid adsorbed on the
resin could be easily regenerated by distilled
water [14,15].
This study was carried out to confirm and sel-
ect operational conditions and ways that need to
develop ion exchange system (IXS). It was com-
posed with a nickel recovery unit (NRU) to con-
centrate the concentration of nickel ion from
rinse water as salt and acid retardation unit
(ARU) to control the pH of the salt solution to
be recycled in the bath. Experiments were con-
ducted on each unit, NRU, ARU, and IXS inte-
grating them in order to build up operational
variables as space velocity (SV) of solutions
flowing into column, H2SO4 concentration and
volumes of distilled water used in regeneration
of the ARU column.
2. Exper i ment
Before the experiment was carried out, the
resin had to be selected and its characteristic un-
derstood. In selecting apt ion exchange resin,
although weakly acidic cation and weakly basic
anion resins have greater affinity than each
strong resin for counter ion, the strong resins
were used because they especially have an
advantage for pH range.
2.1. Materials
T.-H. Eom et al. / Desalination 180 (2005) 163-172
The resin used in this experimental work
was of the DIAION series, made by Mitsubishi
Kasei Co., Japan. It is a strongly acidic cation
resin that separates nickel i on from rinse water,
contains PK 228 that has an Na form as t he
exchange group and a strongly basic anion resin
does PA312. It has t he C1- form and is used to
control t he pH of t he solution recovered by the
cation resin in order that nickel ion may be
recycled in the plating bath without other treat-
ment. Bot h t he cation resin and the anion resin
are porous type. Table 1 shows characteristics
of each resin, strongly acidic cation and strong-
ly basic ani on resin, used in this experiment
[11].
To manufact ure model rinse water, nickel
(II) sulfate (NiSO4, 6H20) and nickel (II)
chloride (NiC12,'rH20) used an extra pure grade
made by Junsei Chemical Co. In order to pre-
treat ion exchange resin to be used in the experi-
ment, an extra pure grade sodi um chloride,
manufact ured by Junsei Chemical Co., and
sulfuric acid manufact ured by Dong Woo Fine
Chemi cal s for t he electronic grade was em-
ployed.
The size of t he col umn composed in each
unit, nickel recovery unit (NRU) and acid re-
165
tardation unit (ARU), had a diana of 25 mm and
length of 500 ram. This is bench scale. The
col umn was packed with PK 228 and PA 312.
In the mini-pilot plant scale test, t he di am and
length of t he col umn was each 34 mm and
570 ram. At this time, all of each column,
bench scale and mini-pilot plant scale, were
packed by usi ng a measuri ng cylinder and
packed more vol ume than col umn volume. The
model rinse water was fed into t he units with a
peristaltic pump made by Masterflex Co.,
model No. 7523-47.
2.2. Pre-treatment of ion exchange resins
Before the test was carried out, the resin had
to be pre-treated. After the resin was packed in
the column, a particle was removed t hrough
backwash below 300 grn. In general, the con-
ditioning met hod is to provide HC1 (4-8%) and
NaOH (4%) by turns. At this time, reagent and
rinse water fl owed into t he col umn by repeti-
tion. The procedure of pre-treatment, however,
is different for the goal of experiment and ionic
form.
In this experiment, pre-treatment process
was comprised with supplying 2N NaOH solu-
tion into the col umn excessively and, after that,
washing ions remained on beads, and 5 vol %
Table 1
Properties of ion exchange resins
Grades PK 228 PA 312
Resin type Porous Porous
Matrix Polystyrene + DVB Polystyrene + DVB
Functional group -SO3-, sulfonate -N(CH3)3CI-, Trimethyl ammonium
Ionic form Na ~ C1-
Specific gravity 1.35 1.1 0-1.16
Total capacity, meq./ml 2.05 1.3
Operating temp., C 120, Na, H form 60, OH form, 80 C1 form
Moisture content, % 37-43 49-55
pH range 0-14 0-14
166 T.-H. Eom et aL / Desalination 180 (2005) 163-172
sulfuric acid and distilled water did so. Through
this step, strongly acidic cation resins packed in
NRU col umn substituted Na + form to H + form
and strongly basic anion resins used in ARU
col umn exchanged C1- form to SO42- form.
2.3. Cont i nuous experi ment
2.3.1. Ni ckel recovery uni t (NRU)
The NRU experiment, bench scale and mini-
pilot scale, used strong cation exchange in order
to recover nickel salt from rinse water. It was
exchanged Na + form with H + form through pre-
treatment. Model rinse water used in this test
was made by dissolving nickel sulfate
(NiSO4,' 6H20) 6.2 g and nickel chloride
(NiC12,-6H20) 1.6 g in 1 L distilled water. The
nickel i on concentration of this solution is
1.8 g-Ni/L. This is the average concentration of
nickel ion contained in wastewater.
To confi rm the worki ng capacity of the
strong resin, nickel-loading test empl oyed the
NRU col umn of bench scale. Model rinse water
was provi ded into t he col umn upward to pre-
vent a drift in the space velocity of 50/h. After
finding out t he capacity, t he experiment pro-
gressed to obtain optimal operational conditions
as t he change of space velocity. At this time,
t he vol ume was supplied in 10, 25, 50 and 75/h.
The regeneration of t he NRU col umn used sul-
furic acid solution. In the first place, the sulfuric
acid solution of 2 N concentration was run into
the NRU col umn adsorbing nickel ion to fred out
the composi t i on of solution regenerated for the
change of the flow rate of sulfuric acid with
2, 3, 4, and 5/h. To examine t he concentration
change of nickel salt recovered by H2SO4, t he
flow rate of reagent fixed in 2/h and t he con-
centration of H2SO4 was changed with 1 N
(2.8 vol %), 2 N (5.3 vol %), 3 N (8 vol %), 4 N
(10.7 vol %) and 5 N (13.3 vol %) concentration.
At this time, nickel salt concentration of eluted
solution in each step was measured by usi ng
ICP-AES (Perkin Elmer Co. Model name - Op-
tima 2000DV) and the pH and ion conductivity
of solution eluted from the col umn did the same
way. The conditions are exhibited in Table 2.
2.3.2. Aci d retardation unit (ARU)
ARU experiment used strongly basic anion
exchange resin (Diaion PA312) whi ch substi-
tutes C1- form to SO42- form to control t he pH
of nickel solution regenerated from NRU
through de-acidification. The concentration of
model solution was 37.3 g-Ni/g and it was
manufactured based on t he composi t i on of
nickel salt recovered from NRU. At this time,
because the pH of the solution from NRU was
1 below, 5 vol % sulfuric acid was added into
the model solution to adjust t he pH. While it
was provided into ARU col umn in SV2, 5 and
10/h, the concentration of nickel i on was
measured on flow rate change.
Regenerating the anion resin in ARU col umn
used ultra pure distilled water (DI water). The
flow rate was changed wi t h 10, 20 and 30/h.
Solutions supplied in ARU loading and regene-
Table 2
The condition of nickel recovery unit test
Feed Class
Concentration
Space velocity, h
Resin type
Loading Regeneration
6.2g NiSO4"6H20 + 1.6g NiC12.6HzO
1.8 g-Ni/L
10, 2 5 , 50, 75
Strongly acidic cation - - PK 228
SulNricacid
1, 2, 3, 4, 5N
2, 3, 4, 5
T.-H. Eom et aL / Desalination 180 (2005) 163-172 167
ration selected t he direction to be upward to
prevent a drift.
The nickel salt concentration of eluted solu-
t i on in each step was measured by using ICP-
AES (Perkin El mer Optima Co., Model
2000DV) and pH and i on conductivity di d so.
Table 3 shows the experiment conditions of
ARU.
2.4. Ion exchange system (IXS) experiment
A systematic experimental apparatus was
desi gned wi t h bench scale and pilot plant scale.
The experi ment was performed to systemize
NRU and ARU t hrough applying the opera-
tional condi t i on gotten by col umn test for re-
covery and recycling of nickel salt.
In t he case of t he bench scale, model rinse
water was suppl i ed into t he NRU of system in
order to recover concentrated nickel salt with
space vel oci t y 10, 50/11. The regeneration of
NRU used 3.8 N (10 vol %) H2SO4 solution and
it was run into t he col umn upward with 2/h.
The solution regenerated from NRU fl owed
straight to t he ARU col umn wi t h t he same
direction of NRU. When the solution was pro-
vi ded to ARU, the hydrogen i on concentration
of t he solution was controlled and to supply
sulfuric acid was broken as t he pH got ready up
to t he concent rat i on that enabled its use in t he
plating bath. After stopping t he provision of
HzSO4, solution that existed bet ween beads of
NRU and ARU col umns was removed by air
bl owi ng-down. Reagent empl oyed ultra pure DI
water to regenerate nickel i on adsorbed on
strongly basic anion resin. The flow rate
changed space velocity 10, 50/h. At this time,
because the solution regenerated by DI water
contained hi gh nickel i on concentration, it made
nickel ion re-adsorbed and used to wash beads
of NRU. The system experiment of bench scale
was operated in a co-current way. In t he case of
the mini-pilot plant, t he operation manner
empl oyed was counter current and did not carry
out air bl owi ng in each step. The results of t he
mini-pilot plant scale were compared wi t h t he
bench scale. Apparatus of IXS, mini-pilot plant
scale, is exhibited in Fig. 1.
3. Res ul t s and di s c us s i on
3.1. Continuous experiment
3.1.1. Nickel recovery unit ~RU)
In the NRU loading test, t he leak of nickel
ion appeared when model rinse water,
1.8 g-Ni/L, flowed into the col umn as much as
20 times the resin vol ume wi t h SV 10, 25, 50
and 75/h. At this breakthrough point, the
strongly acidic cation resin, PK 228, could con-
fu'rn to have a working capacity of 85 mg-Ni/rnl-
resin, 1.7 meq/ml. Nickel i on concentration was
found out to be detected as 22 ppm and it was
removed over 99%. Ion conductivity of solution
eluted from the col umn had increased from
6.57 mS/ cm to 30.7 mS/cm. Also, t he pH was
decreased from 5.5 to 2 bel ow because hydro-
gen i on in the solution increased t hrough ex-
Table 3
The condition of acid retardation unit test
Feed Class
Concentration
Space velocity, h
Resin type
Loading
178g NiSO4'6H20 + 5 vol % Hz SO4
37.3 g-Ni/L, pH 1.0 below
2, 5, 10
Strongly basic anion - - PA 312
Regeneration
Distilled water
10, 20, 30
168 T.-H. Eom et al. / Desalination 180 (2005) 163-172
1.2
1, 0
o
o 0. 8
0
g 0.6.
O
- o 0. 4
iTi 0.2
0.0
it-St t ~m- =~-=t , = =~
/
f
l! '
~ A
1 ,' sv = 10in
':' SV = 2~lh
A / AI~ ,A SV=50~
. . . . . . . . . . . . . . . . . . *
2000 4000 6COO 8000 10000 12000 14000
Acc. f eed vol ume [ml]
Fig. 2. The effect of space velocity on eluted nickel ion,
Ni 2+, concentration in case of NRU loading as initial
nickel concentration of rinse water is 1,800 rng-Ni/L.
Fig. 1. Apparatus of ion exchange system of mini-pilot
plant scale, 500ml.
changing selectively between nickel ion and I-I +
on the resin.
In this case, the capacity of strongly acidic
cation resin which was packed in NRU was not
influenced in the flow rate. Fig. 2 shows the
breakthrough curve on the SV change of rinse
water supplied into NRU.
When aqueous H2504 was supplied with
space velocity 2/h and the sulfuric acid com-
position was 2 N to regenerate NRU, the nickel
ion concentration obtained was 72 g-Ni/L as the
highest concentration.
Although the flow rate of H2SO4 solution
increases, the concentration of nickel ion re-
covered from the column was not increased. It
seems to be taken place dilution of the ion by
H2SO4 at the desorption process. To examine
the effect of reagent concentration, when the
feed rate of H2SO4 was fixed with 2/h and the
concentration of H2SO4 was changed with
1 N (2.8 vol %), 2 N (5.3 vol %), 3 N (8 vol %),
4 N (10.7 vol %), and 5 N (13.3 vol %), the con-
centration of aqueous H2SO 4 could be gained up
to as much as about 120 g-Ni/L. This is
considered as the composition of nickel ion
recovered from regeneration process depends
on H2SO4 concentration. The results are shown
in Figs. 3 and 4.
3.1.2. Acid retardation unit (ARU)
It is possible for the solution regenerated by
sulfuric acid to be used using in plating bath
except having very low pH. To recycle nickel
salt regenerated by HzSO4, the solution needs to
be controlled pH with treatment by using
strongly basic anion resin. ARU maintained over
30 g-Ni/L until the concentrated solution sup-
plied was as much as 400 ml and recovered
over 3.5 while it flowed into the column about
300 ml. These results had no connection with
the flow rate. In aqueous solution, the dissoci-
ation constant (Ka) of sulfuric acid is 103 and
the dissociation constant of bisulfate is 10 -2. Be-
cause the pH of solution employed to ARU is
1.0 below, H2SO4 existing in model solution fed
to ARU has bisulfate form and hydrogen ion
after it passes the first dissociation step. Contact-
T.-H. Eom et al. / Desalination 180 (2005) 163-172 169
8 0
6O
" O
~ . 2o
0
sv = 2fn
[ ] SV : 3fn
SV = 4 / h
,' ~ SV = 5/h
0 108 200 300 400
Acc. reagent f eed vol ume [ml]
Fig. 3. Nickel ion, N i 2+, concentrations on space velo-
cities in the case of NRU regeneration by sulfuric acid
solution.
1 . 0
8 0 , 8
=d 0.6
8
o . 4
0 . 2
o.o

/
/
/ m / sv=10~
100 200 3 0 0 400 500
Feed vol ume [roll
Fig. 5. Space velocity effects on the nickel ion, N i 2+,
concentration of mixed solution in case of ARU load-
ing.
120 1 ~ 1NH=SO, 1 0.030
1 1 ~ 1 ' 0 ' ~ H , S O , / 0 . 0 2 5
4 0 ]:
0 ; - ~ - ~ 2 ~ - - TZ: 0.005
0 1130 20O 300 40O 0,000
Acc. reagent feed volume [m0
Fig. 4. Nickel ion concentrations in eluted solution re-
generated by each sulfuric acid concentration at space
velocity 2/h.
t i ng wi t h t he resin havi ng SO4 2- group by pre-
treatment, hydr ogen i on remaining excessi vel y
in t he sol ut i on is adsor bed on t he strongly basi c
resin and SO4 2- on t he resin is subst i t ut ed wi t h
HS O4 - .
Whi l e this sorpt i on is advanced bet ween bi-
sulfate i on exi st ed in concent rat ed model solu-
t i on and sul fat e ion on the resins, HSO4- in the
sol ut i on is di ssoci at ed wi t h H and SO4 2- again.
Thi s sorpt i on is domi nat ed by Le Chateliers
principle.
k SV= 2tn
SV= 5in U
S V = l ~ /
/
1 [
/
/
0 100 200 300 480
Feed vam-~ [ra]
Fig. 6. H concentration change of mixed solution on
space velocity in case of ARU loading.
It seems to raise t he pH of sol ut i on re-
cover ed from NRU as a result of bei ng di-
mi ni shed hydr ogen i on by this process. But, at
this time, ni ckel i on was adsor bed on t he resin
wi t h I-I +. The changes of the concent rat i on and
t he pH of sol ut i on recovered from ARU on t he
change of fl ow rate are exhi bi t ed in Figs. 5
and 6.
In process regenerat ed ni ckel i on whi ch is
adsorbed in ARU, desorpt i on of ni ckel i on was
170
easily carried out t hrough feeding DI water and
had no connect i on wi t h flow rate of DI water.
This shows that the separation t echnol ogy by
acid retardation is a reversible process. The re-
sults from t he ARU regeneration process are
shown in Fig. 7.
3.1.3. Mi ni -pi l ot pl ant experiment
In order to get a systemized operational con-
dition of the i on exchange system (IXS), a
mini-pilot scale, 500 ml, was operated with
space velocity of 50/h that was selected through
a bench scale test.
It is was found that the breakthrough point
of nickel i on occurs when model rinse water
was fed into t he mini-pilot col umn as much as
25 times. Fig. 8 exhibits the results. The con-
centration of regenerated solution was
80 g-Ni/L. The results compari ng with bench
scale are shown in Fig. 9.
In t he ARU experiment, ARU col umn could
recover more vol umes of solution than bench
scale of whi ch nickel concentration is 30 g-Ni/L
over and its pH is 3.0 over by deacidification.
Figs. 10 and 11 exhibit each of the results
compari ng ARU bench scale and mini-pilot
scale.
300O0
- d
d 20000
8
z
~ 100t70
3
LU
T.-H. Eom et al. / Desalination 180 (2005) 163-172
S V = 1 0 4 q
- - I - - sv = 2o~
- - 4 k - - sv: 3~
. . . . . . . , ~ . . . . . . 5 V = 4 0 , ~ h
- " - 0 . . . . S,,,' = ,50,h
500 1000 1500 2000 2500
water vdume [~]
Fig. 7. The concentration change of eluted solution on
space velocity change in case of ARU regeneration by
DI water.
1,0
"~" o.e
0
~
0.6
~: 0.4
[] 0.2
0.o',
m . . . . .
~ Bench scale (200ml)
Mini pilot (500ml)
20 40 60
Vol ume f r act i on ( ml - f eed/ ml - r esi n)
Fig. 8. Breakthrough curve change for bench scale and
mini-pilot scale in the case of the IXS experiment.
1 2 0
100
0
~ 40
3
rn
20.
0.0
Bench scale (200 rnl)
, , , . . . . , . . . . , . . . . ,
0.5 1.0 1.5 2.0
V o l u m e f r a c t i o n ( r n l - r e a g e n t l r n l - r e s i n )
I
!
Fig. 9. Nickel ion concentration of NRU regeneration
by sulfuric acid, 3.8 N, for bench scale and mini-pilot
scale.
The worki ng capacity of i on exchange resin
relies on variables as resin capacity, the com-
position of model rinse water and void vol ume
etc. For all that, in this experimental work, the
ion concentration and the resin capacity are con-
stant but the void vol ume of the col umn of
mini-pilot plant scale is di mi ni shed due to being
compact l y packed wi t h resin/unit volume.
Therefore working capacity for treating nickel
1.0
0.8
0 ~ 0 . 6
v
8
0,4
0.2
0.0 ~, ~ . . . . . . . . . , . ,
0,0 0.2 0.4 0.6 0.8 1.0 1,2
Vol~'ne fraclJon (ml-feedtml-resin)
T.-H. Eom et al. / Desalination 180 (2005) 163-172
=
/ t t " ~ / 0
, . / / / ~ Benchscale(2OOml)
. . ~ M~ n i pi l ot scal e ( 5 0 0 r nl )
Fig. 10. Nickel ion concentration of solution recovered
from ARU of bench scale and mini-pilot scale.
171
solution has hi gh concentration as the H2804
concentration is hi gh and its flow rate is low.
By basing on these, the space velocity of re-
agent fed with 2/h and the concentration was
3.8 N (10 vol. %). At this time, t he highest
concentration of recovered solution was
83 g-Ni/L. To control pH of t he solution, the
solution recovered from NRU was supplied
cont i nuousl y to ARU until the mi xed pH of
solution from ARU was hol di ng up 3.0 over.
Finally, IXS could recover nickel salt solution
that the concentration of the mi xed solution was
30 g-Ni/L over and its pH 3.0 over. The vol ume
of the recovered solution was the same as t he
vol ume of resin packed in the col umn and t he
0 . 0 1 0
0 . 0 0 8
d
0 . 0 0 6

"~ 0.004
X
0 . 0 0 2
Bench scele(2OOml)
~t[~l b4ni pilot scale (500 mb
J
0 . 0 0 . 2 0 . 4 0 . 6 0 . 8 1 . 0 1 . 2
Volume fraction (ml-feedtml-resin)
i L-- . - 4
Fig. 11. H + concentration of solution recovered from
ARU for bench scale and mini-pilot scale.
ion was enhanced and t he ARU col umn could
treat greater vol ume t han t he bench scale.
highest mi xed concentration of nickel ion was
38 g-Ni/L.
To examine t he effect on operation ways,
bench scale IXS, 200 mi, was carried out wi t h
co-current and in each step, the solution was
removed wi t h air bl owi ng down after pausing to
feed solutions. However, mini-pilot plant scale,
500 ml, applied counter current way without air
blow down. The result had not many differ-
ences bet ween bench and mini-pilot scale.
Only, it needs to give back what is eluted from
NRU regeneration and ARU regeneration to
keep from dilution to NRU feed tank in counter
current operation t hough the solutions contain
nickel ion of very low concentration. The com-
position of t he solution was 30 g-Ni/L and its
pH was 3.0 over and recycled vol ume was
1.3 times the resin volume. Fig. 12 shows t he
concentration recovered t hrough counter current
way.
3.2. Ion exchange system (IXS) experiment
In t he IXS experiment systemized NRU and
ARU mini-pilot scale t hrough integrating
operational condition, model rinse water was
fed into NRU col umn until breakthrough point.
The NRU loading test could find out treating
same vol ume, 25 times of packed resin volume,
wi t h cont i nuous test. While NRU resins are
regenerated by aqueous H2SO4, the recovered
4. Concl usi on
In t he continuous test, NRU treated the solu-
tion of whi ch model rinse water concentration
is 1.8 g-Ni/L as much as 20 times of strongly
acidic cation resin. In this case, worki ng capa-
city was 1.7 meq/ ml resin and it was used about
80%. Nickel i on in rinse water was removed
above 99%. Mini-pilot was operated until
25 times of resin volume. In case of NRU regen-
172
T.-H. Eom et al. / Desalination 180 (2005) 163- 172
30
25
20
o
15
z
, ~ 10
5
1 0.0004
I ~ Feed w ~ d i~ cone.
i - - I - - Feedvs rni=d I. ~onc. ~ [
',, / f - ,
',, / /I
/ /f
100 200 300 400 500 600
R e g e n e r a t e d solul~on r e e d [ ml ]
Fig. 12. Nickel ion concentration and H + concentration
of solution recovered from ARU in case of IXS mini-
pilot scale experiment with counter current.
eration, the highest composition of nickel ion
recovered by H2504 was obtained as H2804
flow rate is 2/h and H2SO4 concentration is high.
It is possible for ARU to control the pH of
t he model concent rat ed sol ut i on of NRU main-
tains 3.0 or mor e and the concent rat i on is mor e
t han 30 gNi / L by aci d retardation.
Bench scale IXS syst emi zed by cont i nuous
operat i onal condi t i on coul d r ecycl e model rinse
wat er as much as resin vol ume and mini-pilot
scal e t reat ed 1.3 times. Also, operat i onal way of
IXS was sel ect ed wi t h count er current.
Acknowledgement
The aut hors wi sh to acknowl edge wi t h
thanks t he Mi ni st ry o f Sci ence and Technol ogy,
Industrial Was t e Recycl i ng R&D Cent er at KI-
GAM, and t he Regi onal Research Cent er for
new material by recycl i ng ( RRC/ NMR) in
Kong Ju Nat i onal Uni versi t y for financial
support.
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