26524.

PDF was P00695 TREATMENT OF ALUMINUM-FINISHING

WASTEWATERS AND SLUDGES

F. Michael Saunders', Mesut Sezgin2 , and Rodney G. Kutz 3

School of C i v i l Engineering
Georgia I n s t i t u t e of Technology
A t l a n t a , GA 30332

A comprehensive s t u d y of wastewaters and s l u d g e s produced i n t h e alumi-

num f i n i s h i n g i n d u s t r y w a s conducted. Emphasis w a s placed on t h o s e wastes
c o n t a i n i n g major q u a n t i t i e s of aqueous aluminum from p a i n t i n g , e t c h i n g and
a n o d i z i n g p r o c e s s e s a t major aluminum f i n i s h i n g p l a n t s . Chemical c h a r a c t e r -
i z a t i o n of n e u t r a l i z e d wastewaters i n c l u d e d measurement of s o l i d s , aluminum,
o r g a n i c carbon, a l k a l i n i t y and p r i o r i t y - p o l l u t a n t metals.

Wastewaters were examined w i t h r e s p e c t t o t h i c k e n i n g , dewatering,

g r a v i t y d r a i n i n g and p o l y e l e c t r o l y t e c o n d i t i o n i n g t r e a t m e n t p r o c e s s e s .
P o l y e l e c t r o l y t e - c o n d i t i o n i n g was shown t o be r e q u i r e d f o r s e t t l i n g and
t h i c k e n i n g of aluminum-finishing s l u d g e s . Improvements i n dewatering and
g r a v i t y d r a i n i n g p r o p e r t i e s w i t h p o l y e l e c t r o l y t e c o n d i t i o n i n g are p r e s e n t e d .
The impact of high-temperature n e u t r a l i z a t i o n on s l u d g e p r o p e r t i e s i s
discussed.

~-

1 Associate Professor
2 P o s t d o c t o r a l Fellow
3 Graduate Research A s s i s t a n t ; c u r r e n t l y Environmental Engineer, Southwire
Co. Inc., C a r r o l l t o n GA.
 Introduction

The use of aluminum in the building and construction, transportation,

electrical, and container and packaging industries continues to expand as
the demand for durable light-weight metal components increases. Over 6.5
x 106 Mg (metric ton) of aluminum are currently produced as mill products
for domestic consumption in the United States with 23% produced as extruded
parts, 42% as sheet, plate and foil, 7% as rod, bar and wire, and 28% as
castings, impacts and powder products (1). These mill products are pro-
duced in over 600 production facilities using a wide variety of surface
treatment and finishing processes.

Aluminum finishing processes include numerous physical and chemical

treatments used to improve surface appearance, durability, and adhesion
properties. Physical surface treatments, such as buffing, brushing or mill-
ing, produce solid wastes and oil-bound suspensions which can be effectively
reclaimed or treated. Chemical surface treatments however result in the
.productionof large volumes of wastewaters which are more difficult to
treat. Chemical finishing processes conventionally utilized by the aluminum
industry include chemical etching, electrochemical etching, painting, chemi-
cal milling, dyeing and anodizing. The wastewaters associated with these
processes generally consist of large volumes of rinse waters and smaller
volumes of chemical spills and spent or contaminated finishing solutions and
suspensions. Dissolved aluminum is the primary contaminant in these waste-
waters and generally dictates subsequent wastewater treatment systems. These
treatment systems conventionally include wastewater neutralization, clarifi-
catiqn and sludge dewatering processes.
The objective of the research presented in this study was to examine
wastewaters and sludges produced by extrusion/anodizing plants. The waste-
waters were specifically to be characterized with respect to chemical char-
acteristics properties and thickening and dewatering properties.

Perspective of Extrusion/Anodizing Industry

Aluminum Finishing

Anodizing is used as a finishing process for extruded architectural and

structural aluminum because of the durable, decorative, and corrosion-resist-
. ance finish applied. Numerous alloys of aluminum are anodized, depending on
surface and structural properties desired. The 6000 series alloys, however,
are most typically employed (1). These alloys contain Cr, Cu, Fe, Mg, Mn,
Si, Ti and Zn at levels ranging from 0 . 0 5 to 2% and may also contain B, Bi
and Pb (2). Regardless of specific alloy used within the 6000 series, alu-
minum content is typically greater than 9 4 % (2).

The use of anodizing to finish aluminum extrusions requires that numer-

ous preliminary finishing steps be employed. These steps are performed in
a series of batch tanks into which racks of extruded aluminum materials are
sequentially immersed. A n initial step is a cleaning step to remove surface
grease and oil, as indicated in Table I. A continuous-flow, counter-current
rinse typically follows the cleaning step, as well as all other subsequent
finishing steps, to remove residual cleaning solution from the aluminum
material.

A chemical etch typically follows the cleaning step and is used to re-
move residual surface oxides prior to anodizing. The chemical etching step

1032
 is an agressive surface treatment using hot caustic soda and results in a
higher removal of aluminum and aluminum-alloy components than all other
finishing steps combined. Following immersion in the etch tank, the extrud-
ed aluminum surface is covered with a thin film (i.e. a "smut" film) of
numerous precipitated alloy metals which are removed i n a desmut step. The
desmut solution is typically HNO (see Table 1) which dissolves the smut
3
film leaving a bare aluminum sur ace for anodizing.

Table I. Aluminum Finishing Steps Used In Anodizing (1,3)

Finishing Purpose of Finishing Step Typical Finishing Tank

-
Clean Remove Surface Contaminants Alkaline Detergents
Y
Temp = 40-60°C

n Etch Remove Surface Oxides Caustic Soda = 2-10%

- Sequestrant = 0.5-5%
Temp = 40-60°C

i Desmut Remove Smudge Film Nitric Acid = 5-30%

se Bright Dip Enhance Luster (Optional) Phosphoric Acid = 70-80%

- Nitric Acid = 3%
Copper = 0.1%
Ammonia = 0.1%

Anodize Provide Protective and Decorative Clear Coat -H2S04:

Surface Coat Sulfuric Acid = 15-20%
Temp = 20-3OoC
Hard Coat -H2S04:
Sulfuric Acid =I 0.3-0.52
Organic Acids = 0.5-15%
Temp = 15-25°C

Dye Apply Surface Color (Optional) Proprietary Dyes

d
t- Seal Form Aluminum-Oxide-Mono- Nickel Acetate = 0.1-0.5%
n Hydrate to Seal Surface Oxide pH 5-6.5
Y
Temp = 40-60°C

Numerous anodizing processes are available for use depending upon the
surface quality, durability and appearance desired (3). Two anodizing
- finishes are, however, typically utilized in the anodizing of architectural
and structural aluminum materials. These are clear-coat sulfuric acid
anodizing and hard-coat sulfuric acid anodizing. Clear-coat finishes are
e clear, durable, matte finishes which do not change the color of aluminum.
.t Clear-coat anodizing is performed in 15 to 20% H2SO4 with the extruded alu-
minum material serving as the anode during the passage of current through
the tank. A hard-coat finish is bronze to black in color and is applied in
a manner similar to clear-coat anodizing using lower concentrations of H2S04
and in the presence of one or more of organic acids (e.g. oxalic acid,
sulfophthallic acid, sulfanilic acid). Acid dissolution of aluminum occurs
1 during clear-coat anodizing to levels of 10-20 g/1 (3). However, aluminum

1033
levels greater than 0.6 to 1 g/l have a negative impact on hard-coat finish-
es and aluminum must be continuously removed from the anodizing solution
with an in-line cation exchange resin.

Following rinsing, anodized aluminum is sealed using a hot-water solu-

tion or with a dilute solution of nickel acetate. As indicated in Table I,
two optional finishing steps may also be used in the process of anodizing
aluminum materials. A bright-dip process is used to improve metal luster
while a dyeing step is used to color the anodized aluminum surface.

i
c;
Treatment of Aluminum Finishing Wastewaters It
H
Wastewaters from aluminum finishing processes contain a variety of in- m
! E
organic and organic contaminants originating in finishing chemicals and con-
taminants from the aluminum alloys being treated. These contaminants are e
discharged to a wastewater collection system in rinse water discharges and e
dragout and spills of finishing solutions. Spent finishing solutions and
blowdown from finishing processes constitute a major source of the total
mass of discharged wastewater contaminants, especially aluminum.

Wastewater Characteristics. Water consumption rates for aluminum ex-

- .plants are high for metal finishing industries, e.g. 25-
trusion/anodizing
70 m3/kg aluminum finished ( 4 ) . - High water use rates are, in part due to
heavy liquid films dragged out of viscous process tanks, such as alkaline
etch tanks, and the resulting need for large volumes of water to remove
these films. Racking techniques for aluminum products being finished, in
addition, add to increased water use. Extruded aluminum parts are frequent-
ly long, thin sections which are densely racked. Sagging of thin aluminum
strips is minimized with supports but is not eliminated. Aluminum parts
must also be placed on racks to minimize gas pocketing. Both of these rack-
ing procedures result in increased dragout of finishing solutions, increas-
ing rinse water requirements.

High dragout rates result in high levels of waste aluminum and other
contaminants in rinse water effluents. The high levels of aluminum (1-75
g/l) contained in spent etch and anodize wastes, which are frequently used
to neutralize combined plant wastewaters, contribute significantly to waste- e
water aluminum content. A survey of aluminum finishing plants indicated ii
that 0.9 to 2.4% of the mass of aluminum extruded and finished in extrusion/ di
anodizing plants was dissolved and discharged to waste (1). UJ
WJ
Wastewater Treatment Systems. In conjunction with the research pre- t:
sented herein, The Aluminum Association, Inc. conducted a survey of 37 in- at
dustrial aluminum finishing plants, of which 22 were extrusion/anodizing r:
plants (1). The results of the survey indicated that the conventional flow w7

scheme for treatment of combined rinsewaters, concentrated spills and spent wl

process solutions and suspensions typically included (i) pH neutralization P'

and precipitation of aluminum, (ii) coagulant (polyelectrolyte) addition s;
and (iii) gravity clarification. Clarified effluents are typically dis- Wl
charged to a receiving stream or domestic sewerage system.

Regarding sludge treatment and disposal systems, the average sludge

(dry solids) production rate for the 22 plants was 1.6 Mg/d, with a range
of values of 1.4 x to 5 . 8 Mg/d. Half of the plants disposed of sus-
pended solids collected during gravity sedimentation without further treat- P'
ment. Gravity clarlfier iir;derflcw s u s p e n s i m s had an average sgspended ar
solids concentration of 22 g/1 with a range of 0.1 to 50 g/l. C!'
P"
 Of the plants using slud e dewatering systems, vacuum and pressure
filtration and sand drying bess were used predominantly, although a belt
filter and a centrifuge were used at two plants. Solids content for me-
chanically dewatered sludge solids ranged from 1-20% (dry solids) and aver-
aged 16.5%. Disposal of thickened and dewatered sludges included (i)
placement in domestic and segregated landfill sites, (ii) discharge to la-
goons, (iii) blending with soil and, (iv) stockpiling on plant site for sub-
sequent recovery.

A primary concern of the majority of the industries was the increasing

difficulty associated with disposal of the typically gelatinous aluminum
hydroxide sludges with low solids content. To bring aluminum sludge dis-
posal into proper perspective, if aluminum is assumed to be the primary
metallic component of an anodizing wastewater sludge and it is precipitated
as Al(OH)3, a dewatered sludge at 16.5% dry solids content (i.e., the aver-
age survey value (1)) represents 16.9 kg of wet sludge for each kg of
aluminum precipitated. Furthermore, if 0.9 to 2.4% of the aluminum finish-
ed is dissolved during finishing (l), a typical extruxion/anodizing plant
will generate 0.15 to 0.4 kg of wet dewatered sludge for each kg of aluminum
finished. If dewatered solids content is less than 16.5%, the quantity of
dewatered sludge available for disposal will approach anodizing production
levels. The extrusion/anodize industry is therefore faced with the dis-
posal of a waste sludge which may equal 40% of the mass of its finished
extruded product.

The research reported herein is initial research focused on this sludge

disposal problem. The primary objective of the initial work was to chem-
ically characterize extrusion-anodizing wastewaters and to establish base-
line data with regard to sludge thickening and dewatering properties.

Experimental Methods and Materials

Participating Plants

To examine actual anodizing wastewater suspensions and sludges, three

extrusion/anodizing plants were identified for participation in the project
in conjunction with The Aluminum Association, Inc. The three plants were
designated Al, A2 and A3 and are all located in the southern region of the
United States. As indicated in Table 11, a variety of finishing processes
were employed at the plants. At plant Al, slightly more than half of the
total aluminum production is anodized using clear- and hard-coat finishes
and the associated finishing processes of dyeing and bright dipping. The,
remaining portion of the aluminum production is painted. Painting waste-
waters are treated for chromate reduction and combined with anodizing waste-
waters for subsequent neutralization, gravity sedimentation and discharge.
Plants A2 and A3 do not paint aluminum but use anodizing as the primary
surface finishing process. Both plant A2 and A3 use clear-coat anodizing
while plant A3 also uses a hard-coat anodizing process.

Wastewater Sampling Procedures

Grab samples of wastewater were collected in volumes of 0.4-1.2 m3 at

plant sites during periods of typical plant operation by.plant personnel
and shipped directly to the laboratory for analysis. The wastewaters were
collected following neutralization, immediately prior to the addition of
polyelectrolyte conditioners, and placed in lined O.2-m3 barrels for direct

1335
shipment. Shipments from the individual plants were staggered to allow for
immediate analysis of each wastewater upon receipt. Control testing pro-
cedures were utilized to assure that wastewater characteristics remained
constant during the period of laboratory analysis (1).

Table 11. Participatinp Extrusion/Anodize Plants

A1 Production Finishing Waste Treatment

Plant Rate Processes Processes

A1 9 x 105 kg/mo Anodize: Wastewater

Hard Chromate Reduction
Clear Lime Precipitation
Dyeing Neutralization
Bright Dip Sedimentation
Painting : Sludge:
Conversion- Lagoon
Coating

A2 3.6 x 105 kg/mo Anodize: Wastewater:

Clear Neutralization
Dyeing Sedimentation
Bright Dip Sludge:
Vacuum Filtration
Landfill

A3 6.8 x 105 kg/mo Anodize : Wastewater:

Clear Neutralization
Hard Sedimentation
Sludge
Pressure Filtration
Land

Chemical Characterization

Immediately upon receipt of a wastewater, representative samples were

collected and immediately analyzed for pH, temperature, total, dissolved and
suspended solids, filtrable and total alkalinity, filtrable and non-filtrable
aluminum and filtrable inorganic (SIC) and organic (SOC) carbon. Samples,
in addition, were collected and prepared for detailed metal analysis for
major and trace metals. Procedures for sample preservation, metal analysis,
as well as for the above conventional analyses were as presented in Standard
Methods (5).

Thickening and Dewatering Procedures

Thickening data were collected in 6-cm stirred cylinders at an initial

sludge depth of 36 cm (1). A stirrer rotational speed of 1 rpm was used in
all experiments. Data were also collected in 9- and 15-cm stirred cylinders
at initial sludge depths of 36 and 100 cm. Sludge dewatering characteristics
were determined using specific resistance measurements. Standard procedures
ssing a vacuurn-assisted Buchner funnel apparatus were fd.lnwed (6).

Sludge drainability studies were conducted on conditioned and

 unconditioned sludges using eight acrylic sand beds. The diameter of the
cylindrical beds was 8.9 cm and each bed contained layers of gravel and
sand (1). Drainable water was collected and measured in cylindrical columns
connected to the beds by vinyl tubing. A 1-liter volume of sludge was
routinely applied to the sand beds and filtrate volume was recorded with
time. The beds and filtrate collection cylinders were covered and inter-
- connected with vinyl tubing to minimize evaporational losses.

- Sludge Conditioning. Polyelectrolyte conditioners were investigated

to determine their effects on sludge thickening, dewatering and draining
- characteristics. Four polyelectrolytes were used, including three poly-
electrolytes used at the participating plants and a control polyelectrolyte,
as indicated in Table 111. All polymers were anionic polyacrylamide poly-
)n electrolytes. Sludge conditioning was routinely performed in a 3.2 liter
In baffled cylindrical mixing chamber which had a diameter of 12.7 cm (1). A
standard sludge volume of 1 liter was mixed in the chamber with a single-
blade (2.6 cm x 7.8 cm) stirrer operated at 200 rpm for 60 s. When examin-
ing the effects of polymer conditioning on sludge characteristics, both
unconditioned and conditioner sludge samples were treated in the above man-
ner, without and with polymer addition, respectively.

Table 111. Polyelectrolyte Conditioners

Polyelectrolyte Charge Mol. Wt . Plant

6
Caraflok 9 1 M a Anionic 9 x 10 Control
~ ~ - 1 9 0 ~ Anionic (Medium) A1

on Purifloc A23' Anionic > lo6 A3

- Separan AP 273" Anionic 3 x lo6 A2

a. Carus Chemical Co.; LaSalle IL

b. Amchem Products Inc.; Ambler PA
c. Dow Chemical Co.; Midland MI
nd
ble
Results

s,
rd Wastewater Chemical Characteristics

General. The characteristics of wastewater samples collected follow-

I ing neutralization at the plant sites are presented in Table IV. Two
samples were collected at plants A2 and A3. The two samples from plant A2
were taken during a period of routine week-day plant operation when only
1 I rinse waters and spills were being treated (i.e. sample 242-79) and during
n a weekend period when finishing operations were not in use (i.e. sample
rs 319-79). During this latter period, only spent finishing solutions and
ics suspensions (e.g. spent etch and spent anodize solutions) were being dis-
es charged to the treatment system. All other samples were taken during week-
day periods when routine finishing operations were in use since neither
plant A1 or A3 used a segregated treatment scheme similar to that at plant
A2.

i
1027
 Table IV. Characteristics of Anodizing Aluminum Wastewaters from exam
Neutralization Basin Effluents as ii
the
cadm
antii
Plant A1 A2 A3 incl
Proc
Sample Identification 21-80 242-79 319-79 161-79 201-79

Solids tot=
Total, g/l 9.04 1.72 108.6 9.78 7.23 in II
Volatility, % 15.6 14.5 12.4 - 10.9 antii
were
Suspended, g/1 3.21 0.41 57.26 4.35 1.84
Volatility, % 25.5 28.9 16.1 - 21.7

Dissolved, g/l 6.04 1.34 52.43 5.43 5.39

Volatility, % 10.3 12.7 8.0 - 7.2 c _

pH 7.0 8.0 7.0 7.2 10.5

Alkalinity, mg CaC03/1
Total 311 159 2800 535 1134
Filtrable 75 74 120 54 78

Aluminum
Filtrable, mg/l 0.4 3.9 2.5 118
Non-Filtrable, mg/l 950 116.1 15,600 862
Non-Filtrable, g/kgISS* 397 398 324 598
Carbon
SOC, mg/I 15.7 4 81.5 93
SIC, mg/l 11.8 19 0

*ISS = Inert Suspended Solids

As indicated in Table IV, the wastewater samples were neutral or

slightly alkaline in pH except sample A3-201-79 which had a pH of 10.5.
Filtrable alkalinity values were typically low indicating that most of the
suspension alkalinity was due to the precipitated aluminum solids. Sus-
pended solids ranged from 1.84 to 4.35 g/1 for plants A1 and A3. While the
dilute rinse wastewater at plant A2 (i.e., A2-242-79) contained a low level
of suspended solids, the wastewater resulting from treatment of concentrat-
ed finishing solutions (i.e., A2-319-79) contained an extremely high level
of suspended solids due to the treatment of high levels of aluminum contain-
ed in spent finishing solution. Total dissolved solids varied from 1.34 to
6.04 g/1 for all samples, except sample A2-319-79 which contained 52.43 g/l.

Filtrable aluminum concentrations were low for suspensions at or near

neutral pH and the majority of wastewater aluminum was in suspension as
expected from aluminum solubility data (7). The inert suspended solids in
the wastewater suspensions at or near neutral pH contained 32-40% aluminum.
These values were in agreement with the theoretical composition of precipi-
tated aluminum hydroxide (Al(0H) ), i.e., 34.6% aluminum. The sludge sample
at an elevated pH value, i.e., Aj-201-79, contained 59.8% aluminum based on
inert suspended solids and the chemical form was apparently altered from
that of A1(OH)3.
Trace Metal Composition. The neutralized wastewater samples were

1038
examined with respect to toxic metals. Thirteen priority-pollutant metals,
as identified by the U. S. Environmental Protection Agency, were chosen as
the metals of concern and were silver, Ag; arsenic, As; beryllium, Be;
cadmium, Cd; chromium, Cr; copper, Cu; mercury, Hg; nickel, Ni; lead, Pb;
antimony, Sb; selenium, Se; thallium, Ti; and zinc, Zn. Metals examined
included those used to examine the toxicity of sludges in the EPA Extraction
Procedure (8), i.e. Ag, As, Cd, Cr, Hg, Pb and Se.

Metal distribution in dewatered sludges was examined by analysis of

total and dissolved metals following acid digestion (1) and are presented
in Table V as dissolved and suspended metal concentrations. The metal
antimony (Sb) and thallium (Ti) were not detected in any sludge samples and
were not included in the table.

Table V. Trace Metal Composition of Neutralized

Wastewaters at Plants Al, A2 and A3.

Plant A1 A2 A3
Dissolved Suspended Dissolved Suspended Dissolved Suspended
ugll mglkg ugll- mdkg udl ngJc9c

Metals
Ag, Silver - - 49 1.6 - -
As, Arsenic 18 <3 160 <3 54 3

Be, Beryllium - - 1.7 0.2 - -

Cd, Cadmium 5.6 15 1.2 0.9 0.8 1.2

Cr, Chromium 1500 2600 180 21 9 * 89

Cu, Copper 25 140 130 35 48 23

Hg, Mercury - - 28 <0.1 - -

Ni, Nickel 78 115 74 64 260 2200

Pb, Lead 1.4 19 24 24 1 10

Se, Selenium 130 <1 1700 1 38 <1

Zn, Zinc 1500 3000 1400 <26 70 120

. . .

For plant Al, chromium (1500 ug/l) and zinc (1500 Pgfl) were the major
dissolved metals detected. The source of the chromium was attributed to
dichromates contained in paint-line wastewaters which were discharged with
anodizing wastes t o a common neutralization facility at plant Al. Although
dissolved chromium and zinc levels were relatively high, 99.4% of each was
contained in the suspended form in a dewatered sludge with a solids content
of 8.3%, indicating a high degree of metal precipitation. In addition,
with the exception of selenium ( 4 2 % ) , more than approximately 96% of all
metals were contained in the suspended form of the sludge.

1039
 Significant quantities of dissolved selenium (1700 ug/l) were detected
in plant A2 sludge and the selenium may have been attributable to a dyeing
line at the plant. The majority of the selenium was contained in the dis-
solved form (i.e. 87.3%) and was therefore ineffectively removed with the
thickened sludge following neutralization and precipitation. With the
exception of mercury (49.5%), from 82% to 99% of the metals detected were
contained in the suspended form in the wet sludge containing 19.8% solids.

Dissolved metals in plant A3 sludge were relatively low with nickel

being the major trace metal and other metals being at or below 70 ug/l.
With the exception of selenium (78%), the majority (89% to 99.9%) of the
metals were in the suspended form.

In summary, most of the heavy metals in the aliminum-finishing sludges

examined were present in the suspended solids and not dissolved in inter-
stital water. The major trace metals contained in the suspended form of
all sludges were Cr, Cu, Ni, Pb, and Zn. Only sludge from plant A2 con-
tained Hg, which was mostly in the dissolved form. In addition to,Sb and
Ti which were not detected in any samples, Ag, Be, and Hg could virtually
be neglected because they were only detected in sludge from plant A2 in
very low concentrations. While As, Cd, and Se were in all sludge samples,
the amounts present were also low. Sludges from plants A2 and A3 had 20-
fold less Cr than sludge from plant A1 while plant A3 sludge contained
approximately 20 to 35-fold more Ni than other sludges. Finally an overall
assessment of sludge metal content indicated that all trace metals con-
stituted a very small portion of the total sludge suspensions.

Sludge Thickening

Control settling tests were conducted to determine the effects of

settling column diameter (6-15 cm) and sludge height (36-100 cm) on zone
settling velocity data. As indicated in Figure 1, variations in zone
settling velocity data for a single sludge at various column diameters and
initial sludge heights were minimal. All subsequent zone settling data
were therefore collected in 6-cm diameter cylinders with an initial sludge
height of 35 cm.

Unconditioned Wastewaters. Zone settling data for anodizing waste-

waters with neutral or near-neutral pH values are presented in Figure 2.
The data for all suspensions, except A2-319-79, were very similar. Data
for the wastewater from plant A1 and the dilute rinse wastewater from A2
(i.e., A2-21-80) were virtually identical while those for plant A3 were
slightly higher.

A major difference in settling characteristics was apparent for the

two wastewaters collected at plant A2. A t similar suspended solids con-
centrations, the wastewater suspension resulting from neutralization of
concentrated spent finishing solutions and suspensions (i.e., A2-319-79)
settled more effectively than did that collected following routine neutrali-
zation of dilute plant rinse waters (i.e., A2-242-79). The differences in
settling velocities for plant A2 sludges were between one and three orders
of magnitude, over the range of similar suspended solids concentrations.
Neutralization of concentrated finishing solutions containing strong acids
and bases as done at plant A2, would appear to result in the production of
a suspension with greatly improved thickening properties.

Conditioned Wastewaters. Anionic polyelectrolytes typically used at

plants Al, A2 and A3 were used to determine the effects of polyelectrolyte

1040
 1 1 10 100

LUSPENDED SOLIDS CONC, JI

Figure 1. Effects of Column Height and Diameter on Zone Settling Velocftg

I I

Figure 2. Settling Properties of Unconditioned Aluminum-Finishing Sludges

1041
conditionkg on suspension thickening characteristics. To determine an
appropriate polyelectrolyte dose, a series of suspension samples was dosed
with increasing levels of the selected polyelectrolyte and examined to
determine sludge settling velocity. A s indicated in Figure 3, increasing
levels of polyelectrolyte initially resulted in a significant increase in
sludge settling velocity followed by a decrease. Increased polyelectrolyte
addition and resulting agglomeration of sludge particles, in addition to
improvement in sludge settling characteristics, frequently resulted in a
transition from true zone settling to hindered flocculent settling behavior.
Since the prime objective was to monitor effects of polyelectrolyte addition
on wastewater thickening and not clarification characteristics, a poly-
electrolyte dose resulting in the highest zone settling velocity for a
suspension was selected for further testing. Therefore, from the data in
Figure 4, it is apparent that a polyelectrolyte o f 10 mg/l resulted in the
most improved settling characteristics, for the sludge examined. This dose
was then normalized using the suspended solids concentration of the suspen-
sion being tested to a polyelectrolyte dose rate for use in subsequent test-
ing with a broad range of suspended solids concentrations. Similar data were
collected for each wastewater.

Polyelectrolyte conditioning data are presented in Figure 4 for all

plants. When compared with data presented in Figure 2, it is readily appar-
ent that conditioning resulted in significant improvements in all wastewater
samples examined. This is more graphically apparent in Figures 5 and 6 where
data for samples A1-21-80 and A3-161-79 are presented, respectively.

To determine if significant variations occurred in the conditioning

response of the polyelectrolytes, wastewater suspensions were conditioned
with each polyelectrolyte to determine the most effective application rate.
Settling data were then collected using each polyelectrolyte with samples of
a single wastewater suspension. Data for the A2-242-79 wastewater sample
from plant A2 are presented in Figure 7. As previously indicated in Figures
2 and 4 and also shown in Figure 7, polyelectrolyte conditioning of the waste-
water from plant A2 resulted in significant improvements in wastewater thicken-
ing characteristics. Secondly, it is apparent from Figure 7 that there were
no significant differences in the extent of improvement provided by the three
polyelectrolytes examined.

Dewatering Properties

Anodizing wastewater samples from plants A l , A2 and A3 were examined to

determine their dewatering properties with and without polyelectrolyte con-
ditioning.

Unconditioned Suspensions. The dewatering characteristics of anodizing

wastewaters were determined using specific resistance valugs, as indicated in
Table VI. To compare dewatering characteristics, specific resistance data for
a suspended solids concentration of 10 g/l, a commonly achieved concentration
for gravity thickened sludges, are presented. Significant variations occurred
with specific resistance values ranging from 3.6 x 10l1 to 4 . 1 x 1OI2 m/kg
at a suspended solids concentration of 10 g/l. The sludges from plant A2
were both the most difficult (i.e., A2-283-79) and the easiest (i.e. A2-319-
79) sludges to dewater, based on specific resistance values. The sludge pro-
duced by neutralization of concentrated finishing solutions and suspensions
(i.e. A2-319-79), in addition to having improved thickening characteristics
over all other anodizing wastewaters, was apparently one of the easiest
sludges to dewater, It should be noted, however, that the unconditioned
sludge from plant A3 (i.e. 161-79) had specific resistance values which
 100
I I I I 1 I I I

PLANT A2 (242-79)
1 I

-I
SS CONC. - 1.6 dl
-
?.
-

..
)n -
o io 20 30 40 50 60 70 80 90 100

!
SEPARAN AP 273, mdl
.-
!re Figure 3 , Optimum Polyelectrolyte Dose Determination
for Settling of Sludge Sample A2-242-79
1QI I

I-

r
re

10 -

S
te-
ken-
3 1.0 -
e 1s
I-
ee
5
ai0 -
3

d \
5
in
)r
aoi - PLANT
SAMPLE
NO. POLYMER
POLYMER
0056 SYMBOL
I t
)n
red

aooi I I
a1 1 10
>-

Figure 4 . Settling Properties of Conditioned Aluminum-Finishing Sludges

 b

AI

I I I I

1 I I I

i
were similar to those for the concentrated A2 wastewater sample (i.e. A2-
319-79)

Table VI. Specific Resistance, r, of Unconditioned Aluminum Sludges

r r
Specific Resist. Specific Resist.
Plant (at ss = 10 gll) S S Range Range
m/kg all mlkg

A1 19.2 1.3-13.3 20.7-26.9

A2 (283) 41.0 1.3-16.4 41, -52.

A2 (319) 3.6 3.3-79.7 1.8- 4 . 1

A3 3.8 3.4-36.1 2.8-3.5

Conditioned Suspensions. To determine the effects of conditioning on

sludge dewatering characteristics, a series of sludge samples was dosed
with increasing levels of polyelectrolyte and specific resistance values
were determined. Typical results presented in Figure 8 indicate an effec-
tive polyelectrolyte (Separan AP 273) dose of 4.8 g/kg S S . Specific re-
sistance values were then determined for a range of suspended solids con-
centrations using the predetermined effective polyelectrolyte dose. Data
presented in Table VI1 indicate the effective polyelectrolyte doses and
the associated specific resistance values for the suspended solids con-
centrations of the three anodizing sludges.

Table VII. Polymer Conditioning of Aluminum-Finishing Sludges:

Specific Resistance and Dewatered Cake Solids

Polymer Sludge
, Specific Resist. Cake Solids
Plant Type Dose Conc. Uncond, Cond. Uncond. Cond.
- g/kgSS p/1 1011 m/kg m/kg % %

A1 HF-190 4.58 3.3 22.2 3.1 9.4 9.0

A1 91-AP 4.58 3.3 22.2 1.7 9.4 9.1

A2 AP-273 4.8 6.3 42.0 0.9 7.6 8.1

(283)

A2 AP-273 1.05 9.5 3.0 1.2 19.1 17.2

(319)

A3 A 23 0.76 10.5 3.6 2.6 8.2 6.9

Polyelectrolyte conditioning resulted in improved sludge dewatering

characteristics for all sludges. The improvement, however, varied with

1045
 11 SI
WE
WE
irr
CE
re

-3e
dd
i 1.JJ

l
s
fL
Y
Y
f

a 1 I I I
a0 40 W W loo
0)
AP2n.W e

Figure 8. Optimum Polyelectrolyte Determination

for Dewatering of Sample A2-283-79

11 1 I I

PLANT A1 121-801
ss CONC.. pn SYMBOL

0.n

7.8

3 0.6
3
9
5 0.4
2
Y

a2

0. I 1
10 loo 1aK) 1M

DRAINAGE TIME, mln

Figure 9. Gravity Drainage Properties for Sample A1-21-80

sludges. S p e c i f i c r e s i s t a n c e v a l u e s f o r s l u d g e s which had t h e b e t t e r de-
w a t e r i n g p r o p e r t i e s p r i o r t o c o n d i t i o n i n g ( i . e . , A2-319-79 and A3-161-79)
were reduced by f a c t o r s of 2.5 and 1 . 4 , r e s p e c t i v e l y . However, t h e remain-
i n g s l u d g e s which d i d n o t dewater w e l l p r i o r t o c o n d i t i o n i n g , had s i g n i f i -
c a n t l y improved dewatering p r o p e r t i e s f o l l o w i n g c o n d i t i o n i n g . S p e c i f i c
resistance v a l u e s f o r t h e s e s l u d g e s were reduced by f a c t o r s of 7 t o 47 i n -
d i c a t i n g major improvement i n dewatering p o t e n t i a l when u s i n g p o l y e l e c t r o -
l y t e conditioners.

P o l y e l e c t r o l y t e c o n d i t i o n i n g d i d , however, n o t r e s u l t i n any s i g n i f i -
c a n t improvement i n t h e s o l i d s c o n t e n t of t h e f i n a l dewatered cake c o l l e c t -
ed d u r i n g t h e s p e c i f i c r e s i s t a n c e tests. I n a l l cases b u t one ( i . e . , A2-
283-79) cake s o l i d s c o n t e n t d e c r e a s e d f o l l o w i n g p o l y e l e c t r o l y t e c o n d i t i o n i n g .
This r e s u l t e d from a s l i g h t i n c r e a s e i n water r e t e n t i o n by t h e h y d r o p h i l l i c
p o l y e l e c t r o l y t e o r w a s a n anomolous r e s u l t due t o t h e i n c r e a s e d r a t e o f
water removal and r e s u l t i n g i n c r e a s e d p o t e n t i a l f o r t h e cake t o c r a c k p r i o r
t o t h e removal of a l l f r e e and p o r e water.

G r a v i t y Drainage P r o p e r t i e s

.Sludge g r a v i t y d r a i n a g e p r o p e r t i e s were examined t o determine t h e r a t e

of removal of water on sand d r y i n g beds. Small s i m u l a t e d beds were used t o
examine b o t h unconditioned and c o n d i t i o n e d s l u d g e s .

Unconditioned Suspensions. Data p r e s e n t e d i n F i g u r e 9 f o r s l u d g e from

p l a n t A 1 i n d i c a t e t y p i c a l d r a i n a g e p a t t e r n s f o r t h e aluminum-finishing
s l u d g e s examined. An i n i t i a l slow rate of d r a i n a g e preceeded a p e r i o d o f
r a p i d l y i n c r e a s i n g d r a i n a g e which w a s followed by an a b r u p t d e c r e a s e i n
d r a i n a g e rate. A s suspended s o l i d s c o n c e n t r a t i o n i n c r e a s e d , less d r a i n a g e
volume w a s c o l l e c t e d f o r any f i x e d p e r i o d of t i m e . However,gravity d r a i n a g e
w a s t y p i c a l l y complete i n less t h a n 1000 min (0.7 d ) . F u r t h e r d r y i n g by s o l a r
e v a p o r a t i o n , a l t h o u g h n o t e v a l u a t e d i n t h e s t u d i e s r e p o r t e d h e r e , would re-
s u l t i n t h e removal of a d d i t i o n a l q u a n t i t i e s of water.

Conditioned Suspensions. To d e t e r m i n e t h e e f f e c t s of p o l y e l e c t r o l y t e s
on g r a v i t y d r a i n a g e p r o p e r t i e s , s u s p e n s i o n s w e r e c o n d i t i o n e d w i t h v a r y i n g
levels of p o l y e l e c t r o l y t e and allowed t o g r a v i t y d r a i n on c l e a n sand d r y i n g
beds. The t i m e t o a c h i e v e 50% of t o t a l d r a i n a g e w a s used t o normalize d r a i n -
age d a t a f o r e v a l u a t i o n purposes. Data p r e s e n t e d i n F i g u r e 10 f o r a p l a n t
A 1 s u s p e n s i o n were t y p i c a l of t h o s e c o l l e c t e d . Although n o t i n d i c a t e d i n
F i g u r e 1 0 , t h e t o t a l volume of g r a v i t y d r a i n a g e d i d n o t v a r y w i t h poly-
e l e c t r o l y t e d o s e , however, t h e rate of d r a i n a g e w a s s i g n i f i c a n t l y a f f e c t e d .
The optimum d o s e of p o l y e l e c t r o l y t e w a s s e l e c t e d as t h e l o w e s t dose r e s u l t -
i n g i n t h e most r a p i d d r a i n a g e , e . g . 20 mg/l of HF-190 ( F i g u r e 10) a t a sus-
pended s o l i d s (SS) c o n c e n t r a t i o n of 3.3 g / l o r 6.06 g/kg SS. T h i s and o t h e r
similar p o l y e l e c t r o l y t e doses were used t o examine s u s p e n s i o n d r a i n a g e
p r o p e r t i e s o v e r r a n g e s of suspended s o l i d s c o n c e n t r a t i o n .

Data p r e s e n t e d i n Figure 11 i n d i c a t e t h e e f f e c t s of two p o l y e l e c t r o -

l y t e s on t h e d r a i n a g e p r o p e r t i e s of t h e s u s p e n s i o n from p l a n t A l , It i s
a p p a r e n t t h a t p o l y e l e c t r o l y t e a d d i t i o n r e s u l t e d i n s i g n i f i c a n t improvements
i n t h e r a t e of d r a i n a g e . It is a l s o a p p a r e n t t h a t t h e e x t e n t of improve-
ment v a r i e d w i t h suspended s o l i d s c o n c e n t r a t i o n . G e n e r a l l y t h e g r e a t e s t
improvement w a s achieved a t o r n e a r t h e suspended s o l i d s c o n c e n t r a t i o n a t
which t h e optimum p o l y e l e c t r o l y t e dose r a t e w a s e v a l u a t e d . It w a s there-
f o r e a p p a r e n t t h a t p o l y e l e c t r o l y t e dose v a r i e d w i t h suspended s o l i d s con-
c e n t r a t i o n and should be determined a t o r n e a r t h e suspended s o l i d s con-
c e n t r a t i o n t o b e a p p l i e d t o a d r y i n g bed.

1047
 PLANT A1 (21-80)

-
ICONC. b3 dl

t OPTIMUM DOSE

I I I 1 I
M 40 60 80 loo 120 i
HF-190, moll

Figure 10. Optimum P o l y e l e c t r o l y t e Dose Determination

f o r G r a v i t y Drainage of Sample A1-21-80

I I I I I

/-
P U N T A1 12160)

POLYMER SYMBOL

~l*p-ldl)fi#bs 0

HF-1W - bl SS

"E 0
I I I I I
5 6 0 12 16

SUSPENDED SOLIDS CONC., fi

Figure 11. E f f e c t of P o l y e l e c t r o l y t e Conditioning on

G r a v i t y Drainage of Sample A1-21-80
 Conclusions

Wastewaters generated in the aluminum extrusionfanodizing industry are

generated in numerous rinsing and finishing processes which may vary from
industry to industry. However, in virtually all cases examined in this re-
search (l), variations in the properties of the conventionally-generated
wastewater suspensions were not extensive enough to result in separate clas-
sifications for the suspensions.

The sludge suspensions contained aluminum as the primary metallic

constituent. Suspended solids data indicated 32 to 60% of the inert sus-
pended solids were aluminum which was generally consistent with a therotical
formulation for the sludge of aluminum hydroxide, A1(OH)3. Dissolved solids
for conventional suspensions varied from 1.34 to 6.04 gfl indicating a
relatively high level of salt addition through use. The majority of the
dissolved solids were inorganic constituents since organic carbon levels
were typically low, i.e. 4 to 93 mgfl. Of the toxic metals examined, Cr,
Se and Zn were the only metals detected in mgfl levels, i.e. 1.4 to 1.7
mgfl. Concentrations of these metals were not, however, consistently high
and were detected at much lower concentrations in several samples. The re-
maining metals (Ag, As, Be, Cd, Cu, Hg, Ni and Pb) were detected in the
dissolved form at concentrations less than or equal to 260 pgfl indicating
a low composition of toxic metals. Furthermore, the majority of all toxic
metals except Se were contained in the suspended form and were effectively
fixed in the sludge suspensions following treatment by neutralization at
the individual plants.

With respect to sludge treatment, thickening .properties of uncondition-

ed suspensions were unacceptable and polyelectrolyte conditioning is a
necessary requirement. Polyelectrolyte selection must be performed with
consideration of the effect of varying suspended solids concentration on
the optimum range of application. Proper application can, however, result
in major improvements in sludge thickening properties although thickened
sludge concentrations of 1 to 2% solids may be all that can be achSeved.

Sludge dewatering properties of aluminum-finishing sludges were gen-

erally poor but were typical of other metal-hydroxide sludges (1). Poly-
electrolyte-conditioning resulted in improved dewatering properties but
the improvements were not as dramatic as those noted for thickening prop-
erties. While water was more rapidly removed from the sludge suspensions
following polyelectrolyte-conditioning, the extent to which dewatering was
achieved was not improved. That is, the solids content of dewatered cakes
did not increase following polyelectrolyte conditioning, but in fact de-
creased slightly. Therefore, polyelectrolyte-conditioning resulted in im-
proved rates of water removal but did not improve the extent to which water
was removed.

Dewatering of sludge suspensions by gravity drainage was shown to be

an effective treatment alternative. Prediction and control of solar
evaporation however are major drawbacks to this mode of dewatering. Poly-
electrolyte-conditioning resulted in improved drainage rates but did not
increase the extent to which water was removed from the dewatered cake.
Optimum polyelectrolyte dose was shown to vary with suspended solids con-
centration.

With respect to overall characteristics of aluminum-finishing sus-

pensions, the suspension composed of solids generated from neutralization
of concentrated spent finishing solutions (i.e. sample A2-319-79) con-
sistently had the best properties with respect to sludge treatment.

1049
Thickening properties of the suspension were superior to the conventional
suspensions and specific resistance values were among the lowest for the 9.
suspensions examined. Furthermore, cake solids content of unconditioned
and conditioned samples of A2-319-79 were as much as 2.5 times those of
conventional sludges. These improvements in treatment properties were
attributed to the conditions under which the suspension was generated.
Discharge of concentrated etch and acid wastewaters at plant A2 to a neu- 10.
tralization basin without the discharge of rinse waters resulted in the
production of elevated temperatures. At elevated temperatures the form
of the aluminum hydroxide precipitated is much more crystalline-like than
the gelatinous precipitates produced at lower temperatures as illustra-
ed in detail by Saunders et al. (9) and Medero (10). Therefore, the high-
temperature neutralization achieved f o r convenience of operation at plant
A2 resulted in the production of a sludge which could be more effectively
treated for disposal.

Acknowledgment

The research presented was sponsored by the Aluminum Association Inc.,

the Aluminum Extruders' Council and by the U. S. Environmental Protection
Agency. The generous cooperation of the sponsoring organizations and the
participating plants is gratefully acknowledged.

References

1. Saunders, F. M. , and Sezgin, M. , "Characterization Reclamation and

Final Disposal of Aluminum Bearing Sludges;" Final Report to The
Aluminum Association Inc., Washington, D. C., p.239, SCECIT-81-101,
School of Civil Engineering, Georgia Institute of Technology,
Atlanta, GA (1981).

2, The Aluminum Association, Inc,, Aluminum Standards and Data 1979,

6th edition, Washington, D. C. (1979).

3. Brace, A. W . , and Sheasby, P. G., The Technology of Anodizing

Aluminum, 2nd edition, Technicopy Limited, England (1979).

4, Steward, F. A,, and McDonald, D. C., "Effluent Treatment from Aluminum

Finishing Processes'' Proc. 66th Annual American Electroplaters Society
Technical Conf., American Electroplater's Society, Winter Park, FL

5. Standard Methods for the Examination of Water and Wastewater, 14th

edition, American Public Health ASSOC., Washington, D.C. (1976).

6. O'Connor, J. T., Editor, Environmental Engineering Unit Operations

and Unit Processes Laboratory Manual, 2nd edition, Assoc. Environ.
Eng. Professors, Austin, TX (1975).

7. Stumm, W., and Morgan, J. J., Aquatic Chemistry, 2nd edition, Wiley
Interscience, Inc., New York, N. Y. (1981).

8. Environmental Protection Agency, Test Methods for Evaluating Solid

Waste - Physical/Chemical Methods, EPA-SW-846, Washington, D.C. (1980).

1950
11
9. Saqnders, F. M., Sezgin, M. and Ramirez R. R., "High Temperature
! Treatmeqt of Concentrated Ahninum Finishing Wastes", Proc. 67th
Annual American Electroplaters Society Technical Conf., Milwaukee,
Wisc., American Electroplaters Society, Winter Park, F'T., (1980).
- 10. Medero, J. M., "Effect of High-Temperature Precipitation of Aluminum-
Finishing Wastes on Sludge Dewatering Characteristice", School of
Civil Engineering, Georgia Institute of Technology, Atlanta, GA (1981).
n

n-
t
?

- 9

1051