Physicochemical

Physicochemical Treatment of Wastewater
Author(s): Walter J. Weber, Jr., Charles B. Hopkins, Ralph Bloom and Jr.
Source: Journal (Water Pollution Control Federation), Vol. 42, No. 1 (Jan., 1970), pp. 83-99
Published by: Water Environment Federation
Stable URL: http://www.jstor.org/stable/25036447
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PHYSICOCHEMICAL
TREATMENT
OFWASTEWATER
Walter J.Weber, Jr., Charles B. Hopkins, and Ralph Bloom, Jr.
It has become apparent over the treatment required by more stringent

past several years that achievement of effluent standards (1) (2).
high levels of water quality demanded However, common philosophy re
by progressive water use and reuse re garding application of advanced phys

quirements, and by requirements for icochemical processes for wastewater
more effective water pollution control, treatment generally has centered on
necessitates expanded utilization of ad providing ''tertiary'' treatment for
vanced technologies for wastewater wastes which already have undergone
*' ''
treatment. Conventional "secondary" conventional secondary biological
biological treatment processes do not treatment. The addition of tertiary
provide the degree of treatment re level physicochemical processes to con
quired for most water reuse applica ventional biological processes incurs
tions, nor do they provide a completely significant additional treatment ex
satisfactory measure for protecting penses. Further, the effective opera
natural waters from pollution by waste tion a tertiary
of treatment system
discharges. depends on consistent and efficient
Well operated modern biological operation of the biological secondary
waste treatment plants can provide ap process, which remains subject to prob
proximately 90-percent removal of sus lems arising from changes in waste
pended solids and biochemical oxygen composition, from large variations in
demand (BOD). Although the qual flow which often have to be diverted,
ity of the effluent from such plants has and from the presence of toxic ma
been adequate to meet most discharge terials which disrupt biological oxida
regulations and standards in the past, tion processes.
recent increases in both population and The present work represents a major
in standard of living have resulted, divergence from the traditional con
in the face of a relatively fixed total cept of "tertiary'' treatment, and ex
water resource, in more stringent de amines the direct application of a
mands for better water quality and physicochemical process for treatment
more effective pollution control. As a of primary wastes. The process de
result, significant interest has focused veloped and tested in this research
over the past decade or so on develop program includes chemical clarifica
ment of physicochemical processes ca tion, filtration, and adsorption by ac
pable of accomplishing the degree of tivated carbon.
The concept of applying the process
Walter J. Weber,
Jr., is Professor of Civil
directly to a primary waste rather
and Water Resources
Engineering, University
Ann Arbor. Charles B. Hop than to a secondary effluent derives
of Michigan,
kins and Ralph Bloom, Jr., are, respectively, partially from observations regarding
Research Engineer and Manager, FMC Cor the apparent of removing
difficulty
N. J.
poration, Princeton, final traces of organic material from
The paper was presented at the 42nd An
secondary effluents by treatment with
nual Conference of the Water Pollution Con
trol Federation in Dallas, Texas, October 5 activated carbon, as well as from the
10, 1969. relative economics of two-stage vis-?
83
84
JOURNAL WPCF January 1970
vis three-stage treatment systems. On the basis of the encouraging re

Several investigators have
reported sults obtained in the bench-scale lab
leakage of certain organic fractions oratory investigations, a direct physi
through activated carbon columns cochemical process has been developed
when the latter were used to treat sec and extensively field tested for one
ondary effluents (3) (4). While the year in a 7,200-gpd (273-cu m/day)
nature of this leakage is not exactly pilot-scale facility. The essential find
known, there is strong indication that ings of these field studies are (a) that
it is comprised partially of non-adsorb chemical clarification followed by fil
able cell fragments produced during tration can remove essentially all of
the biological treatment stage, and the suspended solids present in a pri
partially of small organic molecules mary effluent; (b) that adsorption on
which have been hydrolyzed exten activated carbon provides an effective
sively in the biological treatment stage means for removing the soluble or
and thus rendered more soluble and ganic fractions left in the wastewater
less subject to adsorption from the after the solids have been removed;
waste solution. These observations sug and, (c) that the chemical clarification
gest that a primary wastewater might step also accomplishes effective re
therefore be more suitable for direct moval of phosphate, while any nitrate
treatment with activated carbon than present in the primary effluent is es
after it had undergone biological pre sentially completely reduced in the
treatment. Laboratory studies were activated carbon stage of treatment.
performed several years ago to test Without benefit of a biological treat

this hypothesis, and the results indi ment step, overall organic waste mat
cated that high levels of removal of ter removals of 95 to 97 percent have

organic material could be obtained by been maintained consistently, despite
direct treatment of primary waste variations in organic loadings and the
waters with activated carbon (5). presence, at times, of toxic chemicals
|||||M?iitf
FIGURE 1A.?Packed-bed and expanded-bed adsorption columns and

appurtenances at the pilot plant. Building in background houses clari
fication units, pumps, controls, and automatic sampling equipment.
Vol. 42, No. 1 PHYSICOCHEMICAL TREATMENT 85
which would affect normal biological

processes adversely. Of the total or
ganic matter removal, approximately
65 percent is achieved in the chemical
clarification stage of the process. The
high quality, clear effluent is essen
tially free of solids, and contains ap
proximately 5 mg/1 or less of organic
matter expressed as either total or
ganic carbon (TOC) or as BOD, com
pared to about 30 mg/1 for the same
wastewater treated conventionally. In
addition, the direct physicochemical

treatment generally achieves a high
degree of removal of the inorganic
and nitrate, ma
nutrients, phosphate
terials which are not removed effec
tively by conventional biological waste
water treatment operations.
Pilot-Plant Facility
The pilot plant for field testing of
the direct physicochemical process was
constructed and operated at the waste
water plant of the Ewing-Lawrence FIGURE IB.?Upflow clarifier and pumps
Sewerage Authority (ELSA) near in the pilot plant.
Trenton, New Jersey. This trickling

filter plant serves most of the residen prised of approximately 25-percent in
tial, commercial, and industrial areas dustrial waste and about 75-percent
within the two townships of Ewing and domestic waste. The treatment plant
Lawrence. The wastewater is com is designed for an average daily flow
FIGURE IC.?Flow metering and control panel in the pilot plant.
86 JOURNAL WPCF January 1970
PRIMARY EFFLUENT
CHEMICAL
FILTER
CLARIFICATION
i rx n.
TLTLl X T
EXPANDED-BED ADSORBERS PACKED BED ADSORBERS
FIGURE 2.?Schematic flow diagram for the pilot facility.
of 9 mgd (34,065 cu m/day), with a adsorbers and a series of four ex
pumping capacity of 30 mgd (113,550 panded-bed adsorbers, the two series

cu m/day). The average daily flow is operating in parallel on the same
about 7 mgd (26,495 cu m/day). The chemically clarified primary effluent.
pilot facility is shown in Figure 1A, This was to provide a comparison of
B, and C. the relative performance and operat
A schematic flow diagram for the ing characteristics of expanded-bed
pilot plant is presented in Figure 2. and packed-bed modes of contacting.
The adsorption stage of the plant con The relative advantages and disadvan
sisted of a series of four packed-bed tages of packed-bed and expanded-bed
5.5 gpm
FEED
CLARIFIED
OUALMEDIA
RESERVOIR
UP-FLOW CLARIFIER FILTER
SIDE
45"?d.4'STRAIGHT 38'?d.
PRIMARY^!
EFRUEtSSJ 60* CONEBOTTOM
PUMP
FIGURE 3.?Schematic flow diagram for the clarification system.

(In. X 2.54 = cm; ft X 0.3 = m; gpm X 3.8 = 1/min.)
adsorbers have been discussed previ gravity filter. The piping in the pilot
ously (6) (7) as have the results of an plant was so arranged that either
extensive comparative pilot study of chemically clarified or untreated pri
both types of contactors for applica mary effluent could be fed to any one
tion to treatment of secondary effluents or more of the eight activated carbon
(8). Figure 3 presents a more de columns, depending on the test condi
tailed schematic flow sheet for the tions desired.
clarification and filtration elements of The columns were constructed of 10
the pilot treatment system. in. (25.4-cm) diam (ID) steel pipe
Primary effluent was piped by grav coated with epoxy paint. Four of the
ity from one of four primary sedi 8 columns were 9 ft (2.7 m) tall; these
mentation basins through a 1.5-in. (3.8 were used for packed-bed operation.
cm) polyethylene line to the pilot The remaining four columns were 12 ft
plant site, and then fed at a closely (3.6 m) tall for use for expanded-bed
controlled rate of 5.5 gpm (20.8 1/min) operation. Each column contained 85
to a rapid-mix chamber in a sectioned pounds (38.6 kg) of 12- X 40-mesh
off portion of an epoxy-coated steel granular activated carbon #, which pro
55-gal (208-1) drum, the bottom sec vided a 6-ft (1.8-m) deep bed of set
tion of which served as the first of two tled carbon. In the expanded-bed con
flocculating chambers. The waste en
tactors, the carbon was supported on a
tering the rapid-mix chamber was 6-in. (16.2-cm) layer of gravel and
mixed thoroughly with the coagulant, coarse sand over a 5-in. (12.7-cm) cone
ferric chloride, which was fed by a shaped distributor, as shown in Figure
proportioning pump as a 30-percent 4. The top 1-ft (30.5-cm) section of
(by weight) aqueous solution. Mixing each of the 12-ft (3.6-m) columns was
was accomplished by a stirrer operat made of transparent plastic to permit
ing at about 1,500 rpm. When neces observation of the effluent from the ex
sary, sodium carbonate solution could panded carbon beds, as well as to pro
be fed to the rapid mix tank to main vide a visual check to ensure that the
tain the alkalinity in the range re carbon was not being washed out of
quired for effective coagulation, al the column.
though the need for addition of Four pumps

constant-displacement
alkalinity was infrequent. After rapid were provided so that separate, con
mixing for approximately 2 min, the trolled feed streams could be supplied
wastewater flowed into the flocculator simultaneously to as many as four ad
portion of the 55-gal (208-1) drums, sorber systems. The pumps were
where detention time was about 15 min driven by electric motors through
and the rotation speed of the floccula variable speed drives to allow for ad
tor blades about 18 rpm. of flow through the systems.
justment
The up-flow clarifier was designed All connecting lines consisted of f-in.
specifically for this project and shop (1.6-cm) diam (ID) rubber hose. All
fabricated. Detention time at 5.5-gpm flow controls, including in-line valves,
(20.8-1/min) flow was approximately pressure gauges, flow meters, and sole
1 hr. Sludge was discharged from the noid sampling valves were mounted on
bottom of the clarifier at a controlled one central operating panel. Stream
rate, by means of a timer-operated flows were maintained at constant rate
pump, and disposed of in the waste by adjustment of pump drives, the flow
water treatment plant return line to being measured continuously with
water meters.
the primary settling basins.
The clarified feed was Twenty-four hr composite samples
chemically
filtered through a dual-media *
(anthra Pittsburgh CAL activated carbon, Calgon
cite coal and sand on gravel retainer) Corp., Pittsburgh, Pa.
FOR
HOSE CONNECTION
COLUMNFEEDOR PRODUCT
Hin. OD ACRYLIC PIPE

3/8 in. WALL
EXPANDEDBED ONLY
1/8 in. RUBBER GASKETS
3/4 in. BOLTS
10 in. STEEL PIPE 1/4 In.WALL

1501b FLANGES
BED DRAIN
3/4 in. I.P. COUPLING
HOSE CONNECTIONFOR
COLUMNFEED OR PRODUCT
PLASTIC CONE 5in. DIA
COVEREDWITH GRAVEL
w tHj
FIGURE 4.?Detail of the adsorption column. (In. X 2.54 = cm;

ft X 0.3 = m; lb X 0.454 = kg.)
were collected in polyethylene bot formed at the main laboratory of the

tles. Timer-controlled solenoid valves Central Research Department, FMC
opened automatically at 20-min inter Chemicals Group, near Princeton, N. J.
vals to draw 100-ml samples for com Analytical determinations included to
positing. These samples were com tal organic carbon (TOC), soluble or
posited in an acid medium to maintain ganic carbon (SOC), BOD, suspended
stability and prevent deterioration or solids, turbidity, phosphates, and ni
biological activity over the 24-hr com trates.
positing periods. For BOD determi

nations, spot samples were obtained
Analytical Procedures
and brought, unacidified, to the labora
Suspended solids were measured by
tory for immediate analysis.
The system was designed for essen filtration of samples through 0.45-ju,
automatic A tech membrane filters (9). The membrane
tially operations.
nician visited the plant daily to take filters were washed in distilled water
and dried in individual desiccators to
samples, adjust flows, and perform any
routine maintenance required. Chemi constant weight before and after filtra
cal and biochemical analyses were per tion of the samples. The filtrate was
collected to provide a sample for anal systems were operated as expanded

ysis for soluble organic carbon (SOC). bed adsorbers. systemEachtreated
A carbonaceous analyzer was used approximately 3,600 gpd (13.6 eu m/
for determination of organic carbon, day) of wastewater, corresponding to
directly for TOC, and after filtration a carbon column loading of approxi
through a membrane filter, for SOC. mately 5 gpm/sq ft (0.2 cu m/min/sq
Determinations for BOD were per m) of surface area.
formed by the dilution method de The third, and most significant,
scribed in "Standard Methods" (10). phase of the investigation was a long
Turbidity was determined with a term study of two complete physico
photoelectric turbidimeter. chemical systems consisting of chemi
Total phosphate was determined by cal clarification, and adsorp
filtration,
ASTM procedure D515-60T on sam tion on activated carbon, in that order.
ples which had been digested to con One of the systems included a 24-ft
vert all phosphate to the ortho form, (7.2-m) deep packed-bed adsorption
and nitrate was determined by ASTM stage, wThile the other system utilized
procedure D992-52 (11). an expanded-bed mode of operation
for carbon contacting with the same
Experimental Program amount of carbon. The experimental
facilities for this third phase of the
The experimental program for this
project, during which the treatment
investigation consisted of four rela
The first phase systems were operated continuously for
tively distinct phases. 125 days, were as shown in Figures
involved a detailed 2,
laboratory study of in an earlier
the chemical 3, and 4, and as described
clarification stage of the section of this paper.
process. Standard jar-test coagulation
A fourth phase of the project ex
studies with iron, alum, and lime were
on the primary amined the relative advantages and
conducted effluent from
disadvantages of providing chemical
the ELSA plant. Several anionic,
clarification and filtration following
nonionic, and cationic polyelectrolytes
the carbon adsorption stage, vis-?-vis
also were investigated, as well as a
chemically clarifying and filtering the
number of combinations of inorganic
water prior to adsorption. The poten
coagulants and/or polyelectrolytes.
a second tial advantage of post clarification is
Parallel studies under
to provide a final polishing to remove
phase of the experimental program ex
any particulate matter which is re
amined the relative effectiveness of
leased from the carbon contactors. It
treating primary effluent by activated
is recognized generally that biological
carbon alone, without chemical pre
growths develop on carbon surfaces
clarification. These studies were con
during treatment of wastewaters.
ducted at the pilot-plant facility over
an operating These growths lead to solids generation
period of approximately
in the carbon contactors, with some
75 days. Four adsorption systems were
suspended solids thus being released to
used for this phase of the study, two
on unclarified the effluent. A final, post clarification
systems operating pri remove sus
step can be used to these
mary effluent and two on chemically
pended solids to produce a very high
clarified effluent. Each carbon system
quality effluent. Shifting the clarifica
contained a 12-ft (3.6-m) depth of ac
in each of tion step to follow the adsorption step
tivated carbon, 6 ft (1.8 m)
rather than precede it results in some
two columns. One of the two systems
unclarified effluent considerable operating difficulties for
treating primary
and one of the two treating clarified packed-bed type adsorbers. Expanded
effluent were in bed adsorbers, on the other hand, are
primary operated
packed-bed mode, while the other two not nearly as subject to fouling and
90
plugging, and can operate effectively effluent. Because of the relative ease
without preclarification. of handling and feeding the quantities
Of the four phases of this pilot proj required for the pilot-scale study, iron
ect, the third, in which the complete was selected for use as the coagulant
physicochemical treatment systems for the plant operations, although lime
were operated continuously for ap may well be preferred for larger scale
proximately four months, is of most operation. Dosages of iron used for
immediate interest, and is the focal coagulation during the pilot studies
point of the present discussion. ranged between 150 to 190 mg/1 as
FeCl3, the average dose being about
Experimental Results 170 mg/1 FeCl3, or approximately 58
mg/1 of Fe(III). Coagulation and
In brief summary of the results of
filtration in the pilot studies were ac
the laboratory jar tests performed in
complished as illustrated schematically
the first phase of the project, good in Figure 3.
coagulation of the primary effluent was
The carbon adsorption systems em
obtained with an iron dosage of ap
250 as ployed for the third phase of the proj
proximately mg/1 FeCl3 6H20, ect consisted of parallel packed and
with about 250 mg/1 of alum as
expanded-bed adsorbers. Each of the
AI2O3 18H20, and with about 300
two parallel systems consisted of four
mg/1 of lime. These doses of primary columns in series, as illustrated sche
coagulant reduced the turbidity of the
matically in Figure 2, with each column
primary effluent from about 30 to 40
containing 85 lb (38.6 kg) of 12- X 40
Jackson turbidity units (JTU) to
granular activated carbon. This
about 1 to 2 JTU. Combinations of
amount of carbon corresponded to a
lime and FeCl3 were about equally settled depth of 6 ft (1.8 m) in each
effective at approximately the same
column; the carbon in the expanded
total coagulant dose. Alum required bed adsorbers was expanded by about
close control of pH to obtain good co
10 percent to a depth of approximately
agulation, while ferric chloride gave
clarification and
6.6 ft (2.0 m) during operation with
consistently good an hydraulic of about 5 gpm/
of floe with an essen loading
rapid settling
sq ft (0.2 eu m/day/sq m).
tially neutral clarified water (pH 6
The results of the 125-day pilot
to 7).
study with the expanded-bed adsorber
Several anionic, nonionic, and cat
with respect to removal of total or
ionic organic polyelectrolytes were
ganic carbon (TOC) are presented in
tested in doses ranging from 0.1 to 5
Figure 5. The uppermost trace in this
mg/1, but none was found to be par the TOC of the efflu
effective as a primary figure represents
ticularly coagu
ent from the primary settling basins
lant. As secondary floe strengtheners,
of the ELSA treatment plant. Ap
used in combination with iron or alum,
proximately 50 percent of the TOC was
some of the polyelectrolytes produced
removed by primary sedimentation.
larger floe particles, which settled more in TOC in the pri
The sharp decrease
rapidly than those formed with alum
mary effluent after a flow of about
or iron alone. Turbidity removal was
no and the 300,000 gal (1,135 eu m) through the
generally better, however, to a heavy
could not pilot plant corresponded
dosage of primary coagulant
rainfall in the area
and prolonged
be reduced much below that required
when only the metal salt was used.
served by the ELSA plant.
From Figure 5 approximately 65
It was concluded from the labora
studies that either percent of the TOC remaining in the
tory coagulation
iron or lime could be used for effective primary effluent was removed by the
chemical clarification of the primary chemical clarification step, as indicated
Vol. 42, \,No. 1 PHYSICOCHEMICAL TREATMENT 91
i-1-i-r
50 100 150 200 250 300 350 400 450

VOLUME TREATED 1.000 GAL
FIGURE 5.?Removal of total organic carbon by clarification and adsorption in a series

of adsorbers. = 3.8
expanded-bed (Gal XL)
by the next lower trace in the plot of (24-ft or 7.2-m) carbon contacting
TOC vs. volume treated. units in the series. It is apparent from
The remaining traces in Figure 5 the lowest trace in Figure 5 that the
represent TOC concentrations in the effluent from the complete physico
effluents from the first (6-ft or 1.8-m), chemical treatment system was of an
second (12-ft or 3.6-m), and fourth exceptionally high quality, averaging
T-1-1-T
0 10 20 30 40 50 60
TOTAL ORGANIC CARBON APPLIED, lb
FIGURE 6.?Cumulative sorption of total organic carbon for packed
bed and expanded-bed adsorbers as a function of TOC applied. (Lb X
0.454 = kg; ftX0.3 =
m.)
JOURNAL WPCF
92 January 1970
in the neighborhood of three to five stance, with the carbon providing an

mg/1 of total organic carbon. This excellent surface for concentration of
quality was maintained throughout the organic biological substrate materials.
entire four-month period of operation Activated carbon does appear to be
of the plant, during which time nearly somewhat unique in this regard, as has
500,000 gal (1,890 eu m) of primary been shown in previous comparative
wastewater were processed. investigations of biological activity in
The total quantities of TOC re columns of activated carbon and an
moved by the individual adsorbers for thracite coal (8). The biological ac
both systems are presented in Figure tivity does not appear to hinder the
6 as functions of TOC applied. There adsorption process in any observable
are no practical differences in the per fashion, but it does seem to enhance
formance of the expanded-bed and the overall capacity for removal of or
packed-bed adsorbers. It is significant ganics, thus affording longer periods
to note that the amount of TOC re of effective operation than might be
moved by the carbon in each system is predicted.
approximately 45 lb (20.4 kg) for a Although there were no practical
24-ft (7.2-m) depth, or for 340 lb differences in the performance charac
(154.4 kg) of activated carbon. It is teristics of the expanded-bed and
quite reasonable to estimate that the packed-bed adsorbers, there were, as
TOC represents about 50 percent of observed previously in pilot studies on
the total mass of organic matter re the treatment of secondary wastewater
moved from the wastewater by the ac effluents (8), some significant opera
tivated carbon. Thus, the amount of tional differences. None of the four
organic material removed represents expanded-bed adsorbers required any
approximately 90 lb (40.8 kg) per 340 cleaning or maintenance over the four
lb (154.4 kg) of active carbon, or about month period of operation; flow rates
27 percent by weight loading of the remained constant without appreciable
active carbon. Still, even at this point increases in head loss through the four
the quality of the effluent from the series columns. Conversely, even with
system remains as high as it was at a highly clarified primary effluent, the

the beginning of the operation. head loss in the packed-bed adsorbers
Even more remarkable is the amount increased steadily, requiring increased
of loading that has occurred for the pumping pressures and eventual clean
first column in each of the two adsorp ing and backwashing. The packed col
tion systems. The TOC removed by umns were backwashed whenever the
each of these columns over the 4-month required pumping pressure across the
system increased to 50 psi (3.5 kg/sq
period of operation was approximately
25 lb (11.4 kg), or an estimated 50 lb cm). Thus, over the 125-day period,
(22.8 kg) of total organic material. the first packed-bed adsorber in the
For an 85-lb (38.6-kg) quantity of ac series of four was cleaned and back
tivated carbon, this a very washed approximately 50 times, or
represents
high removal capacity of approxi about once every 2.5 days. The re
60 percent by weight to this maining three packed-bed columns re
mately
of with significant ca quired less frequent cleaning; about
point operation,
yet remaining. One five cleanings for the second column,
pacity apparently
observation with regard to two for the third column, and only one
pertinent
these very high organic loading ca cleaning was required for the last col
is that some biological activity umn in the series.
pacities
did occur on the activated carbon in Figure 7 is a plot of BOD concen
the adsorption systems. However, this trations in the primary effluent, in the
appears to be a fortuitous circum chemically clarified wastewater, and in
60
50
| 40 PRIMARY
o"
om EFFLUENT
30 h
CLARIFIED PRIMARY EFFLUENT
20 h
lOh o Do PACKED
BED
D EXPANDED
oo BED
a 00 8 o&
o D %r a
ooD?8o 0 D
a
GG O
MAY JUN. JULY AUG.

FIGURE 7.?Removal of BOD by clarification and adsorption in
packed-bed and expanded-bed adsorbers.
the product waters from the parallel reduced the BOD to an average level
pilot treatment systems. As in the of about only four to five mg/1. Fur
case of TOC, the primary treatment ther, it was determined that approxi
stage at the ELSA plant removed ap mately one to two mg/1 of this ob
proximately 50 percent of the BOD served BOD actually was present as
present in the raw waste wat er. The IDOD, or immediate dissolved oxygen
chemical clarification stage reduced the demand. Thus, the true or corrected
BOD remaining in the primary effluent range for the 5-day BOD of the efflu
from an average of about 50 mg/1 to ent from the physicochemical plant
an average of approximately 15 mg/1. was approximately 2 to 3 mg/1, indi
As may be noted in Figure 7, the ac cating a very high-quality product
tive carbon adsorption systems further water.
MAY I JUNEI JULYI AUGI

FIGURE 8.?Removal of turbidity by clarification and adsorption in packed-bed
and expanded-bed adsorbers.
The IDOD observed in the effluent

likely was due to the presence of iron,
which carried over as Fe(III) from
the coagulation stage and was reduced
to Fe(II) under anaerobic conditions
in the carbon adsorption systems.
Periodic anaerobic biological activity
in the carbon columns was evidenced
by an occasional occurrence of the char
acteristic odor of hydrogen sulfide in
PRIMARY
EFFLUENT the otherwise high-quality product
water. This development was not ob
served in the second and fourth phases
of the project, which were carried out
during periods of late fall, winter, and
early spring. The third phase was
O
carried out during the period from
IOr early May through August, however,
during which time the ambient tem
perature of the wastewater was con
CLARIFIED
PRIMARY
EFFLUENT
5h siderably higher.
^EXPANDED
BED Several different procedures were
?*VvV o-PACKEDBED attempted

condition
for control of the anaerobic
in the adsorbers. Addition
of hypochlorite to the chemically clari
MAY JUNE IJULY
fied water before it entered the ad
FIGURE 9.?-Removal of total phosphate
clarification and in packed sorbers was moderately effective in
by adsorption
bed and expanded-bed adsorbers. reducing the hydrogen sulfide odor.
VoL 42, No. 1 PHYSICOCHEMICAL TREATMENT 95
Aeration of the clarified effluent par the primary effluent was approximately
tially reduced the odor, but tended to 7 to 10 mg/1 as N; this was decreased
produce a biological floe which rapidly to about 2 to 3 mg/1 by chemical clari
plugged and fouled the packed-bed ad fication and further to about 1 mg/1
sorbers. The solution finally chosen by adsorption. Somewhat surpris
involved bleeding oxygen from a cylin ingly, nitrate levels ranging as high
der of the compressed gas into the in as 15 mg/1 NO3- were observed in the
fluent to the adsorbers whenever there primary effluent at the ELSA plant.
was evidence of the presence of hydro The nitrate was affected only slightly
gen sulfide in the product water. by chemical clarification, but was re
The chemical clarification stage of duced to an average of less than 0.5
the physicochemical treatment plant mg/1 during the adsorption stage.
was very effective in removing sus The observed reduction in nitrate is
pended solids. As evidenced by the most likely a result of biological activ
turbidity data presented in Figure 8, ity in the carbon columns. This con
the adsorption systems, both packed clusion is substantiated at least par
bed and expanded-bed, provided even tially by the fact that very little ni
further clarification to produce a clear, trate removal occurred in the activated
colorless, effluent water. The final carbon systems during the first day or
product from the adsorbers had an av two of operation, during which time
erage turbidity of about only 1 Jack biological activity was just beginning
son unit, compared to an average tur within the adsorption systems.
bidity of approximately 35 Jackson
units in the primary effluent. Proposed Physicochemical Treatment
In addition to providing a high de Plant Design
gree of clarification of the wastewater, On the basis of the results obtained
the coagulation stage also accomplished in the four phases of this pilot project,
very effective removal of phosphorus. a physicochemical wastewater treat
Figure 9 is a plot of total phosphorus
ment plant design concept can be ad
(as P043_) in the primary effluent, the vanced. A recommended flow sheet for
effluent from the chemical clarification
such a treatment plant is given sche
step, and the final product waters from in 10. In this treat
matically Figure
the two adsorption systems. As may
ment system, coagulant is added to de
be observed from the data presented in
gritted raw wastewater, and the clari
Figure 9, the phosphorus was reduced
fier replaces the primary settling basin.
from an average value of about 30
of
It is anticipated that coagulation
mg/1 in the primary effluent to an
raw degritted wastewater rather than
average level of approximately 2 to 3
primary settled wastewater will not
mg/1 in the final product water.
alter coagulant dosage requirements
Periodic were made for am
analyses
significantly. Coagulant dose should
and nitrate
monia, organic nitrogen, be a function primarily of the concen
in the primary effluent and in the tration of finely divided suspended
product waters from the various stages solids, and not be dependent to any
of the physicochemical pilot plant. extent on the solids
appreciable gross
Neither coagulation nor carbon adsorp in raw wastewater.
the
tion significantly affected the concen The activated carbon adsorption units
tration of ammonia, which ranged in the proposed physicochemical treat
from 20 to 50 mg/1 in the primary ment would be
system preferably op
effluent. The organic nitrogen, on the erated in an expanded mode. This
other hand, was reduced by both chem would permit the use of simple open
ical clarification and by adsorption. top concrete carbon contacting basins,
The organic nitrogen concentration in and afford relatively trouble-free op
PRELIMINARY COAGULATION
TREATMENT CLARIFICATION
GRIT SLUDGE
COAGULANT
DUAL CARBON
BACKWASH " MEDIA
i FILTER ADSORBERL I
ti
PRODUCT
WATER
J FILTER OR COAGULANT
SLUDGE THICKENER _^.MriMFDATc_^
-INCINERATE -
-^CENTRIFUGE RECOVERY
I
FIGURE 10.?Proposed clarification-adsorption process for wastewater
treatment.
eration. The use of open tanks with Based on the physicochemical treat
trough-type overflows should have the ment plant design concept presented
effect of providing intermediate aera above, capital and operating costs have
tion of the wastewater during treat been estimated for several plant sizes
ment, thus avoiding anaerobic condi ranging from 0.1 to 100 mgd (379 to
tions such as those which developed in 378,500 cu m/day) ; these are pre
the closed column and piping system sented in Table I. Data published by
of the pilot plant. Smith (12) on the costs of conven
In the proposed treatment system tional and advanced operations for
the filtration step, if used at all, would treatment of wastewater served as the
follow the carbon adsorption stage. basis for these preliminary cost esti
The purpose of this treatment step mates. The data presented by Smith
would be to provide a high level of should be valid at least for estimation
polishing if an exceptionally clear of comparative costs for different types
effluent is desired for some particular of treatment operations. To develop
reuse application. This "post" filtra the total construction and operating
tion step would remove any suspended costs for the physicochemical process,
material generated in the carbon col cost estimates for the individual com
umns and eventually released in the ponents were combined. The operat
effluent from the adsorbers. Experi ing costs include amortization at 4.5
ence with the pilot plant at Ewing percent for 25 yr, and have been ad
Lawrence suggests that the product justed to June 1967 (12). Costs for
water following coagulation and ad sludge disposal are not included, al
sorption will be sufficiently low in sus though the coagulation costs include
pended solids for most reuse applica those associated with coagulant recov
tions, thus generally obviating the ery (recalcination).
need for filtration. These estimates indicate that the
The sludge from the clarification physicochemical clarification-adsorp
stage of the proposed treatment scheme tion process requires substantially less
will be thickened and incinerated, capital for large plants (> 1 mgd or
whereupon the coagulant will be re 3,785 cu m/day) than does the acti
covered for reuse. vated sludge process. Below 1 mgd
(3,785 cu m/day) the capital costs for the physicochemical process is substan
the physicochemical process are some tially less for all plant sizes?about 50
what greater, while for a 1-mgd (3,785 percent less for a 1-mgd (3,785-cu m/
cu m/day) plant the estimated costs day) and more than 50 percent less
for the two processes are about the for larger plants. The operating costs
same. are also less for all sizes, with a dif
Operating costs for the physico ference of $0.10/1,000 gal (3.8 eu m)
chemical process are consistently at 10 mgd (37,850 cu m/day) and
greater than those for secondary bio $0.06/1,000 gal (3.8 eu m) at 100 mgd
logical treatment on the basis of cost (378,500 cu m/day).
per unit volume of waste treated, but These preliminary cost estimates re
the difference decreases as plant size quire further substantiation with op
increases. It may be more logical, erating data from larger demonstra
however, to compare the processes on tion plants. Nonetheless, the cost es
the basis of cost per unit of TOC, timates all have been formulated on
BOD, or phosphate removed, in which the same basis and should be valid for
case the economic comparison defi purposes of comparisons between proc
nitely would favor the physicochemical ess options.
treatment process.
When with the conven Conclusions
compared
tional activated sludge process plus A physicochemical coagulation/ad
tertiary treatment, the capital cost for sorption process for direct treatment
TABLE I.?Estimated Wastewater Treatment Plant Costs
Plant Size (mgd) 0.1 0.5 1.0 10.0
Estimated Construction Costs in 1,000 $
Physicochemical process
Preliminary treatment 4 10 15 65
Coagulation-sedimenation 10 30 52 400
Filtration* 20 57 90 410
Granular carbon 100 250 380 1,600
Chlorination 3 9 15 70
Total 137 386 552 2,545
Other processes
Primary treatment 80 220 350 1,750
Activated sludge process 100 310 550 3,100
Activated sludge plus
tertiary treatmentf 230 647 1,072 5,510
Estimated Operating Costs in c/1,000 GalJ
Physicochemical process 58 36 29 16
Primary treatment 21 14 12 7
Activated sludge process 31 22 19 11
Activated sludge plus
tertiary treatmentf 56 47 26
*
Filtration is considered an optional step which may be elected if an exceptionally clear
effluent is desired for a particular reuse application.
f Tertiary treatment includes coagulation and adsorption processes plus an optional filtra
tion step.
? Include amortization charges, 4.5 percent, 25 yr.
Note: X 3,785 = cu m/day.
Mgd
JOURNAL WPCF
98 January 1970
of wastewater has been developed and $0.11/1,000 gal (3.8 cu m). If ter
field tested for a 1-yr period in a pilot tiary treatment is added to the latter
facility treating approximately 7,200 to achieve the same high degree of
gpd (27.3 eu m) of wastewater. The treatment achieved in the physico
concept of applying physicochemical chemical process described here, the
treatment directly to a primary waste total cost is estimated to be $0.26/1,000
water, rather than to a water which gal (3.8 eu m). A factor which does
has undergone biological secondary not appear in these figures, but which
treatment, represents a significantly should be pointed out, is that the
different concept in the application of physicochemical process would occupy
advanced processes for wastewater only about 25 percent of the land area
treatment. required by a biological treatment
Consistent TOC and BOD removals plant of the same capacity (13) (14).
of 95 to 97 percent have been main Another significant advantage of the
tained, despite variations in waste physicochemical treatment system is
strength and composition. Toxic sub flexibility afforded in plant design,
stances which adversely affect biologi relative to both plant capacity and to
cal treatment processes have little or degree of treatment. The physico
no effect on the physicochemical proc chemical process permits plant design
ess. The effluent produced by the for modular additions to accommodate
physicochemical process is essentially growth in size as well as to accommo
free of suspended solids and contains date increasing requirements for efflu
only about 5 mg/1 or less of TOC and ent quality. For example, an effluent
to that obtained
BOD, compared with average TOC and quality comparable
BOD values of about 30 to 35 mg/1 from an activated sludge process can
for the same wastewater when treated be achieved with a carbon adsorption
system providing a relatively brief car
conventionally.
In addition, the bon contact period; as requirements
physicochemical
treatment achieves a for improved effluent quality develop,
process generally
of removal of phosphate additional adsorption units simply can
high degree
and nitrate be added to provide more contact time,
(about 90 percent) (about
and more effective removal of organic
95 percent), inorganic algal nutrients
which normally are not removed effec material. Similar flexibility is pro
vided with respect to removal of sus
tively by conventional biological waste
water treatment. pended matter by coagulation and fil
cost estimates, based on tration, and removal of phosphates by
Preliminary
published cost figures derived from precipitation.
on actual plants, have indi It is anticipated that results similar
statistics
cated that this high degree of treat to those reported here will be achieved
ment is achieved at reasonable cost. readily in larger plants scaled up from
treatment of an aver the pilot plant. It appears desirable
Physicochemical
to produce now to demonstrate the effectiveness
age municipal wastewater
to meet of this type of treatment on a scale of
an effluent quality sufficient
most demands for reuse and for con 0.5 to 1 mgd (1,892 to 3,785 eu m) to
trol of receiving water pollution obtain final criteria for design of phys
may
icochemical treatment plants of any
cost about $0.16/1,000 gal (3.8 eu m),
amortization of the capital. desired size.
including
On a comparable basis, conventional
primary-secondary biological treat Acknowledgments
ment, which can achieve only about 80 This work was carried out under
to 90-percent organic removal and lit Contract 14-12-459 with the Federal
tle or no nutrient removal, costs about Water Pollution Control Administra
tion. The authors wish to thank Wil Water Pollution Research." Proc. 3rd
Intl. Conf. Water Poll. Res., Water
liam Behn of the FMC Corporation for
Pollution Control Federation, Washing
his assistance in the operation of the
ton, D. C, Vol. 1, 253 (1967).
pilot facility, and the Ewing-Lawrence 7. Keinath, T. M., and Weber, W. J., Jr.,
Sewerage Authority (N. J.) for their "A Predictive Model for
''
the Design
and assistance in making of Fluid-Bed Adsorbers. Jour. Water
cooperation Toll. Control Fed., 40, 741 (1968).
facilities, space, and appropriate back
8. Hopkins, C. B., W. and
Weber, J., Jr.,
ground data available for this study.
Bloom, R., Jr., "A Comparison of Ex
panded-Bed and Packed-Bed Adsorp
References tion No.
Systems." Rept. TWRC-2,
1. Stephan, D. G., and Weinberger, L. W., R. A. Taft Water Res. Ctr., U. S.
" '
Water Reuse-Has it Arrived?' Dept. of the Int., Cincinnati, Ohio.
Jour. Water Poll. Control Fed., 40, 74 pp. (1968).
529 (1968). 9. Winneberger, J. H., Austin, J. H., and
<'
2. "Advanced Waste Treatment Research/' Klett, C. A., Membrane Filter Weight
FWPCA Publ. No. WP-20-AWTR-19, Determinations." Jour. Water Toll.
R. A. Taft Water Res. Ctr., U. S. Control Fed., 35, 807 (1963).
Dept. of the Interior, Cincinnati, Ohio, 10. "Standard Methodsfor the Examination
96 pp. (1968). of Water and Wastewater." 12th Ed.,
3. Joyce, R. S., Allen, J. B., and Sukenik, Amer. Pub. Health Assn., New York,
"
V. A., Treatment of Municipal N. Y. (1965).
Wastewater Activated Car 11. "Manual on Industrial Water and In
by Packed
bon Beds." Jour. Water Poll. Control dustrial Wastewater." American So
Fed., 38, 813 ciety for Testing and Materials, Phila

(1966).
4. Parkhurst, J. D., Dryden, F. D., McDer delphia, Pa. (1963).
"
mott, G. N., and English, J., Pomona 12. Smith, R., "Cost of Conventional and
Activated Carbon Pilot Plant.'' Jour. Advanced Treatment of Wastewater."
Water Poll. Control Fed., 39, R70 Jour. Water Toll. Control Fed., 40,
(1967). 1546 (1968).
"
5. Weber, W. J. G., Pre 13. Rizzo, J. and R. E., "Sec
J., Jr., and Kim, L., Schade,
Evaluation of the Treatment ondary Treatment with Granular Ac
liminary
of Raw and tivated Carbon." Water and Sew.
Sewage by Coagulation
Adsorption." Technical Memorandum, Works, 116, 307 (1969).
San. and Water Resources 14. Hager, D. G., "Adsorption-Filtration in
TM-2-65,
The University of Michigan, the Treatment of Municipal and In
Eng. Div.,
Ann Arbor (1965). dustrial Wastewater." Paper pre
6. Weber, W. J., Jr., "Fluid-Carbon Col sented at the 42nd Annual Conference,
umns for Sorption of Persistent Or Water Pollution Control Federation,
Pollutants." In "Advances in Dallas, Texas, Oct. 5-10, 1969.
ganic

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Physicochemical

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Physicochemical Treatment of Wastewater

It has become apparent over the treatment required by more stringent

by progressive water use and reuse re garding application of advanced phys

vis three-stage treatment systems. On the basis of the encouraging re

performed several years ago to test Without benefit of a biological treat

cated that high levels of removal of ter removals of 95 to 97 percent have

FIGURE 1A.?Packed-bed and expanded-bed adsorption columns and

which would affect normal biological

addition, the direct physicochemical

Trenton, New Jersey. This trickling

FIGURE IC.?Flow metering and control panel in the pilot plant.

of 9 mgd (34,065 cu m/day), with a adsorbers and a series of four ex

pumping capacity of 30 mgd (113,550 panded-bed adsorbers, the two series

FIGURE 3.?Schematic flow diagram for the clarification system.

though the need for addition of Four pumps

Hin. OD ACRYLIC PIPE

1/8 in. RUBBER GASKETS

3/4 in. BOLTS

10 in. STEEL PIPE 1/4 In.WALL

3/4 in. I.P. COUPLING

FIGURE 4.?Detail of the adsorption column. (In. X 2.54 = cm;

were collected in polyethylene bot formed at the main laboratory of the

positing periods. For BOD determi

collected to provide a sample for anal systems were operated as expanded

50 100 150 200 250 300 350 400 450

FIGURE 5.?Removal of total organic carbon by clarification and adsorption in a series

in the neighborhood of three to five stance, with the carbon providing an

system remains as high as it was at a highly clarified primary effluent, the

CLARIFIED PRIMARY EFFLUENT

MAY JUN. JULY AUG.

MAY I JUNEI JULYI AUGI

The IDOD observed in the effluent

?*VvV o-PACKEDBED attempted

TABLE I.?Estimated Wastewater Treatment Plant Costs

Plant Size (mgd) 0.1 0.5 1.0 10.0

Estimated Construction Costs in 1,000 $

Total 137 386 552 2,545

Estimated Operating Costs in c/1,000 GalJ

Fed., 38, 813 ciety for Testing and Materials, Phila

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