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Treatment of an Anodizing Waste to Water
I
Quality-Based Effluent Limits 2 6 SI 3.PDF
by M. Naziruddin and G.C. Patrick
Jordan, Jones & Goulding Inc., Atlanta, Ga.,
and L. McCune
Tredegar Industries, Newnan, Ga.
T redegar Industries owns and oper-
ates an architectural aluminum
production facility. Raw aluminum is
smelted, extruded into various shapes,
and finished by a selected combination
of chemical etching operations. The
majority of wastewater generated at
this plant comes from the finishing
step, where the contents of the finish-
ing tanks and rinsewaters makeup the
flow to the wastewater treatment plant.
The rinsewaters overflow the tanks and
discharge continuously into the waste-
water treatment plant. The concentra-
tion tanks are discharged when the
effective strength of the chemical solu-
tion weakens or when a manufacturing
change is ordered. In addition, storm
water runoff from areas that may be
contaminated with oil or grease or
chemical reagents is discharged into
the waste treatment plant.
BACKGROUND
In December 1989, a project was
initiated to upgrade the existing waste-
water treatment plant. The upgrade was
performed to replace the existing sedi-
mentation facilities and to provide
equalization. Additionally, the new
treatment system would be designed to
contain sludge thickening and mechan-
ical dewatering.
During December 1989, the Na-
tianal Po!!a:ant Discharge Diminattion
System (NPDES) permit for the exist-
ing treatment plant was reissued. The
new limits were based upon water-
quality-based standards, whereas the
previous limits had been based upon
categorical standards. Because the
plant discharged into a stream that had
a 7-dayIl0-year low flow of zero, the
effluent limits for the stream were
calculated using no dilution.
The new metal limits for the NPDES
permit are shown in Table I. For the
water-quality-based limits, there is no
distinction between average and maxi-
'1
FEBRUARY 1992
mum values. For these metals there is
no average limit, only a maximum
limit. For aluminum, the only metal
limit that was not based upon water
quality criteria, there were maximum
and average permit limits.
Since new, more stringent limits
were being established by the regula-
tory agency, it was decided to conduct
wastewater treatability studies to as-
sure that the new plant would meet
these limits. The focus of the studies
was to evaluate metal precipitation of
the anodizing wastewaters. The exist-
ing treatment system employed a metal
precipitation process using lime and an
alkaline manufacturing by-product (fil-
ter wash); therefore, the tests were
performed to identify the optimum pH,
the best alkaline reagent, whether sul-
fide precipitation would be beneficial,
and whether certain compounds would
affect performance of the precipitation
process. Concurrent activities included
evaluation of the potential to recover
aluminum from the precipitate, and
analysis of sludge dewatering by plate-
and-frame pressure filtration.
WASTEWATER
CHARACTERIZATION
Prior to initiation of the treatability
studies, it was necessary to character-
ize the influent in terms of metal
concentration, PI: ani: flow m e . Tfie
wastewater flows included the anodiz-
ing wastewater and stormwater runoff
from process areas. Discussions with
Table 1. Permit Limits Based on Water-Quality Standards
Discharge Limitations
Effluent AveraGe
Characteristic (lb/day) (mg/L)
Aluminum 11.3 - 22.8
Chromium 0.470 0.370
Copper - 0.021
Nickel - 0.280
Zinc 1.40 0.1 90
A?
~
~
plant personnel revealed that segrega-
tion and treatment of runoff was not a
cost-effective alternative; therefore, the
treatment system was designed to store
and treat stormwater runoff that was
currently received.
To determine the wastewater charac-
teristics, laboratory analyses were per-
formed on three different samples of
the untreated anodizing wastewater.
The first analysis was performed on a
composite sample from the anodizing
wastewaters while the second and third
analyses were performed on grab sam-
ples. The data are reported in Table I1
and show that, of the metals in the raw
wastewater samples, aluminum had the
highest concentration. The analytical
data show other metals (copper, nickel,
and zinc) to be present in the waste-
water.
Also, shown in Table I1 are data of
the influent metal concentrations at
other aluminum anodizing plants and
the permit limits.'g2 The metal charac-
teristics of the Tredegar plant are
within the range of metal concentra-
tions reported in the literature; the
influent samples used for the treatabil-
ity testing were therefore considered to
be representative of anodizing waste-
waters. Because the concentrations of
these metals were higher than the
permit limits, removal of these metals
was required.
TL-
1 iir: prl of the ariodizirig wastewater
-T
ranged from 2.0 to 4.2, necessitating
lime or caustic addition for neutraliza-
tion. The low pH of the wastewater
Detection
Maximum Limit
(lb/day) (mg/L) "I
- 0.1 0
1.30 0.370 0.010
- 0.021 0.020
- 0.280 0.01 0
3.76 0.1 90 0.01 0
69
Table II. Anod king Wastewater Characteristics
Sample ID Date
Anodizing line 1 12/13-15/89
Anodizing line 3 12/13-15/89
Misc. process/stormwater 12/1 3-1 5/89
Waste composite 12113-1 5/89
Anodizing lines 1 and 3 2/27/90
Anodizing lines 1 and 3 311 3/90
Literature data
Ward, R.C.
Cornwell, D.A.
Permit Limit
The December 1989 sampleswere comprisedof grab samples collected 3 times a day. The two 1990 sampleswere grab samples. In January 1990, anodizing line
2 was started up and line 1 was shut down. The referencesfor the literature values can be found in references 1 and 2.
indicated that all the metals initially
present were in the soluble form, and
precipitation of metals by pH adjust-
ment to an alkaline state was identified
as the appropriate treatment procedure.
WASTEWATER TREATABILITY
TESTS
TEST METHODOLOGY
The wastewater treatability tests
were performed with a jar test appara-
tus that simulated rapid mixing, floccu-
lation, and sedimentation. The appara-
tus consists of six paddles connected to
a common drive allowing the paddles
to agitate the wastewater samples for
the same length of time and at the same
paddle speed. The paddle speed was
adjusted (20-100 rpm) to develop
different mixing intensities.
First, the chemical reagents were
added to the beakers and mixed at 60
rpm. Following chemical addition, poly-
mer was added and mixed at 60 rpm for
one minute. After polymer introduc-
tion, the solution was flocculated at 20
rpm. The suspension was then allowed
io settie [or one hour. A portion of the
supematant was decanted and analyzed
for metals. The supematant was fil-
tered through a Gelman type A/E
glass-fiber filter and analyzed for dis-
solved metals.
The study consisted of a series of
five sets of tests, each with different
objectives. For the first set of tests, pH
adjustment was performed to evaluate
metal precipitation using three differ-
ent chemical reagents: lime, caustic,
and a filter wash. The filter wash was a
by-product waste stream that contained
sodium hydroxide. The first set of tests
70
Metals Concentration (mg/L)
PH Zn cu
2.4 0.31 0.86
4.2 0.28 0.12
9.8 0.18 0.03
3.2 0.29 0.17
N.A. 1 .o 0.28
2.0 N.A. 0.64
3.2-1 0.3 0.1 1-0.49 0.17-1.2
- 0.1-0.9 0.48-2.2
0.19 0.021
evaluated metal hydroxide precipita-
tion at pH values of 8, 9, and 10. The
procedure for the second set of tests
was identical to the first except that the
range of pH values tested varied from
7.0 to 10.5 and only lime was used for
pH adjustment.
In the third set of tests, the effective-
ness of sodium sulfide and ferric
chloride to aid in the removal of copper
was tested. The test consisted of so-
dium sulfide and ferric chloride addi-
tion following lime addition. A fourth
set of jar tests was conducted to
determine if ammonia complexes inter-
fered with removal of copper and
nickel. In the fifth and final set of tests,
the samples from the existing wastewa-
ter neutralization basins were collected
and analyzed to evaluate metal precipi-
tation on a continuous basis. The
results from each set of tests are
discussed separately.
RESULTS
Test I
The supematant metal concentra-
iulls measwed fm the first sei of
treatability tests are presented in Table
III. Also shown in the table are the
permit limits for zinc, copper, nickel,
and aluminum. A pH of 8.0 was the
only one of the three tested at which all
permit limitations for metals were met.
Higher pH conditions led to excessive
aluminum discharge; however, zinc,
copper, and nickel were within permit
limits. At the higher pH values, the
aluminum present in the supematant
was in the soluble or dissolved form
making precipitation of aluminum in-
effective.
AI Ni TSS (mg/L)
114 0.02 -
78 0.09 -
-
~
37 co.01
94.5 0.05 - I
130 0.41 50
267 0.16 N.A.
~
11-200 0.02-0.79 -
400 17-22 -
2.26 0.28
This test also evaluated the perform-
ance of different neutralizing reagents.
Only lime and the filter wash yielded
results within limits and these only at
pH 8.0; however, the tests using lime
produced the best performance with
respect to the removal of total sus-
pended solids (TSS). For the treatment
system, both lime and filter wash will
be used because filter wash is available
as a manufacturing by-product. The
total aluminum concentrations of the
tests that used caustic were higher than
those of tests that used lime and the
filter wash for metal precipitation.
Test 2
A second set of tests was performed
to evaluate metal precipitation at a
lower pH value (7.5) and to confirm
the results of test 1. The supematant
metal concentrations and the permit
limits are presented in Table IV. The
permit limit for zinc (0.190 mg/L) was
achieved at all pH values tested (7.5 to
10.5). At all the pH values tested (7.5,
8.1, 9.2 and 10.5), the supematant
aluminum concentration exceeded the
permit limit on the monthly average
basis; however, at a pH of 7.5, the
aluminum concentration was within
the maximum daily allowable concen- ~
tration (4.5 mg/L). At a pH of 8.1, the
dissolved aluminum concentration was
below the detection limit (0.05 m a ) ,
so all the aluminum present was in the
particulate form. This was different
from the results obtained at the higher
pH values (9.2 and 10.5) that showed
aluminum to be present in the dis-
solved form.
The permit limit for nickel (0.280
mg/L) was met at the higher pH values
(9.2 and 10.5), but was not achieved at
METAL FINISHING
I Table 111. Anodizing Wastewater Treatability (Test 7)
Metal Concentration in the SupernatanP
Unfiltered Sample Filtered Sample
Final Supernatant Zn cu Ni AI AI Zn cu Ni AI AI
Reagent pH TSS (mg/L)a (mg/L) (mg/L) (mg/L) (mg/L) (Ib/day)lC (mg/L) (mg/L) (mg/L) (mg/L) (lb/day)lC
Raw - - 0.29 0.17 0.05 94.5 473 - - - - -
8.0 7 <0.02 <0.02 <0.01 0.84 4.2 c0.02 c0.02 <0.01 0.02 0.02
Lime 9.0 <5 c0.02 c0.02 <0.01 6.9 34.5 <0.02 c0.02 ~0.01 3.61 18.1
10.2 12 0.02 c0.02 <0.01 33.1 165.6 <0.02 <0.02 <0.01 29.0 145.1
8.0 c5 <0.02 0.02 ~0.01 2.95 14.8 - - - - -
Caustic 9.0 18 ~0.02 ~0.02 <0.01 8.70 43.6 - - - - -
8.0 14 <0.02 ~0.02 0.02 2.06 10.3 - - - - -
Filter Wash 9.0 28 ~0.02 ~0.02 ~0.01 6.48 32.4 - - - - -
10.0 53 ~0.02 ~0.02 ~0.01 6.48 32.4 - - - - -
Permit Limit 0.19 0.021 0.28 - 11.3 0.19 0.021 0.28 - 11.3
aARer the desired pH was reached, the sludge produced was allowed to settle for one hour and the supernatant was analyzed for TSS.
bAfter the desired pH was reached, the sludge produced was allowed to settle for one hour and the supernatant was analyzed for metals.
CCalculationsare based on a flow rate of 600,000 gpd.

Table IV. Anodizing Wastewater Treatability (Test 7)

Metal Concentration in the Supernatant
Unfiltered Sample Filtered Sample
Final Supernatant Zn cu Ni AI AI Zn cu Ni AI AI
Reagent pH TSS (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (Ib/day)la (mg/L) (mg/L) (mg/L) (mg/L) (Ib/day)a
Raw 50 1.00 0.28 0.41 130 - - - - - -
7.5 50 0.10 0.15 0.41 2.7 13.5 c0.02 0.077 0.325 <0.05 c0.25
Lime 8.1 30 0.11 0.11 0.35 6.7 33.5 <0.02b 0.037b 0.171b ~ 0 . 0 5 ~<0.25
1 9.2 10 0.12 0.19 0.10 24.0 120 <0.02b 0.036b 0.215b 8.10b 40.5
10.5 10 0.15 0.44 0.11 47.0 235 c0.02 0.039 0.231 8.60 43.0
Permit Limit 0.19 0.021 0.28 - 11.3 0.19 0.021 0.28 - 11.3
aCalculationsare based on a flow rate of 600,000 gpd.
bSamplewas allowed to settle for several days, but was not filtered.

Table V. Anodizing Wastewater Treatability (Test 3)

Metals Concentration in the Supernatant
(Filtered Sample)
Test Neutralization FeCI, Na$ Final pH of cu Ni AI AI
Reagent Added Dosage (mg/L) Dosage (mg/L) Treated Waste (mg/L) (mg/L) (mg/L) (lb/d)a
Raw - - - 2.0 0.64 0.16 267 -
1 Lime 0 0 8.0 co.01 <0.01 0.90 4.5
1 Lime 0 0 9.0 co.01 <0.01 7.4 37
26 Lime 0 10 8.0 <0.01 <0.01 1.24 6.2
26 Lime 0 10 9.0 co.01 co.01 5.65 28.2
3c Lime 0 10 8.0 co.01 <0.01 0.66 3.3
3= Lime 0 10 9.0 co.01 co.01 5.43 27.1
4d Lime 10 10 8.0 0.m e 0.02.9 5.35e --.-
3fi ne
4d Lime 10 10 9.0 <0.01 0.02 7.56 37.8
Permit Limit 0.021 0.28 - 11.3
_____

a Based upon a flowrate of 0.6 mgd.

bNa$ added after lime addition.
CNa,S added after lime addition and solids separation.
dNa,S and FeCI, added after lime addition and solids separation.
eSettledbut not filtered.
-~

the lower values (7.5 and 8.1). Thus,
the data collected for the second set of
tests showed that the optimum pH for
precipitation of aluminum was below
8.0 while the optimum pH for precipi-
tation of nickel was 9.2 and higher
making two-stage metal precipitation
necessary. All samples tested (filtered
and unfiltered) exceeded the permit
limit for copper (0.021 m a ) ; how-
ever, the concentration of copper in the
filtered samples (0.037 m g b ) was
much less than the unfiltered samples
(0.18 to 0.19 mgb). Filtration of the
sample was therefore found to be
effective for copper removal.
Test 3
A third set of tests was performed to
compare hydroxide precipitation, sul-
fide precipitation, and iron coprecipita-

FEBRUARY 1992 71
Table VI. Anodizing Waste Treatability Study (Test &Effects of Ammonia on shown in Table V. All samples were
Metal Precipitation) filtered prior to analysis. The data
indicate that precipitation, clarification
pH after Sludge Supernatant Analysis of
Initial NH, Lime Volume Filtered Sample (mo/L)
and filtration were effective for remov-
Test# pH (mg/L)a Addition (mU100OmL) AI Ni cu ing copper and nickel to concentrations ~

- - below the permit limits. This was

Raw 3.4 0 163 0.06 0.18
1 3.4 0 7.2 250 0.08 <0.02 c0.02 observed at both pH values tested (8.0 I
2 3.4 0 8.4 220 1.44 10.02 <0.02 and 9.0) and using only lime, lime and
3 3.4 0 9.2 21 0 10.4 c0.02 10.02 sodium sulfide, and the combination of _____
4 3.4 19 7.3 150 0.10 <0.02 c0.02 the three reagents. The data for alumi-
5 3.4 19 8.4 300 1.73 <0.02 <0.02 num showed that compliance was
6 3.4 19 9.0 330 8.55 <0.02 <0.02
7 3.4 57 7.2 300 0.78 c0.02 <0.02 achieved at a pH of 8.0, but not at a pH
8 3.4 57 8.4 220 1.82 <0.02 c0.02 of 9.0. This was also observed for all
9 3.4 57 9.2 220 9.08 c0.02 <0.02 three combinations of reagents. This
Permit Limitb 2.26 0.28 0.021 set of tests showed precipitation of
aluminum to be more effective at a pH
a If ammoniawas added it was added prior to pH adjustment. of 8.0 and precipitation of nickel and
Permit limits based on an average flowrate of 0.6 mgd.
copper to be effective at the two pH
values tested.
Table VII. Daily Analysis of Effluent from Neutralization Basin (Test 5)
Test 4
Supernatant Analysis In the second set of tests, all the
Not Filtered Filtered
AI Ni Cu TSS NH, AI Ni cu samples tested had copper concentra-
tions above the permit limits; however,
this was not observed in the first and
2.9 130.00 0.04 0.16 <5 2.4
3.1 109.00 0.03 0.13 <5 2.0 third set of tests. It was suspected that
5.0 4.74 co.01 0.05 <5 2.2 the high copper concentrations could
5.1 37.50 0.04 0.12 c5 2.6 have been caused by copper complex-
5.6 0.21 0.05 0.05 <5 3.9 ing with a m m ~ n i a .To
~ test this hy-
6.0 0.21 co.01 <0.02 c5 2.4
6.0 0.76 0.03 <0.02 <5 1.7 pothesis, a fourth set of tests was
6.2 0.38 0.03 <0.02 <5 3.7 conducted. The results of these tests
6.2 0.39 co.01 c0.02 c5 1.6 are summarized in Table VI. The tests
6.3 1.96 0.41 <0.02 25 28.0 were conducted at three different con-
6.5 1.34 0.04 c0.02 c5 2.4 centrations of ammonia (0, 19, 57
6.5 3.06 <0.01 0.14 <5 1.9
6.5 0.39 0.01 <0.02 <5 2.6 mg/L) and three different final pH
6.5 0.71 0.53 c0.02 <5 34.0 targets (7.0, 8.0 and 9.0). The superna-
6.5 1.18 0.03 <0.02 <5 1.8 tant analysis of these tests showed that,
6.6 0.53 0.02 c0.02 c5 1.1 irrespective of ammonia concentration,
6.8 5.30 0.02 <0.02 14 2.5
6.8 0.66 0.04 c0.02 c5 2.6 copper was reduced from an initial
6.9 0.29 0.03 <0.02 <5 2.0 concentration of 0.18 mg/L to a con-
7.0 3.25 0.03 c0.02 10 2.2 centration below the detection limit
7.0 0.31 0.02 <0.02 <5 2.2 (0.020 mg/L).
7.0 0.41 0.10 c0.02 c5 2.7 These results suggest that the higher
7.3 0.64 0.04 c0.02 <5 2.1
7.4 0.24 <0.01 c0.02 <5 2.4 concentrationsof copper observed in the
7.4 0.30 0.01 <0.02 <5 1.9 treated wastewater used for the second
7.5 0.50 0.01 c0.02 <5 2.4 tests may not have been caused by
7.5 0.84 co.01 <0.02 <5 6.0 cnmplexztion with mmmia. Further-
7.5 0.86 <0.01 <0.02 c5 0.8
7.7 0.38 <0.01 <0.02 <5 1.4 more, the removal of the other metals,
7.8 0.90 0.01 c0.02 <5 2.5 aluminum and nickel, was consistent
with the observations made in the
~

7.8 0.80 <0.01 <0.02 <5 3.2

8.0 3.71 co.01 <0.02 <5 2.1 previous tests. Aluminum was removed
8.4 0.51 <0.01 c0.02 c5 3.2 to below the equivalent permit concen-
8.8 21.40 <0.01 c0.02 29 1.4
9.0 17.10 <0.01 <0.02 23 2.0 tration of 2.26 mg/L at pH values of 7.0
9.2 53.80 co.01 <0.02 81 1.2 and 8.0; however, at a pH of 9.0,
9.2 61.40 <0.01 c0.02 5 1.1 aluminum was found to be above the
9.4 78.10 <0.01 <0.02 47 I .5 permit limit. Nickel was removed to a
Permit concentration below the permit limit at
Limit 2.26 0.28 0.021 - - all pH values and ammonia concentra-
tions that were tested. These observa-
tions indicated that ammonia was proba-
tion. The supernatant metal concentra- lime, sodium sulfide, ferric chloride, or bly not affecting the removal of metals
tions for the jar tests that used either a combination of these reagents are by hydroxide precipitation.

73 hAETdl ClhllCUlhlC
 ,
~"IIxaIII"IIIK"
- - S
Anodizing ~
Waste
Bash
Backwash
4
L Decant
Filter
Press
Fig. 1. Process flow diagram for anodizing wastewater treatment.
Test 5
A fifth set of tests was pedormed to
evaluate the variability of the precipita-
tion process and to determine whether
a filter would be required for polishing
of the clarifier effluent. To perform the
test, the effluent of the existing waste-
water neutralization system was col-
lected twice a day for 19 days. After
collection, the sample was allowed to
settle for approximately 60 minutes in
a four-liter graduated cylinder. After
settling, the sludge volume was re-
corded and the supematant decanted
and analyzed for the three metals
(aliiminiim, nickel and copper), pE,
ammonia, and TSS.
The results from the fifth set of tests
are summarized in the Table VII. To
facilitate analysis of the data, the
results summarized in Table VI1 are
reported with respect to pH. It is
apparent that when the pH of the
treated wastewater was between 7.0
and 8.0, nickel and copper were within
*their permit limits and aluminum was
within the equivalent permit concentra-
tions (average) of 2.26 mg/L, except on
two occasions. On these two occasions,
aluminum concentrations were lower
FEBRUARY 1992
Flocculator
Two-Stage
Neutralizntion
,
than the equivalent maximum limit of
4.52 m a . For one of the two excep-
tions, the sample was filtered and the
dissolved aluminum was found to be
within the average permit level. This
confirmed previous results that showed
that most of the aluminum present at a
pH value of 8.0 or less was in the
particulate form.
Samples were filtered and analyzed
for aluminum to evaluate the relation-
ship between total and dissolved alu-
minum. As listed in Table VII, the
aluminum concentration of the filtered
samples that had pH values from
7.i)-8.0 varied from 0.i24.53 mg/L.
The maximum permit limit of 22.6
lb/day meant that the aluminum con-
centration could not be higher than
4.52 mg/L. The difference between the
maximum observed soluble aluminum
concentration (0.53 mg/L), and the
permit limit was 3.99 mg/L. This
concentration represented the maxi-
mum allowable particulate aluminum
concentration. To determine a maxi-
mum allowable TSS concentration, an
analysis of the sludge was performed
to develop a ratio of aluminum to TSS,
This analysis yielded a 23% aluminum
to TSS ratio. Therefore, the maximum
allowable TSS concentration was
found to be 17.2 mg/L.
Summary
The five tests show that the adjust-
ment of pH with lime to values
between 7.0 and 8.0 was optimum for
the removal of aluminum. Lime was
observed to produce precipitate that
settles effectively. It was also con-
cluded that TSS concentrations over 17
mg/L would cause a violation of the
permit limits.
Most of the tests demonstrated that
precipitation of copper and nickel at
pH values between 7.0 and 8.0 pro-
duced an effluent within the regulatory
limits for these metals. One set of data
(test 2) indicated an increased nickel
removal at higher pH values (9.2 and
10.5). For this set of data, optimum
aluminum removal was obtained at a
pH of 7.5. For this reason, a two-stage
metal precipitation process was shown
to be necessary for the test 2 sample.
Therefore, a two-stage precipitation
system was considered to be advanta-
geous for metal precipitation.
The data showed that even after
73
filtering, one set of samples had copper
values that exceeded the permit limit.
The failure of these samples to meet the
limit could have been caosed by other
factors including the presence of other
chemical complexes such as phosphates
or chelating agents or insufficient reac-
tion time. These factors were not inves-
tigated due to time constraints.
CONCEPTUAL DESIGN OF AN
ANODIZING WASTE
TREATMENT SYSTEM
Based on the information from the
anodizing wastewater characterization
and treatability studies, a treatment
process utilizing hydroxide precipita-
tion was recommended. Figure 1
shows a schematic of the proposed
treatment process. The process consists
of equalization, neutralization, clarifi-
cation, pH adjustment and filtration.
Sludge generated is to be thickened
and dewatered.
EQUALIZATION
The basis of the design of the
equalization basin was to provide for
flow storage and concentration equali-
zation. The flow attenuation needed for
stormwater runoff control was a vol-
ume of 190,000 gallons. Additional
volume of 90,000 gallons was neces-
sary for equalization of concentrated
anodizing tank dumps. Thus, a volume
of 280,000 gallons was provided for
storage and equalization.
NEUTRALIZATION
The treatability test results show that
the metal precipitation process was
sensitive to pH. To ensure that the
proper pH conditions are obtained, a
two-step neutralization system was
recommended. In the first step, the pH
was raised to approximateiy 6.0 using
either lime or the filter wash. The
second neutralization step was de-
signed to increase the pH to 7.5 using
lime only. The mixing times for the
two tanks were 20 and 12 minutes,
respectively. These times were selected
to ensure that lime would dissolve
completely and to provide time for the
precipitation reactions to occur.
The neutralization system was de-
signed to incorporate two-stage metal
precipitation. For two-stage metal pre-
74
cipitation, the first neutralization tank
would raise the pH to 6.0 and the
second would raise the pH to 9.0.
Using this scenario, the clarifier would
remove the solids generated by the first
stage and the filter would remove the
solids produced in the second stage.
CLARIFICATION
Based upon TSS data, the clarifier
feed TSS concentration was estimated
to be 800 mg/L. Settling tests per-
formed on the precipitate determined
that a clarifier designed for 800 gpd/ft2.
would be adequate for both hydraulic
loading and solids loading. A floccula-
tion type clarifier with a diameter of 40
ft. was selected.
For two-stage metal precipitation,
the clarifier operates at a pH of 9.0. All
the treatability test data collected at pH
values of 9.0 or less showed that most
of the aluminum initially present was
removed. For example, test 1 had an
initial aluminum concentration of 95
mg/L and a supematant aluminum
concentration of 6.9 m a ; therefore,
most of the sludge produced in the
two-stage metal precipitation process
will be generated in the clarifier.
FINAL pH ADJUSTMENT
After clarification, the wastewater
flows to a final pH adjustment tank.
For the two-stage metal precipitation
process, the neutralization/clarification
process operates at a pH of 9.0, and the
filtration process operates at a pH of
7.5. To lower the pH from 9.0 to 7.5, a
pH-adjustment step with sulfuric acid
additian facilities was placed between
the clarifier and the filter.
POLISHING FILTER
A polishing filter was designed to
remove the residual solids, thereby
reducing the metal concentration of
the effluent. In the two-stage metal
precipitation, an aluminum precipitate
is generated when the pH is lowered
from 9.0 to 7.5. The precipitate must
be removed by filtration. Analyses of
the treatability test data show the
maximum aluminum concentration at
a pH of 9.0 or less was 17.1 mg/L.
Since most of the aluminum is precipi-
tated as aluminum hydroxide, the
resultant TSS concentration is 49
mg/L. A value of 50 mg/L was used in
specifying the TSS loading for the
filter.
SLUDGE DEWATERING
SYSTEM ~
A 32,900-gallon sludge holding tank
was designed for this system to accom- I
modate the sludge generated during an
average day. The tank was specified to _____
be equipped with decant pipes at
various heights to allow for the gravity
thickening.
The recommended dewatering sys-
tem also included a 150 ft2 plate-and-
frame, recessed-chamber filter press.
The press was designed to dewater
6,700 pounds per day of sludge (based
on dry weight) by operating at 3.2
cycles per day. The solids content of
the discharged sludge was predicted to
average 20%, which is typical for
sludges of this type.
CONCLUSIONS
Treatability tests performed on the
anodizing wastewaters demonstrated
that hydroxide precipitation was a very
effective treatment process for removal
of aluminum, copper, nickel and zinc.
The tests showed that water-quality-
based limits for these metals could be
achieved by single-stage precipitation
consisting of pH adjustment, clarifi-
cation and filtration.
The optimum pH range for precipi-
tation was 7.0 to 8.0. Because one set of
tests showed optimum metal perform-
ance at pH values of 7.0 and 9.0,
two-stage metal precipitation capabil-
ities were incorporated into the design.
Under this arrangement, the first stage
would consist of pH adjustment to 9.0
followed by clarification, and the sec-
ond stage would consist of pH adjust-
ment to 7.5 followed by filtration.
MF
References
1. Comwell, D.A. “Aluminum Production from ~
Aluminum Etching Wastes,‘ Proceedings of
the 37th Annual Purdue Industrial Waste
Conference, 1983
2. Ward, R.C. “Aluminum Anodizing Was-
tewater Treatment and Reuse,” Proceedings
of the 36th Annual Purdue Industrial Waste
Conference, 1982
3. Chu, TJ., et al., “Removal of Complex
Copper-Ammonia Ions from Aqueous
Water with Fly Ash,” Proceedings of the 35fh
Annual Purdue Industrial Waste Conference,
1982
METAL FINISHING