EPA-600/2-76-227
October 1976
Environmental Protection Technology Series
NAVAL STORES WASTEWATER PURIFICATION AND
REUSE BY ACTIVATED CARBON TREATMENT
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-76-227
October 1976
NAVAL STORES WASTEWATER PURIFICATION AND REUSE BY
ACTIVATED CARBON TREATMENT
Frank H. Gardner, Jr.
Alvin R. Williamson
Hercules Incorporated
Hattiesburg, Mississippi 39^01
Grant No. S-80lU31
Project Officer
Herbert S. Skovronek
Industrial Environmental Research Laboratory-Cincinnati
Edison, New Jersey 08817
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO U5268
For male by the Superintendent of Document*, U.S. Government
Printing Office, Washington, D.C. 20402
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DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory-Cincinnati, U.S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorse-
ment or recommendation for use.
ii
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FOREWORD
When energy and material resources are extracted, processed, con-
verted, and used, the related pollutional impacts on our environment
and even on our health often require that new and increasingly more
efficient pollution control methods be used. The Industrial Environmental
Research Laboratory-Cincinnati (lERL-Ci) assists in developing and demon-
strating new and improved methodologies that will meet these needs both
efficiently and economically.
This report, "Naval Stores Wastewater Purification and Reuse by
Activated Carbon Treatment", documents the full-scale evaluation of
carbon adsorption for secondary treatment of complex industrial wastes.
Although carbon adsorption has been used widely as a final polishing
operation, very little attention has been given to its potential use in
areas where biological treatment is less than desirable. In demonstrating
that a system including such a physico-chemical process can remove more
than 95% of the organic pollutants (COD) at a reasonable incremental cost
for secondary carbon treatment (31C/1000 gal), EPA has shown that viable,
economical technology is available to meet current and even future dis-
charge or receiving water standards without adversely affecting air or
land quality. For further information on the subject, contact the
Industrial Environmental Research Laboratory-Edison, NJ field station,
08817.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
iii
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ABSTRACT
A laboratory and pilot scale investigation of activated carbon adsorption
for secondary wastewater treatment led to the installation of a system to
provide treatment of a complex chemical plant wastewater. An up-flow,
packed-bed adsorption tower design was chosen, and facilities were included
to provide onsite reactivation of the spent carbon.
The adsorption system satisfactorily treated the wastewater for removal of
dissolved organics at design loading, typically removing 19% of the in-
fluent loading as measured by TOG or COD. The adsorption system was not
capable of removing large concentrations of suspended solids or oil and
grease at design flow rates. The pH of the wastewater feed had to be
neutral or slightly acidic to maintain an adequate removal of dissolved
organics .
The multiple hearth furnace system installed for reactivation of the .spent
carbon proved to be very efficient and economical. Carbon losses through
the furnace and the energy requirements of the system were found to be less
than anticipated when compared to published information used in estimating
the reactivation system operating cost.
The secondary treatment system required a capital investment of $1,U22,000.
During the 19 month period of this grant, operating cost averaged
$30 ,186 /month or 31# per 1000 gallons of water treated.
Based on the demonstrated total operating cost and treatment efficiency of
the unit, it can be concluded that activated carbon adsorption is a feasible
method for providing efficient secondary treatment of a complex chemical
plant wastewater.
This report is submitted in fulfillment of Grant Number-S-80lU31 under the
partial sponsorship of the Environmental Protection Agency. Work was com-
pleted as of January 31, 1975-
IV
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CONTENTS
Foreword iii
Abstract iv
List of Figures vi
List of Tables vi
Acknowledgments vii
I Introduction 1
Industry Background 1
Hattiesburg Manufacturing Operations 1
Primary Wastewater Treatment U
Environmental Effects 7
II Conclusions 9
III Recommendations 11
IV Discussion 12
Process Development 12
Design 17
Performance 20
Economic Evaluation 26
Water Reuse 27
V References 28
VI Appendices 29
A. Laboratory Methods 29
B. Detailed Data 29
VII Glossary 33
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Number
LIST OF FIGURES
Page
1 Wastewater Treatment Area Layout 5
2 Wastewater Treatment Area Photograph 6
3 Carbon Isotherms 13
U Carbon Adsorption Pilot Plant Photograph lU
5 Pilot Plant Performance 16
6 Carbon Adsorption Unit Flowsheet 18
7 Carbon Adsorption Unit Performance 2U
LIST OF TABLES
Number
1 Process Area Wastewater Flow and Analyses 3
2 Primary Treated Wastewater Analyses 7
3 Secondary Treatment System Feed
and Effluent Analyses and Performance Data 23
U Typical Total Treatment System Performance Data 23
5 Cost of Operation 26
vi
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ACKNOWLEDGMENT
We wish to acknowledge the cooperation and encouragement of
Mr. Glen Wood Jr., Executive Director, and the Staff of the
Mississippi Air and Water Pollution Control Commission.
vii
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SECTION I
INTRODUCTION
INDUSTRY BACKGROUND
Hercules Incorporated, Hattiesburg Plant, represents an industry that
traces its beginnings to the time men first took to the seas in wooden
ships. The Naval Stores industry takes its name from the fact that pine
pitch was widely used for treating cordage and caulking wooden hulls in
ancient times. One of the tasks of some of the early American Colonists
was the production of pine pitch for use in England to maintain that
country's far flung merchant fleet and navy.
The Naval Stores industry today produces materials finding a broad and much
more sophisticated spectrum of uses—from chewing gum ingredients to insec-
ticides, from floor polish resins to flavoring essences. The industry
still obtains its raw materials from pine trees. Three methods of accom-
plishing this are: (l) collecting oleoresin from living pine trees,
(2) extracting materials from the "fatwood" remaining from the stumps of
previously harvested mature pine trees, and (3) collecting byproducts from
paper mills using pine furnish for sulfate (kraft) pulping processes.
These three sources lead to (l) "gum" rosin and turpentine, (2) "wood"
rosin and terpene oils, and (3) "crude tall oil" (a mixture of resin and
fatty acids) and "pulp mill liquid" (a mixture of terpene oils), respec-
tively. Expanded background information and bibliographies are available
in published form.l
HATTIESBURG MANUFACTURING- OPERATIONS
The Hattiesburg operation uses raw materials from all three sources. Gum
rosin and turpentine are purchased from primary manufacturers for further
processing. Stumps, crude tall oil and pulp mill liquid are processed and
refined to produce rosin and terpene oils. Rosin, turpentine, and terpene
oils so produced are then chemically modified in a variety of processes to
produce a diverse line of industrial chemicals. The various processes used
include hydrogenation, disproportionation, polymerization, adduction,
esterification, saponification, ethoxylation, and ammoniation to produce
resins with enhanced properties. Terpene fractions may be marketed as such
or further processed by hydrogenation, dehydrogenation, hydration, or
oxidation to produce intermediate chemicals, alcohols, hydroperoxides, etc.
Operations carried out at the Hattiesburg Plant but not based upon raw
materials of Naval Stores origin include production of a miticide, a
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specialty synthetic rubber, hydrocarbon resins, and several chemicals for
the paper industry including wet-strength resins, wax emulsions, and de-
fearners.
The plant has three sewer systems. Sanitary sewage is kept separate from
all other wastes and is delivered to the City of Hattiesburg sanitary
sewage system. Waste cooling water (non-contact) is discharged to a system
which bypasses the wastewater treatment unit. Contaminated wastewaters from
the various processes, including process area surface drainage, are col-
lected through a system of sumps and lift stations for delivery to the
wastewater treatment area. Where feasible, process area sumps and lift
stations include provisions for on-the-spot removal of settleable solids
and/or floating oils.
Measurement of the various process area wastewater flows is not presently
instrumented. Flows are measured from time to time as needed by manual
means appropriate to the particular area. In most cases flows are calcu-
lated from timed accumulation in sumps.
To determine the area wastewater contamination levels, grab samples are
secured from.each process area three to five times a week until at least
twelve samples have been taken. Samples are analyzed the same day they are
caught. Free oils and settleable solids are removed by decantation and
the Total Organic Carbon (TOG) content is determined with a Beckman Model
915 TOC Analyzer. Results from the 12 samples are averaged. This procedure
is repeated from time to time as needed to keep the data current. It is
important to note that these analytical data do not include those oils and
solids which are readily separable by decantation. The analytical measure-
ments include dissolved organics plus suspended and/or emulsified organics.
A breakdown of area flows and Total Organic Carbon contents is shown in
Table 1. This kind of information has been invaluable in guiding in-plant
pollution abatement efforts and in distributing treatment costs to the
product cost centers.
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TABLE 1. PROCESS ARIA WASTEWATER FLOW AND ANALYSIS
U)
Process area
Stump processing
Tall oil processing
Flow,
gpd
258,000
18U.OOO
Pulp mill liquid processing — i ,Q OQQ
Terpene hydration — • . *
Rosin hydrogenation
Rosin polymerization
110,000
550,000
Rosin disproportionation — T_ 352 000
Rosin saponification — '
Rosin adduction — i
Rosin esterification 1 — 500,000
Rosin salts —
Rosin ammoniation —
Ethoxylation process
Terpene dehydrogenation
Terpene oxidation
Petroleum resins — ^
Miticide
Paper chemicals
Synthetic rubber
Miscellaneous
Totals
— 306,000
75,000
100,000
1*3,000
19l*,200
2,592,000
Total
mg/1
1,160
1,110
1,150
220
2l*0
275
150
720
1,070
500
1*35
U85
organic carbon
Ib/day
2,500
1,700
190
200
1,100
580
625
1,830
670
200
180
700
10,1*75
content*
% of Total
23.9-1
Basic
16.2 I- processes
1.8 J Ul'9*
1.9-1
10.5
5.5
6.0
17.5-
Modification
processes
1*1. h%
6.1*-i| Non -naval
1.9 1 stores
1.7 I" operations
6.7-* 16. T%
100.0
*After removal of free oils and settleable solids. Represents contaminants present as
dissolved organics and finely dispersed and/or emulsified oils.
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PRIMARY WASTEWATER TREATMENT
The wastewaters from the various processes are delivered to a common waste-
water treatment area, shown in Figures 1 and 2. The water first enters an
impounding basin installed in 1951 to provide 5-6 hours retention time for
equalization and preliminary clarification. Overflow and underflow baffles
permit floating oils to be removed by a skimmer and settled solids to be
removed periodically by dredging.
The pH of the mixed wastewaters in the impounding basin is normally about
3-U. This low pH was found to be very desirable since it minimizes foaming
and emulsification and reduces the solubility of the organics contained in
some of the waste streams, thus enhancing performance of the primary treat-
ment system.
Because of the preliminary clarification accomplished in the impounding
basin, the Total Organic Carbon content of the exit water is well repre-
sented by the totals shown in Table 1 (area flows and analysis) which, as
described earlier, resulted from analysis of partially clarified samples.
The impounding basin exit water still contains suspended and emulsified
organics, however, which are removed in the next treatment stage, the air
flotation clarifier.
The dissolved air flotation clarifier, installed in 1972, is 52 ft in diam-
eter and operates at 8.5 ft water depth, with a rated capacity of U.32 mgd.
Following the clarifier is a two-stage pH adjustment system using 50$
aqueous NaOH to bring the pH up to 6-7-
Typical primary treated wastewater analyses are shown in Table 2. These
results were obtained on daily composites made up from grab samples caught
every two hours (12 samples per day). With average inlet TOC of U85 (Table
l), the average outlet TOC of 193 (Table 2) indicates a contaminant level
reduction of 60%. At the normal flow rate of 2,592,000 gpd, the air flo-
tation clarifier is indicated to remove 6,300 Ib/day of TOC.
Oils recovered from the impounding basin and clarifier are utilized as fuel
in the main plant Power House, thus recovering fuel value. Solids from the
impounding basin and clarifier are presently disposed of by landfill
(private contractor), but we expect to eventually develop the capability of
recovering fuel value from this material also. Laboratory investigation
indicates that dewatering, by adding a light fuel oil, for example, produces
a readily combustible product.
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INLET STREAMS OF
CONTAMINATED WATER
RECOVERED
OIL
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Figure 2. Wastewater treatment area photograph.
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TABLE 2. PRIMARY TREATED WASTEWATER ANALYSIS
Date, 1973
9A
9/7
9/10
9/25
9/26
10/1
10/2
10/3
10 A
12/5
12/6
12/10
12/17
12/19
AVK.
pH
8.0
8.1
6.6
6.9
7.9
6.8
6.6
7-1
6.0
6.0
6.0
7.U
6.0
7.2
6.9
mg/1
COD
70 U
6kQ
896
560
6Ui
720
576
61*0
1077
800
960
688
62k
kkQ
713
TOC
221
191
235
168
192
1U9
183
169
200
221
265
175
167
171
193
Performance of the primary system has been generally satisfactory. As men-
tioned earlier, the pH in the impounding basin and clarifier should be
about 3-k and the unavoidable occasional excursions above this range impair
the performance of the system. Work is in progress to provide a control
system to overcome this difficulty.
ENVIRONMENTAL EFFECTS
Treated effluent from the Hattiesburg Plant is discharged to a city
drainage ditch which leads to the Bowie River (a tributary of the
Pascagoula River System). At Hattiesburg, the Bowie River empties into the
Leaf River, which joins the Chickasawhay River near Merrill, Mississippi,
to form the Pascagoula River.
This is a more or less typical coastal river system with normally murky,
often muddy water and large flow variations. It is used for recreational
fishing and boating, and in the lower reaches (below Merrill) for commer-
cial fishing.
The Leaf River receives municipal wastewaters from the cities of Hatties-
burg and Laurel and industrial wastewater from the Masonite Corporation
plant in Laurel in addition to Hercules' wastewater.
The river system has been surveyed from time to time by various groups. A
survey made in 1961-1962 by the Mississippi State Game and Fish Commission
reported: "The dilution ratio is such in the Hattiesburg area that a
complete deoxygenation of the stream is probably never accomplished but the
water quality is altered to the extent that it is not in the optimum range
for normal aquatic conditions to exist for approximately a twelve-mile
section of the stream".2
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Extensive data are to be found in the "Pascagoula River Basin Water Quality
Management Plan" developed by Pat Harrison Waterway District in 1973.3
The consensus seems to be that the river system assimilates these wastes
without disastrous effects but not without quality deterioration. There
have been fish kills in the system, but most have been attributed to natural
(or unknown) causes. There have been none directly attributable to Hercules'
waste discharge within the experience of the authors (approximately 20
years). The nature of the contaminants in the Hercules wastewater is such
that they have oxygen consuming potential, but there is no evidence that
toxicity to aquatic life is a problem at the dilution levels existing.
In recent years, abatement efforts on the part of all the major dischargers
have resulted in measurable improvement in the river quality. Dr. B. J.
Grantham, a Marine Biologist at the University of Southern Mississippi at
Hattiesborg, was quoted in the Jackson Clarion Ledger (daily newspaper) on
March 30, 1973, as stating that the upper region of the Pascagoula River
"is becoming one of the cleanest stretches of water in the Nation". This
observation predates the startup of the secondary treatment process which
is the subject of this report.
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SECTION II
CONCLUSIONS
An activated carbon adsorption system is capable of providing secondary
treatment of a complex chemical plant waste-water for removal of dissolved
organics provided certain design criteria are adhered to.
Overall removal of dissolved organics from the wastewater as measured by
COD, TOG, and BOD was typically about 79 per cent during periods of steady
state operation with design feed conditions. Reduction across the total
system amounted to ^95 per cent.
Make-up carbon required to replace the carbon lost in the handling and
regeneration cycles amounted to 3-5 per cent per cycle. A treatment cost
(ex-depreciation) of 31.k$ per thousand gallons of water was achieved
during the evaluation period. During steady state operating periods when
the wastewater feed was similar to design quality, a COD removal cost
(ex-depreciation) of 6 cents per pound of COD was achieved.
The regenerated carbon was found to be slightly more active for removal of
organics from the plant wastewater than virgin carbon. This phenomenon can
be attributed to the fact that the organics in this wastewater stream are
adsorbed in the larger pores, and during reactivation of the carbon many of
the smaller pores are fractured to create a higher proportion of large pores
per unit weight of carbon.
With a high Btu value organic load such as present at this plant, fuel re-
quirements for carbon regeneration were significantly lower than expected.
An up-flow, packed-bed adsorption system provides maximum use of the
activated carbon and minimizes carbon inventories. This type of system does
have certain limitations in that the wastewater feed cannot contain more
than 10 ppm of suspended solids or 15 ppm of oil and grease without causing
a high pressure drop across the carbon bed which, in turn, makes premature
pulsing or slugging of the carbon bed necessary.
A build-up of carbon fines in the system occurs after the carbon has gone
through many regeneration cycles, and this leads to high bed pressure drop
problems. Purging of fines by back-flushing the regenerated carbon storage
tank with water satisfactorily corrects this problem.
When pulsing the carbon bed and after completely filling an adsorber, carbon
fines will show periodically in the treated effluent. Provision for re-
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cycling carbon-contaminated effluent is necessary.
Biological activity also occurs in the carbon "beds at times, which increases
the carbon "bed pressure drop "but also increases the efficiency of the. system
for removal of dissolved organics. If the "bed contact time of the waste-
water is long enough to deplete the dissolved oxygen in the water, the
biological activity becomes anaerobic. When this happens, the treated
water develops a characteristic unpleasant odor.
The pH of the feed wastewater must be maintained below a maximum of 7-5 to
provide efficient removal of dissolved organics. If the pH is above 7-5,
the treatment efficiency drops off in proportion until reaching a pH of ap-
proximately 9- When the pH is above 9» the treatment efficiency drops
almost to zero. COD loadings on the carbon of 0.9 pounds COD per pound of
carbon were achieved during operating times when a high bed pressure drop
was not the controlling factor in determining when the bed had to be pulsed.
During periods when there were pressure problems, a COD loading of 0.63
pounds COD per pound of carbon was achieved.
Equipment and piping designed for handling carbon/water slurries should not
be constructed of carbon steel but should be either stainless steel or
epoxy fiberglass to avoid serious corrosion problems.
The activated carbon system also removes a portion of certain metal con-
taminants in the wastewater.
Activated carbon adsorption is acceptable for providing secondary treatment
of a wastewater stream, but as for most systems, it cannot continuously be
overloaded and expected to produce the same quality effluent. The system
will provide a defined capacity for removal of dissolved organics even
under overloaded conditions.
10
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SECTION III
RECOMMENDATIONS
Additional performance data are needed under steady state operating condi-
tions to determine accurately the pressure drop characteristics for acti-
vated carbon loaded with an organic waste that is oily in nature. This
information should be provided before a system is designed for treatment
of this type of wastewater stream.
Before an up-flow packed-bed adsorption system design is chosen for treat-
ment of a wastewater stream, it should be established that adequate control
of the suspended solids, oil and grease, and pH of the feed is provided.
In short, an activated carbon secondary treatment system must be preceded
by an effective primary treatment system if the total unit is to be eco-
nomically and technically acceptable.
Investigation should be undertaken to develop an activated carbon adsorp-
tion system that takes advantage of the biological activity that occurs
in the carbon bed.
The design of a carbon adsorption system should include facilities in the
process for removal of carbon fines that build up in the system after suc-
cessive regeneration cycles.
All piping or equipment that remains in contact with the activated carbon
water slurries should be stainless steel or fiber glass.
11
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SECTION IV
DISCUSSION
SECONDARY TREATMENT PROCESS DEVELOPMENT
In planning for secondary water treatment it had long been thought that we
would follow the time-honored path of biological processing. As the time of
decision drew nearer, the problems we anticipated with a biological system
loomed ever larger. The land area which would be required was available
only on the wrong side of the plant which now finds itself within the resi-
dential portion of the city. In a pollution sensitized community, the odor-
producing potential of the system would be frightening. Nobody really
seemed to have satisfactory solutions to the problem of biological sludge
disposal.
In preliminary discussions with city officials there appeared to be little
interest in joint treatment facilities. One discouraging aspect was that
the Hercules Plant and the city's treatment area are on diametrically op-
posite sides of the city and a new sewer main would be required for the
entire distance.
We knew that carbon adsorption had established utility for tertiary treat-
ment and that a few secondary treatment systems were in operation or being
planned. We therefore undertook laboratory experiments to see how effect-
ive carbon might be on our wastewater stream.
In our laboratories, carbon isotherms revealed that carbon was indeed ef-
fective on our wastes, and adsorption of 0.85 lb COD/lb carbon was indi-
cated. This was a higher loading than we had been led to expect, so we
obtained independent confirmation from other laboratories. Hercules' Envi-
ronmental Services Division's laboratory in Houston, Texas found an adsorp-
tion of 1.2 lb COD/lb carbon, and Calgon Corporation, Pittsburg, Pa., found
an adsorption of 1.0 lb COD/lb carbon. Results of the three studies are
shown in Figure 3-
With the encouragement of high adsorption potentials, we constructed a pilot
plant to test continuous granular carbon treatment of wastewater drawn from
the plant impounding basin. A photograph of this unit is shown in Figure U.
The dissolved air flotation clarifier portion of the primary treatment system
described earlier was still under construction when this work was undertaken,
so a small scale clarifier was included in the pilot plant. The pilot unit
was also equipped for pH adjustment and filtration through "pea" gravel in
12
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2.0
1.0
GRAMS COD
ADSORBED/GRAM
OF CARBON
1
HERCULES E.S.D. LAB.
1.2 LB COD/LB CARBON
HATTIESBURG LAB.
0.85 LB COD/LB CARBON
100
RESIDUAL COD |ppm)
CALGON LAB.
1.0 LB COD/LB CARBON
1000
Figure 3. Carbon isotherms (Calgon Filtrasorb 400).
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Figure 4. Carbon adsorption pilot plant.
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addition to carbon treatment. The carbon treatment columns were 3-in inside
diameter Pyrex glass pipe sections 5 ft long packed with h.h Ib each of
Filtrasorb UOO carbon (Calgon Corporation).
The unit was operated for a total of 52 days exploring the effects of flow
direction (up vs. down), irrigation rate, and contact time. Conclusions
drawn from this work were as follows:
1. Upflow vs. downflow.
We found that treatment efficiency was approximately the same
either way. The upflow pattern is more tolerant of suspended
solids in the feed water and, with slight bed expansion (5%
max.), lower pressure drops can be obtained. As irrigation
rate is increased, however, bed expansion rises sharply and car-
bon losses due to attrition and decantation became significant.
The relationship between bed expansion and irrigation rate varies
with carbon source and condition (organic loading). Downflow
operation, because of the filtration effect of the bed, requires
periodic back washing and pressure drop will average slightly
higher than for expanded bed upflow, increasing as the unit
approaches the need for backwash.
2. Irrigation rate.
Downflow irrigation rates of 3-5 gpm/sq ft were evaluated and
found satisfactory. An upflow irrigation rate of 3 gpm/sq ft
was satisfactory, but 5 gpm/sq ft resulted in excessive bed
expansion and carbon losses.
3. Contact time.
Contact times between U5 and 50 minutes (based on settled bed
volume) were found to give COD removals of 75-85$ within the
range of irrigation rates found satisfactory.
U. Carbon loading.
The COD loadings found by isotherm were confirmed in these tests.
In two tests run to carbon exhaustion, loadings of 1.03 and 0.96
Ib COD/lb carbon were obtained.
The COD removal performance of the pilot plant unit during one of the down-
flow tests is shown in Figure 5.
Having in hand the basic information needed to design a carbon adsorption
secondary treatment unit we faced one more hurdle. The common wisdom of
the day (1970) said that a carbon unit would be significantly more expensive
to build and operate than a biological unit. To clarify this issue we con-
structed and operated a biological treatment (activated sludge) pilot plant.
The basic design and operating parameters were provided by a Hercules sub-
sidiary, Black, Crow and Eidsness, Inc., of Gainesville, Florida. The unit
15
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CHEMICAL
OXYGEN DEMAND
|mg/l|*100
H
ON
12r
10
CARBON ADSORPTION WATER TREATMENT EFFICIENCY
FEED TO CARBON SYSTEM
EFFLUENT FROM CARBON SYSTEM
0 1 23 4 5 6 7 8 9 10 11 12 13 14 15 16
TIME OF OPERATION (DAYS)
Figure 5. Pilot plant performance.
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was "built to process 5 gph of primary treated water with the following op-
erating conditions: 72 hr equalization of the primary treatment effluent,
10.5 hr aeration contact time, pH 6.5-7-5, clarifier settling time 3.6 hr
at 600 gpd/sq ft, 5 gph (l/l) recycle of clarifier bottoms, and mixed
liquor volatile suspended solids level of 2,500 mg/1 - total suspended
solids level approximately 3,600 mg/1. The pilot biological unit was oper-
ated for a period of 28 days with quite variable performance, but a treat-
ment efficiency of 75$ was demonstrated.
Armed with basic design data for carbon and biological treatment systems,
we obtained preliminary construction and operating cost estimates for units
of both types to treat the total plant contaminated wastewater, 2.6 mgd, as
follows:
Estimated cost:
System Type
Biological Carbon Adsorption
Construction $2,013,808 $1,781,000
Operation (annual) 170, 1*93 l8l ,623
These estimates were interpreted as indicating that the choice of type of
system need not be influenced by cost but could be made on the basis of
other considerations. The carbon system was therefore chosen, primarily on
the basis of greater flexibility, tolerance of feed variations, and better
quality water output (particularly better color and lower suspended solids).
In addition, carbon is not affected by chemicals which might be toxic to
biological systems. Although we did not encounter problems with toxicity
in our evaluation of biological treatment, we felt it to be a threat because
of the wide variety of chemicals used and produced in the plant. Protection
from this threat would necessitate extended pre-treatment equalization,
requiring land area not readily available.
TREATMENT UNIT DESIOT
Having settled on carbon adsorption as the system to be used, in-depth en-
gineering design studies were undertaken. Various aspects of the design
studies are discussed below and the final design flowsheet is shown in
Figure 6.
1. Prefiltration.
The effluent from the primary treatment system (after pH adjustment) was
found to contain about 50 mg/1 of suspended solids. Tests indicated that a
high-rate downflow mixed media filter would reduce this to 5 mg/1. The
solids removed were oily in nature and their removal reduced the TOO of the
water by an amount equal to the solids removed (^5 mg/l). Conventional
backwashing plus air scouring was found satisfactory for removing solids
collected in the filter and controlling pressure buildup. The backwash
water could be clarified by dissolved air flotation and therefore, could be
recycled through the primary treatment system. Basic filter parameters
17
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H
00
SECONDARY
WASTE WATER TREATMENT
HATTIESBURG, MISS.
REACTIVATED CARBON SLURRY
REACTIVATED
CARBON SLURRY
FURNACE
FEED
TO
IMPOUNDING BASIN
OVERFLOWS
Figure 6. Carbon adsorption design flow sheet.
-------
were: high rate downflow type, 13 gpm/sq ft feed rate, 3 to 8 "backwash
cycles/day composed of 30 second air scour at 3 cu ft/sq ft, 1 minute set-
tling time, and 5 minute backwash at 15-18 gpm/sq ft. In the final design,
three filters (parallel flow) were provided and they were to operate under
full system pressure, being located in the flow line between the system feed
pumps and the carbon adsorption towers.
2. Carbon adsorption towers.
The adsorption system chosen in the design studies was the up-flow, packed,
bed type.1* This type of system was found to offer lower construction cost
and greater flexibility in operation. A countercurrent flow pattern was
chosen because more efficient use of the carbon results since this system
approaches that of a continuous countercurrent operation when the rate of
carbon bed pulsing is properly designed. Three adsorbers to be operated in
parallel were chosen because of the economics of vessel construction and
shipment cost. Each adsorber was to operate at a minimum bed contact time
of UU minutes at a maximum cross section flow of 7-35 gpm/sq ft. The ad-
sorbers are designed for an average contact time of U8 minutes at a cross
section flow of 6.6 gpm/sq ft. The carbon pulsing system is designed to
remove approximately 5% of the carbon bed daily from the bottom of the ad-
sorber while regenerated carbon is charged at the top. All carbon transfers
are made while the carbon is in a water slurry. External design data for
this type of carbon adsorption system can be found in the U.S. Environmental
Protection Agency Technology Transfer Manual on Carbon Adsorption.5
3. Spent Carbon Reactivation.
The spent carbon is dewatered to approximately 50$ water by weight with an
inclined dewatering screw and discharged by gravity into a multiple hearth
furnace for reactivation. The furnace is a 5 hearth 12 ft OD unit capable
of reactivating 33,600 pounds of carbon per day. In the furnace, the damp
carbon is dried and heated to 1,600-1,800 °F with three burners on each
of two hearths (#3 and #5). The burners are normally fired with natural
gas but can be fired with #2 fuel oil if necessary. Supplemental steam is
added to the furnace to control the reactivation atmosphere at a ratio of
one pound steam per pound of carbon and the hot gases flow countercurrent
to the flow of the carbon. The furnace system is designed to be operated
by automatic controls and with safeguards to permit unattended operation.
An after-burner is included in the furnace design to remove objectionable
odors and to insure complete combustion of the organics in the furnace off
gases.
The exhaust gases then pass through a wet scrubbing system for cooling and
removal of particulate matter before being discharged to the atmosphere.
This system is designed to meet current air pollution laws. The scrubber
discharge water is returned to the primary treatment impounding basin.
U. Overall design performance parameters.
The overall design performance parameters for the secondary treatment system
were:
19
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Performance parameters:
Influent Effluent
System flow, mgd 3.35
Net flow, mgd 3.2k
COD, mg/1 700 125
TOG, mg/1 200 30
BOD, mg/1 250 50
SS, mg/1 50 <5
DS, mg/1 650 1^00
Oil and grease, mg/1... 25 5
pH 6-8 6-8
Temperature, °C 36 36
Carbon flow, Ib/day 21,000
Carbon loss, Ib/day 1,050
TREATMENT UNIT PERFORMANCE
The performance of the activated carbon adsorption system chosen for treat-
ment of the plant wastewater will be described in two phases; l) an evalu-
ation of process equipment with recommendations, and 2) an evaluation of the
process performance with recommendations.
1. Evaluation of Process Equipment.
When the waste treatment system was started up it was noticed that the oper-
ation of the mixed media filters was very rough during a backwashing cycle.
The primary cause of the problem was the high operating pressure of the
filters (175 psig inlet) in conjunction with the abrupt opening and closing
of the butter-fly valves used on the filter. Within U8 hours of operation
start-up the discharge laterals in the filters collapsed allowing the garnet
in the filters to be washed out with the water. The garnet flowed into the
carbon adsorption towers with the wastewater where it mixed with the
activated carbon. As carbon was slugged from the towers and processed
through the reactivation furnace portions of the garnet melted and plugged
up the furnace. In the various carbon handling systems the garnet eroded
the transfer eductors and eroded the flow control valves to each adsorption
tower. After the failure of another set of discharge laterals, the problem
was diagnosed to be due to the filter bed settling as a plug on the unsup-
ported laterals which then collapsed. The original laterals which were ABS
plastic were replaced with stainless steel wire laterals supported inter-
nally with slotted stainless pipe. The valve operation on the filters was
smoothed out by placing needle valves on the operating air supply lines
which could be adjusted to .provide a. smoother slower opening cycle. Since
these modifications were completed, the automatic operation of these filters
has been very dependable and designed operating parameters for the units are
easily attained.
The carbon adsorption unit consists primarily of three sections, the carbon
adsorption towers, the carbon storage and handling system, and the spent
carbon reactivation furnace system.
20
-------
The carbon adsorption towers are constructed of 3l6 stainless steel and no
corrosion problems have been observed. The only alterations in the tower
design have been to provide internal supports for the effluent screens to
prevent them from bending during slugging operations when an air pocket
rises through the adsorption tower and to replace the rupture disc pressure
control system with a vented stack pipe overflow system to handle sudden
surges in the water feed rate. The inlet and discharge piping was installed
with welded joints and carbon steel pipe was used. For handling the feed
water to the adsorbers the steel pipe is holding up satisfactorily but the
discharge piping has been replaced with fiber glass and stainless steel
pipe. The carbon fines which escape with the treated water caused severe
erosion and galvanic corrosion problems at all elbows, welds and the bottoms
of straight run pipe sections. Both the stainless and fiber glass pipe
appear to be holding up satisfactorily.
The tanks used in the handling and storage of the activated carbon are con-
structed of stainless steel and are providing satisfactory service. The
carbon transfer pipe system was originally constructed of mild steel pipe
but as was the case for the adsorber effluent piping it is being replaced
with stainless pipe. Where turns are made in the transfer of carbon slur-
ries, long-sweep rubber sections of pipe were originally used. These joints
do not have any longer life than if the joint were constructed from carbon
steel. It is recommended that all carbon transfer piping be of stainless
steel and that long sweep stainless steel elbows be used for direction
changes. To move the .carbon slurries, the water powered eductors have
proven to be very satisfactory if constructed from stainless steel.
In the original design, no provision was made for removal of carbon fines
which accumulate in the system after successive regeneration cycles. To
correct this problem, a water sparge ring was installed in the reactivated
carbon storage tank so that accumulations of fines could be flushed out of
the system and back to the primary treatment unit.
As previously described, a multiple hearth furnace system was constructed
for reactivation of the spent carbon. This unit has proven to be very ca-
pable of reactivating spent carbon at design rates and conditions. The
unit was shut down and restarted on many occasions during the start-up of
the wastewater treatment system when failures in the laterals of the mixed
media filters occurred. The furnace system was performing well until re-
cently when sections of the brick which make up the #1 hearth started buck-
ling up until the rabble arm teeth broke them loose. The bricks caused
severe erosion of the rabble arm teeth and caused cracks in the rabble arms
of the remaining four hearths. This problem appears to be a common one
since other industries with similar furnace systems have had similar prob-
lems occur recently. Initial studies indicate this problem to be due to
the high moisture content of the spent carbon as it is charged to the first
hearth. To keep the unit in operation, the furnace was shut down and the
remaining bricks in the damaged hearth were removed. At the writing of this
report, the proper repair of the rabble arms and teeth cannot be made until
new parts are obtained from the furnace manufactuer- The furnace was placed
back in operation with very badly damaged rabble arms and three effective
hearths, but it is still producing high quality reactivated carbon at
21
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reduced feed rates.
We recommend that a furnace system such as this one be shut down at least
every 3 months for an inspection of the brickwork and rabble arms and teeth
and that a ceramic coating recommended by the manufacturer be applied to
the brickwork surface in the first hearth. This coating reportedly aids in
preventing a failure of the brickwork due to the high moisture content of
the spent carbon. We understand that this coating has proven satisfactory
for furnaces operated by Calgon Corporation for reactivation of spent
carbon.
2. Evaluation of Process Design and Performance.
The performance of this activated carbon adsorption system for treatment of
the plant wastewater is summarized in Tables 3 and k, Figure 7, and detailed
in Appendix B. The time lapses between periods of data compilation rep-
resent times when operation of the system was impaired by mechanical prob-
lems as previously described.
During the period the secondary water treatment facilities were under con-
struction, additional work was completed to segregate uncontaminated water
from the plant wastewater sewer system resulting in an overall reduction of
flow. Although the flow was reduced 11$, the level of organic wastes in
the water increased during this time.
The water treatment facilities were started up during a period when the
plant wastewater contained 35$ more dissolved organics than the system was
designed to remove. The carbon towers were initially capable of handling
this additional load since the carbon was completely fresh.
Reductions in the COD and TOC of the wastewater of 8^ and 79 per cent re-
spectively were obtained by the carbon system. During this period, carbon
loadings of 1.2 Ib COD per pound of carbon and O.Wi Ib of TOC per pound of
carbon were realized. The system was shut down at times for mechanical
repairs to the mixed media filters and it was observed that biological ac-
tivity was occurring and that this activity could have led to misleading
results in evaluation of the organic loading data. It was observed when
biological activity was occurring that it was anaerobic and led to high
pressure drops across the carbon bed. The biological activity occurred at
the wastewater outlet section of the adsorption tower and disappeared when
normal slugging of the carbon bed was started.
The data compiled during periods of what is described as typical or design
operating conditions illustrate the effectiveness of the system for removal
of wastes from the feed water. Typical operating periods were defined as
times when carbon beds were being pulsed at design rates and the system
wastewater feed quality was similar to that used for calculating design
loading data. COD loadings of 0.9 Ib COD per pound of carbon and TOC load-
ings of 0.38 Ib TOC per pound of carbon were obtained during these periods.
While in continuous service many design problems were discovered and cor-
rective action taken to eliminate them. It was found that the pressure
drop across the carbon bed was approximately 30$ higher than design data.
The reason was that activated carbon loaded with organics has different
22
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TABLE 3. SECONDARY TREATMENT FEED AND EFFLUENT ANALYSES
AND PERFORMANCE DATA
Item
Influent Effluent % Reduction
Removal
lb/day-
Design:
(3.2U mgd)
COD, mg/1
TOG, mg/1
BOD, mg/1
Start-up period:
(2.592 mgd)
COD, mg/1
TOG, mg/1
Typical operation:
(2.592 mgd)
COD, mg/1
TOG, mg/1
600
160
250
975
222
752
203
125
30
50
152
160
79
81
80
Qk
79
79
79
12,800
3,500
5,^00
17,800
3,800
12,800
3,500
Selected samples :
(2.592 mgd)
BOD, mg/1
Phenols, mg/1
Ni, mg/1
Zn, mg/1
Cd, mg/1
Cu, mg/1
Cr, mg/1
TS, mg/1
SS, mg/1
DS, mg/1
Chlorides, mg/1
N02, mg/1
Oil and grease, mg/1
300
U.66
1.02
1.11
0.91
1.29
1.12
1,211
81
1,130
1.82
5.16
28.1
82
0.58
0.33
0.29
0.22
0.36
0.26
965
13
952
0.8U
It. 28
2.2
73
88
68
7U
76
72
77
20
8U
16
U8
17
92
It, 700
88
15
18
15
20
19
5,300
1,500
3,800
19
19
560
TABLE U. TYPICAL TOTAL
(
Parameter
COD
TOG
BOD
SS
Oil and Grease
Raw Waste
Water
(mg/1)
3,200
1,200
1,600
320
500
TREATMENT SYSTEM PERFORMANCE DATA
;g 2.592 mgd)
Primary
Treated
Effluent
(mg/1)
670
198
267
72
25
Secondary
Treated
Effluent
(mg/1)
1U3
37
73
12
2
Overall
Reduction (%}
95.5
96.9
95-^
96.3
99-6
23
-------
12
10
CHEMICAL
OXYGEN DEMAND
(mg/l) X 100
6
ro
CARBON SYSTEM FEED
J I
J I
CARBON SYSTEM EFFLUENT
J I
I I
j I
JUL. ASONDJ FMAM-SO
73 74
TIME OF OPERATION (MONTHS)
N D
J F
75
Figure 7. Carbon adsorption unit performance.
-------
pressure drop characteristics than virgin carton. To counteract this prob-
lem it would be necessary to design the carbon adsorption tower to withstand
higher operating pressures. In the case of this unit the only solution was
to pulse the bed more often to reduce the organic loading on the carbon bed
especially since the organics form an oily, greasy film on the carbon
surface. When evaluating the oil and grease content of the feed wastewater,
it was found that for concentrations of less than 15 mg/1, the pressure drop
across the bed was reduced to within operating limits, but if it was higher,
the flow through the adsorber had to be reduced to lower the bed pressure
drop. Other than the pressure drop problem, the adsorption system operated
as anticipated when organic loadings and other operating conditions were
near design values.
The carbon system was also operated during periods when the feed quality and
system operating procedures were not typical as shown in Figure 7. Neverthe-
less COD and TOG removals still ran approximately 50$.
It was found during periods when the carbon bed was not pulsed on a routine
basis that excessive bed pressure drops occurred and that effluent water
quality deteriorated very quickly. During these periods, it was observed
that anaerobic bacteria became very active in the top of the carbon bed.
Another parameter of the system feed, pH, was found to have a tremendous
effect on the quality of effluent from the carbon bed. It was found that if
the pH of the system feed exceeded 9-0, the effluent water quality was re-
duced as much as 50$ and it took several days of pulsing the carbon bed
(depending on how high the pH was above 9-0) to restore its treatment effi-
ciency. The most significant effluent water quality deteriorations, however,
occurred as a result of inadequate primary treatment. Carbon regeneration
capacity sets a definite limitation on system overload capacity. The furnace
capacity rating of 33,600 Ib/day compared to design carbon consumption of
21,000 Ib/day would indicate an overload capability of 60%. This capability
could probably be realized if the overload was dissolved organics. Our pri-
mary treatment difficulties, however, often resulted in excessive oil and
grease levels which coated the carbon surface with an oily greasy film at
rates which could not be matched by the regeneration furnace.
The reactivated carbon produced by the multiple hearth furnace is actually
more effective than virgin carbon for treatment of the plant wastewater.
Laboratory isotherms comparing the reactivated carbon to virgin carbon indi-
cate an average reactivation efficiency of 10U$. In discussing these
results with various carbon manufacturers they indicated the reason for
these results was that the very small pore sizes of the virgin carbon were
not utilized in treatment of our plant effluent and after reactivation, the
carbon contained a higher percentage of the larger pores and fewer of the
small pores. This condition develops because the smaller pore openings are
more easily fractured during the reactivation process to larger sizes. The
carbon losses through the furnace system and carbon handling facilities are
averaging from 3-5 per cent depending on the maximum furnace temperature.
Typical operation is to fire the Number 5 hearth to a temperature of
1,6"50°F., and to only fire the Number 3 hearth when the temperatures of the
remaining hearths drop below normal for the existing carbon feed rate and
organic loading.
25
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Data presented in Table 2-A (Appendix) indicate significant removals of
phenols and certain metals by the carbon adsorption system. Also in this
Table, the data show increases in nitrogen (ammonia) in all samples ana-
lyzed and in nitrogen (nitrate) in about half of the samples upon passage
through the carbon system. We do not presently have an explanation for
these increases.
ECONOMIC EVALUATION
The costs for operation of the carbon adsorption wastewater treatment
system are summarized in Table 5.
TABLE 5- HATTIESBURG SECONDARY WATER TREATMENT COSTS
7/1/73-1/31/73
Item
Actual avg.
cost/month
Grant
forecast
Operation:
Labor (incl. wage benefits)
Chemical control
Supervision
Overhead
Subtotal
Maintenance:
Labor (incl. wage benefits)
Materials
Subtotal
2,304
537
81
1,909
4,831
4,262
3.357
7,619
4,116
2,150
Utilities:
Electricity
Natural gas
Steam
Subtotal
Activated carbon**
Grand total
Treatment cost***
4,153
675
-0-
¥7828
12,908
30,186
0.314
875
5,886
441
7,202
10,243
28,047
0.292
*Cost not anticipated in forecast.
**Actual carbon usage/month was 33,273 lb; forecast was 32,010 Ib.
***$/1000 gal, @ 96 X 106 gal/month.
The operating cost for the treatment system is slightly higher than fore-
cast due to several minor items. No allowances were made in the forecast
for chemical (analytical) control of the operating system or for overhead
as charged in the plant accounting system. A lower than forecast operating
labor cost partially offset these charges since the number of operating
personnel required was less than forecast.
26
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The maintenance costs for the system were higher than the forecast amount
due to replacement of many process lines constructed of carbon steel pipe
with stainless steel, replacement of the laterals in the mixed media
filters and various minor alterations in the equipment design.
The utilities cost was lower than forecast due to a reduced consumption of
natural gas since it was found unnecessary to fire both hearths in the car-
bon reactivation furnace for proper operation, however, the electrical re-
quirements for the treatment system were found to be higher than antici-
pated which partially offset the reduction in cost by reduced natural gas
consumption.
The activated carbon consumption was slightly higher than forecast due to
losses that occurred when recovering carbon that was contaminated with
garnet when the laterals in the mixed media filters ruptured and to price
increases in the carbon cost.
In summary, the treatment cost for the carbon adsorption facility was very
near anticipated values (29.8^/1000 gal) and averaged Sl.WlOOO gal of
water treated. During steady state operating periods when the wastewater
feed was similar to design quality a COD removal cost of 6^/lb was
achieved. On the average, however, actual cost was about 8<£/lb of COD.
The carbon adsorption system required a capital investment of $1,U22,000.
Depreciation of this investment is distributed to the individual production
accounts through the plant overhead account. The plant is not apprised of
the rate, but 10$/year would amount to $lU2,200/year, $ll,850/month,
15^/1000 gal of water treated, or 3<£/lb of COD removed.
WATER REUSE
An activated carbon adsorption water treatment system requires an adequate
supply of water for the various carbon transfer operations and for the
scrubbing of offgases from the carbon reactivation furnace.
The water supply for scrubbing the off-gases from the carbon reactivation
furnace is provided from the secondary treatment system feed pumps since
the level of dissolved organics in the water has no appreciable effect on
the operation of the scrubbing tower. The water appears to be satisfactory
for this use although it is necessary to clean the scrubber trays periodi-
cally due to the oil and grease in the water condensing out of the trays
and plugging them.
Effluent from the adsorption towers is used to proved the motive water for
the various carbon transfer operations. This water so far has been of ade-
quate quality to serve this purpose although there have been problems at
times when carbon fines were discharged from the adsorption towers after
the bed was pulsed. No other applications for recycle of this water have
been evaluated to date, although several possibilities are under consider-
ation. These include use in contact condensers, vent scrubbers, and
cooling tower makeup.
27
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SECTION V
REFERENCES
1. Skolnik, H., H. I. Enos, Jr., F. H. Gardner, Jr., The Literature of
Wood Naval Stores. In Advances in Chemistry Series, Number 78, Litera-
ture of Chemical Technology, Gould, R. F. (ed.). American Chemical
Society, Washington, D. C., 1968. pp. 3^9-361.
2. Grantham, B. J., Completion Report of Pollution Studies on the Leaf
River. Fisheries and Pollution Division of-Mississippi Game and Fish
Commission, Jackson, Miss., Project F-9-R. May 1, 196l-April 30, 1962.
p. lU.
3. Pascagoula River Basin Water Quality Management Plan. Pat Harrison
Waterway District. Hattiesburg, Miss., June 1973. Vol. I, Chapter VI,
pp. 256-257 and Vol. II, Chapter III, p. U5.
U. Risso, J. L., and R. E. Schade. Secondary Treatment with Granular Acti-
vated Carbon. Water and Sewage Works. Vol. Il6, p. 307, August 1969
5. Process Design Manual for Carbon Adsorption, U. S. Environmental Pro-
tection Agency, Technology Transfer Office, 1973.
28
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SECTION VI
APPENDICES
A. Laboratory Methods
Laboratory determinations were carried out by the procedures described
in:
American Public Health Association, American Waterworks
Association, and Water Pollution Control Federation, "Standard Methods
for the Examination of Water and Wastewater", 13th Edition, American
Public Health Association, Inc., New York, 1971.
The methods used were:
Ammonia — p.
Biological Oxygen Demand — p. k&9
Cadmium — p. k22
Chemical Oxygen Demand — p.
Chlorides — p. 376
Chromium — p. k26
Copper — p. 163
Dissolved Solids — p. 291
Nickel— p. U93
Nitrates — p. k$k
Oil and grease — p.
pH~p. 500
Phenols — p 501
Suspended Solids — p. 290
Total Organic Carbon — p. 257
Total Solids— p. 288
Zinc — p. hkh
B. Detailed Data
Data on many of the days of operation of the water treatment facilities
are listed in the following Tables. Samples analyzed were 2U-hour com-
posite samples made up of a minimum of four individual grab samples.
Composites were not specifically flow proportioned because the streams
sampled flow at relatively uniform rates.
29
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TABLE 1-A. OPERATION OF WASTEWATER TREATMENT FACILITIES
DAILY COMPOSITE SAMPLES (I/DAY)
Date
Startup
7/30/73
7/31
8/1
8/2
8/3
8/28
8/29
8/30
8/31
Typical
9A
9/5
9/7
9/25
9/26
10/1
10/2
10/3
10/U
10/5
12/5
12/6
12/10
12/17
12/19
' / "fc*i'
12/20
Primary
Treatment Effluent
COD TOC
pH (mg/1) (mg/1)
no slugging:
* 9-0
10.0
7-5
6.U
6.7
6.3
7.0
6.8
7-0
operation but
8.0
7-3
8.1
6.9
7.9
6.8
6.8
7.1
6.0
6.9
6.0
6.0
7.U
6.0
7.2
7-2
Very erratic slugging
1AM
1/8
l/ll*
1/15
2/15
*"~ / ^-s
3/1
•mJ / -1"
3/12
—* l J
3/13
^fl J-»J
3/15
3/18
•Jt J-*'
3/19
™// -*->'
3/20
3/21
7A
7-0
5-9
6.3
6.6
6.1
6.1
5.8
5.6
* 10.5
5.7
5-9
6.0
81*8
2520
1360
800
592
5**0
688
61*0
78U
high feed:
70 1*
70l*
61*8
560
6 la
720
576
61*0
1077
1220
800
960
688
621*
1*1*8
875
operation
656
752
1136
___
1088
608
__«
1*61*
966
880
__»
768
—
191
350
266
230
178
173
211
189
209
221
233
191
168
192
1U9
183
169
200
210
221
265
175
167
171
300
when
231
255
295
680
2l*U
125
137
209
205
32 1*
200
181*
151
Secondary
Treatment Effluent
COD TOC
pH (mg/1) (mg/1)
9-1
9-9
7.6
7-0
6.7
7.0
6.9
7.5
7.2
7.U
7.1 '
7.2
7-2
7-0
6.8
7.0
6.8
6.5
6.5
7.3
7-2
7.U
7-0
6.6
7.1
operating:
7.1
7.0
6.3
6.6
6.7
7.2
6.8
6.1*
6.8
8.0
8.0
T.U
7.1
101
95
185
176
276
120
18U
100
131
72
13U
112
lU2
156
166
162
192
189
261
160
212
88
128
188
160
3M
92
272
—
372
292
128
128
220
388
381
372
209
21
20
7^
68
71
27
3U
1*8
1*9
50
26
32
1*3
U9
31
1*7
1*1*
1*8
75
3^
60
22
31
31*
33
63
51
61*
81*
92
66
50
51
57
79
83
87
55
% Removal
COD
88
96
86
78
53
78
73
81*
83
90
81
83
75
76
77
72
70
82
79
80
78
87
79
58
82
78
r\f\
88
76
66
52
—
72
77
56
52
«_
TOC
89
9U
72
70
60
81*
81*
75
77
77
89
83
71*
7U
79
7U
7U
76
61*
85
77
87
81
80
89
73
Qf\
80
78
88
62
1*7
61*
76
72
76
59
53
x-i
6U
30
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TABLE 1-A, CONTINUED. OPERATION OF WASTEWATER TREATMENT FACILITIES
DAILY COMPOSITE SAMPLES (I/DAY)
Primary
Treatment Effluent
Date
Unit operated
6/5
6/13
6/17
Slugging rate
7/6
7/11
7/18
7/22
7/28
8/15
8/21
9/3
9/12
10/27
11/5
11/lU
11/21
12/3
No slugging:
12/10 *
12/17
1/6/75 *
1/lU *
1/21
1/29
2/U
2/12 *
pH
with
6.0
7.2
5.8
COD
(mg/1)
little or
1360
1168
1088
TOC
(mg/1)
no slugging:
19 U
520
2 US
Secondary
Treatment Effluent
COD TOC
pH (mg/1) (mg/1)
'8.0
7.U
7.U
•102U
976
896
150
Uo6
202
% Removal
COD
25
16
18
TOC
23
22
17
increased:
6.0
6.U
8.3
5-2
6.1
6.U
6.3
6.U
6.3
6.U
U.I
6.2
7.8
6.9
8.9
7.3
8.7
9.U
7.5
6.U
7-6
9.3
876
1216
1U72
17UU
U96
688
1616
1312
1U2U
190U
1U72
1397
9UU
838
1200
1U08
1U2U
10UO
15UO
1168
926
1U72
231
222
19 U
307
221
36U
712
288
336
333
312
U05
2UO
2U7
278
337
8UU
367
368
252
2UO
3U5
7.0
7.0
7.5
7.0
7.0
8.6
7.7
7-7
7.1
8.1
7.6
6.8
7.U
7.8
8.8
8.2
8.7
8.9
7.6
7.1
7.3
9.2
UUo
70U
1008
720
192
560
508
1136
62U
288
336
6U7
30 U
U56
896
955
73U
U96
8U8
736
368
976
118
132
157
109
1U8
260
310
235
159
91
85
281
9U
1U3
22 U
216
209
137
232
88
100
2UO
50
U2
32
59
61
19
62
13
56
85
77
5U
68
U6
25
32
U8
52
U5
37
60
3U
U9
Ul
19
6U
33
29
56
18
53
73
73
31
61
U2
19
36
39
63
37
65
58
30
•Denotes periods of high. pH
31
-------
TABLE 2-A. DAILY COMPOSITE SAMPLES (1»/DAY): ANALYSES OF CARBON TREATMENT SYSTEM
PEED AND PRODUCT (mg/1 EXCEPT pH AND TEMPERATURE)
U)
Date
7/22/7»»
8/21
9/12
10/19
10/27
11/5
11/lU
11/21
12/3
1/6/75
2/U
Average
Sample* pH
P.T.E. 5.2
S.T.E. 7.0
% Rem. -
P.T.E. 6.3
S.T.I. 7.7
% Rem. -
P.T.E. 6.3
S.T.E. 7.1
% Rem. -
P.T.E. 6.U
S.T.E. 7.U
% Rem. -
P.T.E. 6.3
S.T.E. 7.8
% Rem. -
P.T.E. 7-3
S.T.E. 7.5
% Rem. -
P.T.E. 6.2
S.T.E. 6.8
% Rem. -
P.T.E. 7-7
S.T.E. 7.7
% Rem. -
P.T.E. 6.9
S.T.E. 7.8
% Rem. -
P.T.E. 8.6
S.T.E. 8.5
% Rem. -
P.T.E. 7.6
S.T.E. 7.3
% Rem. -
P.T.E. 6.8
S.T.E. 7.5
% Rem. -
COD
17l»U
720
59
1616
608
62
lU2l*
62U
56
11*51
U96
66
1521
2l»6
8U
1399
289
79
1397
6U8
5U
9ll*
298
67
838
1*56
1*6
1397
73-;
1*7
926
31*8
62
1330
1*97
63
BOD
792
285
61*
81*0
330
6l
-
_
_
5Ul
301
1.1*
1*1*1
10i»
76
583
111*
80
576
325
UU
686
27 1(
60
515
318
38
50l*
313
38
52U
180
66
600
251*
58
TOC
307
109
61*
712
310
56
336
159
53
1(27
259
39
321
88
73
307
91
70
1*05
281
31
189
88
53
202
151
25
205
Ul
21*0
100
58
3U5
167
52
T.S.
1301*
1078
17
131
121
8
101*0
8l»2
19
1265
695
1*5
1335
680
1*9
1800
161.3
9
1371*
1116»«
19
956
908
5
13»»8
1120
17
I960
2052
-U
786
512
35
1211
979
19
D.S.
1268
1051*
17
111
119
-7
916
8ll*
11
1129
689
39
1139
672
1*1
171*8
1639
6
1271*
> 101*2
18
908
89>*
2
1310
1116
15
1906
2016
-6
716
508
29
1130
960
15
S.S.
36
2U
33
20
2
90
121*
28
77
136
6
96
196
8
96
52
1*
92
100
7l»**
26
1*8
ll»
71
38
1*
89
7U
36
51
70
)»
9l»
81
19
77
Oil &
Grease
352
5U
85
95
1
99
60
8
87
52
6
88
139
20
86
1*9
3
108
> 31
71
13U
32
76
32
3
91
1*1.
21*
1*5
21
3
86
99
17
83
Phe-
nols
3.25
0.22
93
7.23
0.39
95
5.73
0.20
97
8.83
2.30
71*
6.05
0.9!*
81*
1.67
0.1*2
75
0.29
0.03
90
U.21
0.12
97
U.66
0.58
88
N N
(NH3> (N03-) Ni Zn Cd Cu Cr Cl
31.1* 8.56 1.08 1.32 0.96 1.98 1.32 1.91
35.0 7.71 0.56 0.1*1 O.ll* 0.1*3 0.19 0.1*1*
-11 10 1*8 69 85 78 86 77
28.3 6.0U 0.98 1.07 0.89 1.15 1.06 1.1(2
30.3 1*.73 0.19 0.11 0.09 0.23 0.13 0.58
-7 22 81 90 90 80 88 59
12.8 7.31 1.13 1.1*1 0.91* 1.51* 1.16 1.91
21.7 5.0l* 0.36 0.33 0.19 0.1*9 0.28 1.01
-70 31 68 77 80 68 76 1*7
26.8 8.21 1.03 1.1*1* i.iU 1.1*6 1.27 2.08
37.0 1*.86 0.32 0.1*1 0.29 0.1*8 0.37 1.1*3
-38 1*1 69 72 75 67 71 31
26.8 2.1*1 1.51 1.21 0.91 1.15 1.1*2 1.96
37.1 3.02 0.6l 0.1(8 0.29 0.1*1 0.33 l.ll*
-38 -25 60 60 68 6U 77 1*2
U.8 2.,1»8 0.83 0.98 1.09 1.17 1.01 2.0U
9.7 3.31 0.19 0.17 O.Mt 0.3l» 0.21 1.00
-102 -33 77 83 60 71 79 51
3.81 1.12 0.61 0.33 0.1»6 0.61 0.63 1.1*3
1*.32 1.31 0.09 0.11 0.07 0.16 0.28 1.01
-13 -17 l 85 67 85 7"> 56 29
19.2 5.16 1.02 1.11 0.91 1.29 1.12 1.82
25.0 U.28 0.33 0.29 0.22 0.36 0.26 0.9l*
-30 17 68 7"» 76 72 77 1*8
Temp.
38
38
_
31*
31*
-
32
32
-
33
33
-
33
33
-
31
31
-
29
29
-
28
28
-
28
28
-
28
28
-
30
30
-
31
31
-
•P.T.E. » Primary treatment effluent.
S.T.E. ** Secondary treatment effluent.
% Rem. * % Removed.
"•Carbon fines In sample.
-------
BOD
Cd
Chlorides
COD
Cr
Cu
DS
mg/1
NH3
Ni
N03-
pH
Phenols
ppm
SS
TOG
TS
Zn
SECTION VII
GLOSSARY
Biochemical oxygen demand; an empirical bio-assay type proce-
dure which measures the dissolved oxygen consumed by microbial
life while assimilating the organic matter in the water sample.
Usually listed as EOD^, this test is conducted for a 5-day
period to measure the pollutional strength.
Cadmium.
Chloride content.
Chemical oxygen demand; a measure of pollutional strength de-
termined by chemically oxidizing the organic and oxidizable in-
organic substances.
Chromium.
Copper.
Dissolved solids; nonfiltrable residue.
Milligrams per liter (essentially equivalent to ppm).
Nitrogen; ammonia.
Nickel.
Nitrogen; nitrate.
The negative logarithm of the hydrogen ion concentration;
a measure of the functional acidity of alkalinity of a liquid.
Measurement of phenolic compounds in a water sample.
Parts per million.
Suspended solids; filtrable residue.
Total organic carbon; a measure of the organic carbon content
of a water sample by catalytic combustion of the carbon to C02-
Total solids; sum of filtrable and nonfiltrable residue.
Zinc.
33
-------
METRIC CONVERSION CHART
Multiply
Inches
Feet
Square feet
Cubic feet
Pounds
Gallons
Gallons /minute
Feet /second
By
2.5k
0.30U8
0.0929
0.0283
O.h^k
3.79
5.1*58
0.305
To get
Centimeters
Meters
Square meters
Cubic meters
Kilograms
Liters
Cubic met ers /day
Met ers /second
-------
-TECHNICAL REPORT DATA
(I'U'osc rcnil hnujnclioim on the reverse bcjnrc coin/ilclint;!
1. REPORT NO. 2.
EPA-600/2-76-227
4. TITLE AND SUBTITLE
Naval Stores Wastewater Purification and Reuse by
Activated Carbon Treatment
7. AUTHOR(S)
Frank H. Gardner, Jr., and Alvin R. Williamson
9. PERFORMING OHG -\NIZATION NAME AND ADDRESS
Hercules Incorporated
Hattiesburg, Mississippi 39401
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati , Ohio 45268
3. RECIPIENT'S ACCESSION-NO.
5. REPORT DATE
October 1976 (Issuing Date)
G. PERFORMING ORGANIZATION CODE
0. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
1BB610
11. CONTRACT/GRANT NO.
S-801431
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES
1
16. ABSTRACT
This report documents the reasons for selecting a physico-chemical
process instead of a more conventional biological process for secondary
treatment of the complex organic wastewaters generated by a Naval Stores
manufacturing plant. The selected carbon adsorption system is then
discussed in detail including its removal effectiveness, problems en-
countered, and economics of operation. The system, when operated within
specifications, is capable of removing about 80% of the COD and
85% of the TOC remaining after primary treatment at a cost of about
31.4C/1000 gal. The total system achieves 95%+ removals of COD and TOC.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
Industrial wastes; Adsorption; Waste
treatment; Water pollution; Activated
carbon treatment; Operating costs; Fixed
costs; Organic wastes
13. DISTRIBUTION STATEMENT
Public Distribution
b. IDENTIFIERS/OPEN ENDED TERMS
Water pollution control;
Chemical wastes; Or-
ganics; Physico-chemical
treatment; Wood chemical
wastes; Terpenes
13. SECURITY CLASS (This Kfport)
Unclassified
20. SECURITY CLASS (Tliii page)
Unclassified
c. COSATI Field/Group
13B
1
21. NO. OF PAGES
43
22. PRICE
EPA Form 2220-1 (9-73)
S. GOVERNMENT PRIHTING OFFICE: 1976-757-056/5'llS Region No. 5-11
35
------- |