EPA-600/2-76-231
September 1976
Environmental Protection Technology Series
TREATING WOOD PRESERVING PLANT WASTEWATER
BY CHEMICAL AND
BIOLOGICAL METHODS
I
55
\
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-600/2-76-231
September 1976
TREATING WOOD PRESERVING PLANT WASTEWATER
BY CHEMICAL AND BIOLOGICAL METHODS
by
John T. White
T. A. Bursztynsky
John D. Crane
Richard H. Jones
Environmental Science and Engineering, Inc.
Gainesville, FL 32604
Grant No. 12100 HIG
Project Officer
Victor Dal Ions
Industrial Environmental Research Laboratory
Con/all is, Oregon 97330
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents necessarily
reflect the views and policies of the Environmental Protection Agency,
nor does mention of trade names or co-mercial products constitute
endorsement or recommendation for use.
ii
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FOREWDRD
When energy and material resources are extracted, processed, converted,
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 Research Laboratory - Cincinnati
(IEKL-CI) assists in developing and demonstrating new and improved methodo-;
logics that will meet these needs both efficiently and economically.
"Treating Wood Preserving Plant Wastewater By Chemical And Biological
Methods" was a part of the Industrial Pollution Control Division's program
to develop and demonstrate new technology for the treatment of industrial
wastes. This project demonstrated the biological treatment of wood pre-
serving wastes containing pentachloropenols and creosote using complete
mixed activated sludge. The study showed that the system could obtain BOD
removals of 90 percent and phenol removals of 99 percent. The information
will be of value to consultants and industry concerned with installation of
treatment facilities to meet more rigid effluent standards. For further
information, please contact the Food and Wood Products Branch of the In-
dustrial Environmental Research Laboratory, Cincinnati.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
in
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ABSTRACT
A completely mixed activated sludge system was designed for a wood
preserving plant with an average daily wastewater flow of 27,000 /day
(7,150 gal/day), a BOD concentration of 1,100 mg/], and a phenol concen-
tration of 120 mg/1. Included in the design were capabilities for pre-
chlorination and post-chlorination. The activated sludge system lone was
capable of removing 90 percent BOD, 75 percent COD, 99 percent phenol, and
76 percent pentachlorophenol. Shock loadings had minor effects on BOD and
COD removals but reduced the phenol removal and completely prevented penta-
chlorophenol removal.
Post-chlorination dosages of over 50 mg/1 resulted in reductions of
50 and 52 percent for phenol and pentachlorophenol, respectively, during
the study. The Safranin method was used for measuring penta. Later fol-
low-up work by Kbppers using vapor phase chromatography with electron de-
tection showed penta reductions of 5 mg/1 to 0.1 mg/1. There was no reduc-
tion of COD. A pre-chlorination study showed no removal of phenol, penta-
chlorophenol, or COD at the level studies in the full scale plant. Labora-
tory pre-chlorination studies showed removal of phenol and pentachloro-
phenol at chlorine dosages in excess of 250 mg/1.
This report was submitted in fulfillment of EPA Grant No. 12100 HIG
by Environmental Science and Engineering, Inc., Gainesville, Florida, for
Kbppers Company, Inc., Pittsburgh, Pennsylvania, under partial sponsor-
ship of the Water Quality Office, Environmental Protection Agency. The
study was completed as of July 1974.
IV
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TABLE OF CONTENTS
SECTION PAGE NO.
ABSTRACT iv
ACKNOWLEDGEMENTS x
I CONCLUSIONS 1
II RECOMMENDATIONS 2
III INTRODUCTION 3
IV LITERATURE REVIEW AND PRELIMINARY STUDIES 8
V MATERIALS AND METHODS 40
VI RESULTS AND DISCUSSION 54
VII REFERENCES 77
VIII GLOSSARY 83
IX APPENDIX 85
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TABLES
No. Page
1 Efficiencies of Oil Separation Processes 8
2 Effect of Lime Flocculation on COD and Phenol
Content of Treating-Plant Effluent 11
3 Threshold Toxic Levels for Continuous Dosages in
Aerobic Treatment Processes 11
4 Chlorination of Phenolic Materials 14
5 Effect of Chlorination of Pentachlorophenol Waste
on COD 21
6 Substrate Removal at Steady-State Conditions in
Activated Sludge Units Containing Creosote Wastewater 24
7 Reduction in Pentachlorophenol and COD in Wastewater
Treated in Activated Sludge Units 26
8 BOD, COD, and Phenol Loading and Removal Rates for
Pilot Trickling Filter Processing a Creosote
Wastewater 29
9 Relationship between BOD Loading and Treatability
for Pilot Trickling Filter Processing a Creosote
Wastewater 30
10 Sizing of Trickling Filter for a Wood Preserving Plant 31
11 Average Monthly Phenol and BOD Concentrations in
Effluent from Oxidation Pond 34
12 Results of Laboratory Tests of Soil Irrigation Method
of Wastewater Treatment 36
13 Reduction of COD and Phenol Content in Wastewater
Treated by Soil Irrigation 37
14 Analytical Data from Pre-Design Study 42
15 Revised Operating Schedule 51
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TABLES CONTINUED
No. Page
16 Schedule of Analyses 52
17 Startup and Stabilization Data 55
18 Effects of Shock Loading 57
19 Results of Loading Rate Variation 59
20 Laboratory Post-Chlorination Studies 64
21 Effects of Full Scale Post-Chlorination 67
A Daily Log Summary 90
B Post-Chlorination 97
vii
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FIGURES
No. Page
1 Original Wastewater Treatment Flow Diagram,
Koppers Company, Carbondale " 6
2 Effect of Detention Time on Oil Removal by Gravity
Separation 9
3 Reaction Scheme for the Chlorination of Phenol 13
4 Observed Rates of Chlorination of Phenol and
Chlorophenols 16
5 Chlorination of Phenol and the Chlorophenols Formed
at pH7 17
6 Chlorination of Phenol and the Chlorophenols Formed
at pH 8 18
7 Chlorination of Phenol and the Chlorophenols Formed
at pH 9 19
8 Determination of Reaction Rate Constant for a Creosote
Wastewater 23
9 COD Removal from a Creosote Wastewater by Aerated
Lagoon without Sludge Return 25
10 Phenol Content in Oxidation Pond Effluent before and
after Installation in June 1966 of Aerator 33
11 Relationship between Weight of Activated Carbon Added
and Removal of COD and Phenols from a Creosote
Wastewater 39
12 Flowrate Variation with Time 41
13 Percent Dilution vs. BOD 45
14 Schematic of "Package" Treatment System %Q
15 Influent and Effluent Phenol Concentration 63
vm
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FIGURES CONTINUED
No. Page
16 Chlorine Residuals with Time 65
17 Effects of Chlorine on Pentachlorophenol Concentrations
as Measured by Safranin Method 66
18 (a,b) Chlorine Persistence 69,70
19 Effect of Chiorination on Phenolic Concentration
of Raw Wastewater with Activated Carbon 71
20 Effect of Chiorination on Penta Concentration of Raw
Wastewater with Activated Carbon 72
21 COD Removal in the Activated Sludge Process 75
ix
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ACKNOWLEDGEMENTS
ENVIRONMENTAL SCIENCE AND ENGINEERING, 1C.
Environmental Science and Engineering, Inc., (ESE) of Gainesville,
Florida, as a consultant to Koppers Company/ provided overall supervision
of the project. The concepts of the program and the treatment facilities
were developed by Dr. Richard H. Jones, P.E. The Project Manager for
the first year of the project, Mr. T. A. Bursztynsky, P.E., was respon-
sible for planning the technical program. Mr. John T. White supervised
much of the program and contributed substantially to preparation of this
report. Mr. John D. Crane, P.E./ supervised preparation of the final
report and coordinated reviews by EPA and Koppers personnel. Dr. W. S.
Thompson of the Forest Products Research Laboratory, Mississippi State
University, provided valuable consulting services to ESE.
KOPPERS COMPANY
The program was partially funded by Koppers Company, Pittsburg,
Pennsylvania. Mr. Marvin D. Miller, P.E., provided engineering
coordiviation for the project. Mr. Roy Burke served as chief operator
for the treatment plant. Considerable input to the project was also
provided by Mr. G. R. Tallon, Mr. C. W. Fisher, and Mr. Paul A. Goydan
and other members of the Environmental Engineering Section of the
Forest Products Division. Mr. X. P. Laskaris served as Grant Director.
ENVIRDNMENTAL PROTECTION AGENCY
The Project Officer was Mr. Victor Dallons. Technical review
and assistance were provided by Mr. Ralph Scott and Mr. James H. Phillips.
The program was partially funded by EPA" under Grant No. 12100 HIG.
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SECTION I
CONCLUSIONS
It was demonstrated that wastewater from a wood preserving process
utilizing creosote and pentachlorophenol (penta) as preservatives
can be effectively treated by a biological system. The process employed
was the complete mix activated sludge process. The process obtained
a BOD reduction of 90 percent and a phenol removal efficiency of
99 percent.
Pre-chlorination was effective in reducing both penta and phenol
in laboratory tests. However, in the full scale plant, a chlorine/
penta ratio of 300:1 was required to achieve an 80 percent reduction
in penta and the resulting excessive chlorine residuals caused operation-
al problems in the biological treatment system.
Post-chlorination provided considerable color removal and reduced
the penta concentration from about 5 mg/1 to less than 0.10 mg/1.
It also accomplished slight reductions in phenol concentrations. There
was no apparent reduction of COD.
Shock loading tests showed a noticeable decrease in treatment
efficiency. A doubling of the hydraulic loading rate resulted in
a decrease in phenol removal from 99 to 89 percent, in COD from
80 to 72 percent, and penta from 79 to 0 percent. There was little
apparent effect on BOD removal efficiency.
The usefulness of BOD as a pollutant parameter was limited as
the characteristics of the wastewater apparently inhibited the test,
e.g., an increase in dilution in the BOD test from 99.8 to 99.9 percent
resulted in an increase in BOD from 1000 to 2000 mg/1.
The Safranin method for measuring pentachlorophenol was of
questionable reliability in testing the biological treatment effluent;
an increase in penta was indicated across the activated sludge unit.
It should be noted that near the end of the study, vapor phase
chromatography using electron capture detection was found to be a
relative method for penta detection at low levels and indicated that
the Safranin analyses were generally high.
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SECTION II
RECOMMENDATIONS
The activated sludge process provides a potential means as a
viable treatment alternative for the treatment of wood preserving
wastewater where limited land is available for spray irrigation and
lagooning. For plants which have limited land available for spray
irrigation or lagooning, the activated sludge process could represent
the most cost-effective treatment alternative. The activated sludge
process should be recommended to the wood preserving industry as a
potential means of meeting increasingly stringent effluent limitation
standards.
A properly designed and operated preservative recovery system is
recommended before activated sludge treatment. Also, a surge basin is
imperative for successful operation of the activated sludge system.
The key design parameters for the complete mix system are as
follows:
1. Maximum BOD Loading =0.2 kg/day/kg MLSS
2. Maximum COD Loading =0.5 kg/day/kg MLSS
3. Maximum Penta Loading = 6.5 gm/day cu m
U. Minimum hydraulic detention time = Uo hours
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SECTION III
INTRODUCTION
The Koppers Company, Inc., wood preserving plant at Carbondale,
Illinois, was selected by the Environmental Protection Agency in 1971
as a site for a demonstration project to determine the design and
operating parameters for chemical and biological treatment of both
creosote and pentachlorophenol (penta) wastewaters generated by a wood
preserving operation. The wastewater from the Carbondale plant is
representative of wood preserving wastewater in that it has a high
Biochemical Oxygen Demand (BOD) and contains wood preserving compounds
and extractives. The successful development and operation of treatment
facilities at the Carbondale plant alleviates a specific pollution
problem at that plant and, more importantly, provides design parameters
for similar wood preserving plants.
BACKGROUND
A number of methods have been developed to increase the service-
ability of wood*under conditions that promote decay, weathering, insect
destruction, or exposure to fire. Treated or preserved wood is used in
almost every facet of the construction industry. Included among the
various wood materials that are treated with preservatives or fire
retardants are general lumber and timber, bridge ties, foundation piles,
posts, crossties, utility poles, and marine construction wood.
Preservative and Fire Retardant Chemicals
The various preservatives in common use throughout the industry
include creosote, creosote-coal tar, creosote-petroleum and pentachloro-
phenol solutions, as well as water-borne preservatives and fire retardants,
Creosote, creosote-coal tar, and pentachlorophenol-oil preservatives
are used at the Koppers Company facility at Carbondale; however, creosote
is the principal preservative used.
Creosote, a distillate of tar produced by the carbonization of
bituminous coal, is used as a wood preservative both because it protects
wood against wood destroying organisms and has a high degree of perse-
verance. The main constituents of creosote are tar acids.
The mixture of creosote with coal tar is primarily for railroad
ties and marine installations that require a preservative with water-
repelling properties. Common ratios of creosote to coal tar are 80:20,
70:30, 60:40, and 50:50.
Pentachlorophenol, frequently called "Penta", has a relatively low
solubility in water of about 15 mg/1 at normal water temperatures.
It is normally applied with a carrier petroleum oil.
-------
Water-borne preservatives are basically heavy metal compounds of
copper, chromate, arsenite or arsenate, and zinc. One of the chief
advantages of this treatment is that the wood is paintable. Water-
borne preservatives are not used at the Carbondale plant.
Fire retardant formulations are designed to slow the spread of
fire in treated wood. There are generally four formulations used in
the industry, with water used as the preservative carrier. Prior to
the commencement of the investigation, the Carbondale Facility used
a formulation containing a borate.
Description of the Wood Preserving Process
The wood preserving process consists of two basic steps:
(1) preconditioning the wood to reduce its natural moisture content
and (2) impregnating it with the desired preservatives. The moisture
reduction step may consist of (1) seasoning or drying the wood in
large, open yards, (2) kiln drying, or (3) steaming the wood for
several hours at elevated pressures to raise the temperature of the
moisture in the wood cells, and subsequently applying a vacuum to
reduce the boiling point of the water and evaporate it. Nearly
70 percent of the wood produced at the Carbondale plant consists of
crossties and switch ties which are air seasoned in a storage yard.
Approximately 10 percent of the production at the Carbondale plant
is pretreated by steaming. Kiln drying requires from four to ten
days for pretreatment as compared to approximately 12 hours for
steaming.
Pretreatment of wood by steaming may be done in one of three
ways: (1) open steaming, (2) closed steaming, and (3) semi-closed
steaming. Open steaming consists of placing the wood in retorts and
applying steam under pressure to the retorts for a period of several
hours after which vacuum is applied to remove wood water to the
effluent system. As the applied steam condenses on the wood and on
the sides of the retort, it drains down and is eventually removed
as wastewater. This condensate tends to collect preservatives deposited
in the retort from previous processing.
In the closed teaming cycle, water is introduced into the retort
and the wood is heated by steam generated by heating coils in the
bottom of the retort. At the end of the cycle , the water is with-
drawn to a storage tank from which it may be reused. Eventually a
blowdown of the steaming water is necessary because of the buildup
of wood extractives. At Carbondale this blowdown goes to the treatment
system.
The Carbondale plant uses four retorts for the application of the
semi-closed steaming cycle for wood pretreatment. In this process,
steam is added to the retort under vacuum to reduce the condensation
temperature and lower the boiling temperature of water entrained in the
wood. As steam condenses in the retort, the liquid level is allowed
to build up until it covers the heating coils in the bottom of the
-------
retort. Live steam is then turned off and heat is applied to the coil.
At the end of steaming all water is discharged to waste and a vacuum
continues to be drawn to remove additional moisture from the wood.
After the initial pretreatment step, there are several possible
ways to impregnate wood with preservatives. For all creosote and
pentachlorophenol treatments not requiring a heavy saturation of pre-
servatives, the Carbondale plant uses the empty-cell Rueping process.
The full-cell process is used for treatment applications requiring
heavy saturations and for applications of fire retardant.
The empty-cell Rueping process provides greater penetration of
preservative for net amounts of preservative absorbed and allows a
relatively high recovery of excess preservative. The full-cell process
allows a higher saturation of preservative within the wood cells.
Wastewater Sources from the Wood Preserving Process
The basic wood preserving process generates wastewater .streams
consisting of condensed water from steaming, barometric leg cooling
water or surface condenser condensate, boiler blowdown, miscellaneous
wash water, p/ipe and tank leakages, and door pit drips.
In the semi-closed steaming process, by which condensate is
allowed to accumulate in the retort until it covers the heating coils,
the condensate is wasted after oil recovery. The wasted condensates
contain oil, phenolic compounds, and various wood extractives.
When barometric legs or wet-type vacuum pumps are used to produce
vacuum, a water contaminated with the preservative used is generated.
The Carbondale facility employs a vacuum pump preceded by a surface
condenser. Volatile gases are condensed on the surface condenser and
are discharged to waste. The pump is sealed and lubricated by water
circulated through a small pond.
Boiler blowdown is usually a stream of small volume, but one that
can be contaminated with various chemicals such as chromates and phos-
phates used for boiler water conditioning.
Water used to clean equipment is normally contaminated with pre-
servative chemicals, oil and grease, and possibly detergents.
Existing Wastewater Treatment Facilities at Initiation of Project
The wastewater treatment system in employment at the Carbondale
plant at the time of project initiation is illustrated in Figure 1.
Since specific preservatives are used in a retort, it is possible to
segregate wastewaters for pretreatment. Wastewater from the penta-
chlorophenol oil retorts is pumped to a decanter from which the
floating oil fraction containing pentachlorophenol is recovered. The
water fraction, after addition of a polymeric flocculant, is pumped
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POND 4
POND 3
POND 2
POND I
(RESERVE)
SPRAY IRRIGATION FIELD
CREOSOTE SETTLER
x\
PENTA SEPAR
PENTA-OIL TO WORK TANK
^ DRAINAGE TROUGH
KTQR^/^
~\
i
S WORK AREA CONTRIBUTORY S
DRAINAGE FIELD
3
COMMON
SUMP
POLYMERIC
FLOCCULANT
.ADDITION
\
--
>
WORK TAf
^ AND SKI
^- CREOSOTE
Ml Ml
TC
\ /SUMP
...
I 4 CREOSOTE
1 3 CREOSOTE
| Z PENTA
* 1
WS^
PENTA
^
Viy
RETORT
RETORT
RETORT
RETORT
^~&£
=^^-
I
1
1
1
.-•-'
«AO
\
DIVIDING WALL
PRIMARY PENTA-OIL
DECANTER
FIGURE 1. Original Wastewater Treatment Flow Diagram - Koppers Company, Carbondale
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to a secondary recovery tank for further separation. The water from
the second tank is transferred to a common sump.
Wastewaters are collected and handled separately in a similar manner
as the penta-oil wastewaters with recovered creosote returned to the
system. The clarified water is discharged to the common wet well.
The wastewater from the common sump is pumped to the set of four
lagoons which provides equalization, evaporation, and biological
oxidation. A spray irrigation field provides final treatment.
PROJECT OBJECTIVES
The project objectives were to determine the design and operating
parameters of chemical and biological treatment of creosote and penta-
chlorophenol-oil wastewaters from a wood preserving plant. The plan
of operation consisted of design, construction, and operation of treat-
ment facilities for the wastewaters generated by the Koppers Company
wood preserving plant located at Carbondale, Illinois. The operation
and sampling and testing program would be supervised by Environmental
Science and Engineering, Inc., of Gainesville, Florida.
-7-
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SECTION IV
LITERATURE REVIEW AND PRELIMINARY STUDIES
In order to best meet the objectives of the project, an extensive
review of the literature and other previous work related to the
treatment of wood preserving wastes was conducted.
PHYSICAL TREATMENT
The first step in treating wastewater from a plant using creosote
or creosote solutions is usually settling and skimming, not so much for
treating wastewater, but to recover valuable preservatives. The most
common type of separator in use by the industry is modeled after the
separator developed by the American Petroleum Institute (1) which
basically consists of a horizontal tank divided into three or more
compartments. Heavy oils settle to the bottom of the tank and are
removed by a pump to a dehydrator. Floating oils are removed by a
skimmer.
The amount of entrained oils removed by separation equipment
depends in part on whether the oil is in a free or emulsified form.
Data on the percent efficiencies of several separators are presented
in Table 1 (2). The variability of oil removal as a function of
detention time was shown by Wallace, e_t. al_. (3), as illustrated in
Figure 2.
TABLE 1. EFFICIENCIES OF OIL SEPARATION PROCESSES
Source of
Influent
Percent Removal
Free Oils
Emulsified Oils
API Separator
Raw Waste
60 - 99
Not applicable
Air Flotation without
Chemicals
Air Flotation with
Chemicals
Chemical Coagulation and
Sedimentation
API
Effluent
API
Effluent
API
Effluent
70
75
60
- 95
- 95
- 95
10
50
50
- 40
- 90
- 90
The conventional oil-water separators discussed above remove only
free oils. Emulsions may be broken by rotary vacuum filters or by
centrifugation. Both of these methods have been tested at a few wood
preserving plants, but chemical methods involving flocculation and
sedimentation are the most widely used.
-8-
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10
20
30
h-
UJ
o
g 40
Q.
50
UJ
ce
-J 60
o
70
80
AVERAGE TEMPERATURE - 38° C
INITIAL OIL CONCENTRATION- 45 PPM. * 4P.P.M.
0 40 80 120 160 200
SEPARATION TIME IN MINUTES
FIGURE 2
Effect of Detention Time on Oil Removal by Gravity Separation
-9-
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CHEMICAL TREATMENT
Chemical Precipitation
The effluent from the settling and skimming tanks contains a
considerable amount of emulsified oil and creosote. This emulsion
represents a large portion of the BOD in the wastewater; wastewaters
containing emulsified oils often have oil concentrations in excess
of 1000 mg/1 after separation (4).
Middlebrooks and Pearson (5) found that 79 percent of the BOD
and 80 percent of the COD in this type of wastewater could be removed
by chemical coagulation with the addition of approximately 2000 mg/1
of lime and alum. However, the volume of sludge produced was almost
40 percent. Frank and Eck (6) found similar results with sodium
hydroxide and lime after polyelectrolytes alone failed to produce
flocculation. Although the treatment efficiencies were high, the
problem of sludge disposal would suggest that another type of treat-
ment for breaking the emulsion might be more feasible.
Jones and Frank (7) achieved COD and BOD reductions of 83 and
73 percent, respectively, in creosote wastewater using a single
cationic polymer at a rate of 40 mg/1. Anionic polymers failed to
break the oil emulsions. However, Simonsen (8) was successful in
obtaining oil reductions in refinery wastewater of more than 95 percent
by the use of both anionic and cationic polyelectrolytes in combination
with bentonite clay. There was no difference between the two types
of polymers in the results obtained.
Thompson and Dust (9) found ferric chloride to be an effective
flocculant for both creosote and pentachlorophenol wastewaters with
very narrow pH limits. In the same study, from 0.75 to 2.0 gm/1 of
lime appeared to be an optimum dosage for reduction of COD and phenol,
as shown in Table 2.
Lime was also employed by Middlebrooks (10) in dosages of 2 gm/1
to obtain reductions in COD of up to 70 percent in creosote wastewater.
Similar results were obtained with alum. Both lime and alum were used
by Gaspin (11) for treatment of creosote wastewater previously de-
emulsified with sulfuric acid.
Treatment of wastewater containing heavy metals has been success-
fully practiced for many years in various industries. Chromium is
found in wastes from metal plating and finishing operations. It is
present in rinse waters and chromic acid baths and in spent baths
from electroplating and anodizing processes. Wastewaters from similar
processes also contain copper and zinc.
Heavy metals contained in salt-type preservatives and fire
retardants are toxic to microorganisms, even when the metals are in
relatively low concentrations (12) (see Table 3). Other studies (13),
using a combination of metals, showed that the aeration phase of bio-
logical treatment can tolerate chromium, copper, nickel, and zinc, up
-10-
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TABLE 2. EFFECT OF LIME FLOCCULATION ON COD AND PHENOL CONTENT
OF TREATING-PLANT EFFLUENT
COD
Lime
(qm/1)
0.0
0.25
0.50
0.75
1.00
1.25
1.50
PH
5.3
6.8
7.9
9.7
10.5
11.4
11.8
Cone.
(mg/1)
11,800
9,700
7,060
5,230
5,270
5,210
5,210
Percent
Removal
—
23
39
56
55
56
56
Phenol
(mg/1)
83
81
72
78
80
84
83
TABLE 3. THRESHOLD TOXIC LEVELS FOR CONTINUOUS
DOSAGES IN AEROBIC TREATMENT PROCESSES
Metal
Chromium (VI)
Copper
Nickel
Zinc
Wastewater Concentration
(mg/1)
10
1
1-2.5
5-10
-11-
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to a total heavy metal concentration of 10 mg/1, either alone or in
combination, with about 5 percent reduction in overall plant efficiency.
Various other studies (14, 15, 16), both in the laboratory and in the
field, reached similar conclusions.
Chemical analyses to determine heavy metal concentrations should
be conducted on the wastewater from wood preserving plants using
water-borne preservatives. If heavy metal removal is necessary,
chemical treatment related to the specific ions present is applied.
Usually precipitation of heavy metals from wastewater is accomplished
with lime; however, hexavalent chromium must be reduced to a trivalent
state by ferrous sulfate or sulfur dioxide prior to lime precipitation.
The use of sulfur dioxide has been described in detail by Chamber!in
and Day (17) and Fisher (68).
A bibliography dealing with the removal of heavy metals was com-
piled in 1949 by Dodge and Reamms (18) and it has been estimated by the
American Wood Preserver's Association (19) that by 1959 some 500 addi-
tional articles had been published on the subject. Detailed discussions
of heavy metal removal have also been presented by Eckenfelder (20)
and Bliss (21).
Chemical Oxidation
While some information is available on oxidation of phenols using
peroxide, ozone, and other chemical oxidants (22, 23), the vast majority
of literature is concerned with the oxidation of phenolics with chlorine,
especially as related to the water supply area. It has long been common
knowledge that chlorination of phenols may produce tastes and odors in
water supplies. Early studies on chlorination of phenols centered on
chlorine residuals and removal of tastes from water. Based on ratios
of chlorine to phenol, Ingols and Ridenour (24) concluded that a quinone-
like substance was the basic cause of "phenol" tastes. Their work
postulated a succession of chlorination products which ultimately ended
in dichlor-quinone. Further chlorination of dichlor-quinone was postu-
lated to rupture the benzene ring and form maleic acid rather than
completely eliminate any residual taste problems.
Subsequent studies by Ettinger and Ruchhoft (25) substantiated
early work showing increasing taste intensity with increasing chlorina-
tion of phenols and then decreasing taste until no taste was noticeable
and a chlorine residual began to develop. Comparative information was
provided on the chlorination of various phenolic compounds and quantities
of chlorine needed to eliminate detectable taste products. Table 4
indicates that a chlorine to cresol ratio of 5:1 would be adequate to
completely form chlorination end products. Pentachlorophenol could
be oxidized by chlorine at a 1:1 ratio.
The first fact substantiated from early work of researchers was the
progression of chlorination products as illustrated in Figure 3. In
more recent studies, R. G. Burttschell and co-researchers (26) at the
Robert A. Taft Sanitary Engineering Center uses paper chromatography and
infrared and ultraviolet spectrophotometry to determine the actual products
-12-
-------
OH
Oxidation
FIGURE 3. Reaction Scheme for the Chlorination of Phenol
-13-
-------
involved in the chlorination of phenols. According to these studies,
the chlorination of phenol proceeds by stepwise substitution of the
2, 4, and 6 positions of the aromatic ring. Initially, phenol is
chlorinated to form either 2- or 4- chlorophenol. Then 2- chloro-
phenol is chlorinated to form either 2, 4- dichlorophenol or 2, 6-
dichlorophenol while 4- chlorophenol forms 2, 4- dichlorophenol.
Both 2, 4- and 2, 6- dichlorophenol are chlorinated to form 2, 4, 6-
trichlorophenol. The 2, 4, 6- trichlorophenol reacts with aqueous
chlorine to form a mixture of non-phenolic oxidation products.
TABLE 4. CHLORINATION OF PHENOLIC MATERIALS
Material
@ 1 mg/1
Phenol
0-Cresol
M-Cresol
P-Cresol
1 -Naphthol
2-Chlorophenol
4-Chlorophenol
2-, 4-Di chlorophenol
2-, 4-, 6-Trichlorophenol
2-, 4-, 5-Trichlorophenol
2-, 3-, 4-, 6-Tetrachlorophenol
Pentachlorophenol
Chlorine Required to Chlorine Added
Eliminate Taste to Produce Free
(mg/1) Residual (mg/1)
4
5
5
3
4
3
3
2
Could Not be Tasted
Could Not 'be Tasted
Could Not be Tasted
Could Not be Tasted
7
5
5
4
5
5
6
6
3
2
1.5
1.0
The principal taste causing compounds were found to be 2-chlorophenol,
2, 4- dichlorophenol, and 2, 6- dichlorophenol. The development of the
chlorophenolic taste did not occur at pH values less than 7.0 and the
presence of ammonia significantly retarded the rate of reaction between
phenol and chlorine. Of prime importance was the discovery that at a
chlorine to phenol ratio of 10:1, the aromatic benzene ring is destroyed.
An optimum pH of 8 was found to be helpful for rapid chlorination of
-14-
-------
phenolic compounds using hypochlorous acid; however, reaction rates
would be different under acidic conditions using chlorine gas since
molecular chlorine is the most probable reacting agent. Therefore no
information was provided on the mechanism of chlorination or reaction
rates using chlorine gas at low pH values.
Later studies by Lee (27) provided information on the kinetics of
reaction of phenolic compounds and chlorine. According to Lee, the
chlorination of phenol and each of the chlorophenols conforms to a
second-order rate expression in which the rate of change of chlorine or
phenolic compounds is proportional to the product of the formal concen-
trations of aqueous chlorine and phenolic compounds, or:
-dF
Cl = K F F
~dT~ ob Cl PhOH
Rate constants were determined for each phenol compound at various pH
levels and are plotted in Figure 4.
Obviously, the rates of reaction of aqueous chlorine with phenol
vary with pH with the maximum rate of reaction occurring .near neutrality
for most species. It should be noted that the more acidic the phenolic
compound the lower the pH of maximum reaction rate, and, as stated by
Lee, those substitute groups of phenol which tend to make the substituted
phenol more acidic also tend to decrease the rate of reaction of aqueous
chlorine with this compound. Thus, it can be expected that the maximum
reaction rate of chlorine with pentachlorophenol will occur at a pH
somewhat less than 7, and that this reaction will be slower than the
reaction of chlorine with less highly substituted phenols. Further,
it is stated that in reacting with aqueous chlorine, phenol and the
chlorophenols tend to undergo oxidative rupture of the benzene ring
rather than substitution and that this tendency to rupture increases
with more .highly chlorinated phenolic reactants.
Figures 5, 6, and 7 show the reaction of aqueous chlorine with
phenol and the chlorophenols with time. The initial chlorine dosage,
using a stock chlorine solution prepared from gaseous chlorine, was
1.0 mg/1, the initial phenol concentration 50 mg/1, and the temperature
25° C. Figures 5, 6, and 7 represent the reactions at pH levels of 7, 8,
and 9*, respectively. A minimum reaction time of two hours was required
before a significant decrease in total molar concentration of phenolic
compounds occurred.
It should be remembered that these data represent the results of
reactions in distilled water. The presence of ammonia, for instance,
interferes significantly with the reaction of phenol with chlorine.
Weil and Morris (28) indicate that for equal initial molar concentra-
tions of ammonia and phenol at a pH of 8 and a temperature of 25° C,
ammonia chlorinates to form NH2CL about a thousand times faster than
phenol chlorinates to form monochlorophenol. Therefore, the usefulness
of the work of Lee is only qualitatively applicable to a discussion of
chlorination of a heterogeneous wastewater.
15
-------
8000
6000
4000 -
2000 -
^ 1000
7E 800
£ 600
£ 400 .
-Q
O
O
'•M
fC
200 -
o 100
o 80
o 60
«/l
40 -
20 -
10
8
6
4
01
to
Ǥ
2 .
Phenol
2-Chlorophenol
4-Chlorophenol
2,4,6 Tricnloro
phenol
2,6-Dichlorophenol
2,4-Dichlorophenol
FIGURE 4.
45 6 7 8 9 10 11 12 13
PH
Observed Rates of Chiorination of Phenol and Chlorophenols
16
-------
20-,
18 -
16 _
Initial Chlorine 10 ppm
Phenol 50 ppb
Temperature 25° C.
pH 7.0
Phenol
V
^2-Chlorophenol
4-Chlorophenol
\ 2,4-Dichlorophenol
1 2
TIME hrs
FIGURE 5. Chlorination of Phenol and the Chlorophenols Fonned at pH 7,
17
-------
Initial Chlorine 10 ppm
11 Phenol 50 ppb
Temperature 25° C.
pH 8.0
\ /2-Chlorophenol
2,4-Dichlorophenol
2,6-Dichloro-
phenol
i
0.8 1.2 1.6 2.0 2.4 2.8
TIME hrs
FIGURE 6. Chlorination of Phenol and the Chlorophenols formed at pH8.
18
-------
Phenol
oo
o
_x 12 _
01
§
•I-
2
01
0
Initial Chlorine 10 ppm
Phenol 50 ppb
Temperature 25° C.
pH 9.0
2,4-Dichlorophenol
\2,5-Dichlorophenol
FIGURE 7
T-~T — i — r
3456
TIME hrs.
Chlorination of Phenol and the Chlorophenols Formed at pH 9
19
-------
Other researchers have also mentioned the oxidation of phenol
bearing waters using either chlorine gas or chlorine dioxide (29, 30, 31).
Glabisz (31) reported that chlorine dioxide would successfully
convert phenolic wastes from coke works to quinones, organic acids,
and carbon dioxide. Specific data on test conditions were not available
for presentation.
Successful oxidation of phenolics by chlorine was reported by the
American Petroleum Institute (32). Apparently, low dosages of chlorine
produce chlorophenolics which produce taste and odor problems. When
a large excess of chlorine is supplied (5 grams/liter per 100 mg/1 phenol),
the benzene ring is broken and a harmless non-phenolic compound is created.
The theoretical ratio of chlorine to phenol for complete destruction is
6:1; however, other organic compounds present in the wastewater necessitate
as much as 50 parts chlorine to 1 part of phenol. Again, the presence
of ammonia was noted to retard the reaction of chlorine and phenols.
The ratio of chlorine to ammonia to oxidize the ammonia is 10:1. Reaction
times for chlorination were reported in terms of one to several hours.
In conformity to the observed chlorination rates shown in Figure 5, at
a pH less than 7 a predominance of chlorophenolics was noticed, while
at higher pH levels (above 7) phenols were oxidized more rapidly and
completely.
In a study by H. R. Eisenhauer (22), chlorination was applied to
an artificial 80 mg/1 concentration phenol solution and a refinery
effluent of 78 mg/1 phenol and 627 mg/1 COD. Chlorine was added as
sodium hypochlorite at a pH of 4 and a temperature of 50° C. Creation
of chlorophenols and their destruction was directly related to increasing
chlorine dosages. There was no measurable phenol after the addition
of 200 mg/1 chlorine to the artificial solution, and the end products
stabilized at dosages over 1000 mg/1 of chlorine. In the refinery
effluent, 1000 mg/1 of chlorine were needed to remove all traces of
phenol and the final chlorination product was achieved with less than
5000 mg/1 of chlorine. A pH in the range of 4 to 10 was not found to
be an influencing factor.
Work performed by Dust (33) substantiates the value of chlorination
for pentachlorophenol removal. Table 5 presents data on the removal
of pentachlorophenol from an actual wood preserving wastewater. Increasing
dosages of chlorine as calcium hypochlorite were added at pH levels of
4.5, 7.0, and 9.5. Similarly, gaseous chlorine was added at pH levels
of 4.5, 7.0, and 9.5 and at dosages from 0.0 to 5.0 grams/liter. The
hypochlorite and gaseous chlorine were added to samples flocculated
with lime at 18 mg/1 and 20 mg/1 of cationic polyelectrolyte and to
samples not pretreated. Flocculation removed much of the chlorine
demanding substances from the wastewater and the chlorine required for
pentachlorophenol removed appeared to decrease with increasing pH.
The reaction of gaseous chlorine with pentachlorophenol appeared to be
less vigorous than when hypochlorite was used, especially at low concen-
trations (2.0 to 4.0 rng/1) of pentachlorophenol.
20
-------
TABLE 5. EFFECT OF CHLORINATION OF PENTACHLOROPHENOL WASTE ON COD
Test Conditions
Calcium Hypochlorite
pH » 4.5
Calcium Hypochlorite
pH = 7. a
Chlorine Gas
pH = 4.5
Chlorine Gas
pH - 7.0
Available Chlorine
(g/liter)
0.0
0.5
1.0
1.5
2.0
3.0
4.0
5.0
0.0
0.5
1.0
1.5
2.0
3.0
4.0
5.0
0.0
Of
.5
1.0
1.5
2.0
3.0
4.0
5.0
10.0
0.0
Of*
.5
1.0
1.5
2.0
3.0
4.0
5.0
10.0
COD
(mg/ liter)
24,200
10,650
10,600
10,300
23,800-
10,300
10,200
10,050
20,400
10,250
10,600
10,200
23,600
9^60
10,700
11,250
21
-------
BIOLOGICAL TREATMENT
Activated Sludge
Cooke and Graham (34) performed laboratory scale studies on the
biological degradation of phenolic wastes by the complete mixed acti-
vated sludge system. While many of the basic parameters needed for
design such as MLSS were not presented, the final results were conclu-
sive, The feed liquors contained phenols, thiocyanates, ammonia, and
organic acids. Aeration varied from 8 to 50 hours. Influent concentration
and percentage removal of phenol averaged 281 mg/1 and 78 percent,
respectively at a volumetric loading of 144 to 1609 kg/100 m3/day
(9 to 100 lb/1000 ft3/day).
Badger and Jackman (35), studying bacteriological oxidation of
phenols in aerated reaction vessels on a continuous flow basis, with
a loading of approximately 1600 to 2400 kg/1000 m3/day (100-150 Ib
phenol/1000 ft3/day) and a MLSS of 2000 mg/1, found that with wastes con-
taining up to 5000 mg/1 phenol, a two day retention period could produce
removal efficiencies in excess of 90 percent. Because the investigators
were working with a coke gasification plant waste, the liquor contained
thiocyanates. Higher oxidation efficiencies could be achieved with a
reduction of the thiocyanate in the waste. Gas chromatography indicated
no phenolic end products of degradation with original waste being a
mixture of 36 percent monohydric and 64 percent polyhydric phenols.
Pruessner and Mancini (36) obtained a 99 percent oxidation efficiency
for BOD in petrochemical wastes. Similarly, Coe (37) reported reductions
of both BOD and phenols of 95 percent from petroleum wastes in bench-scale
tests of the activated sludge process. Optimum BOD loads of 2247 kilo-
grams/1000 m3 per day (140 pounds/1000 ft3 per dayjwere obtained. Coke
plant effluents were successfully treated by Ludberg and Nicks (38),
although some difficulty in start-up of the activated sludge system was
experienced because of the high phenol content of the water.
The complete mixed, activated sludge process was employed to process
a high-phenolic wastewater from a coal-tar distilling plant in Ontario (39).
Initial phenol and COD concentrations of SOO and 6,000 mg/1Her, respec-
tively, were reduced in excess of 99 percent for phenols and 90 percent
for COD.
Coal gas washing liquor was successfully treated by Nakashio (40)
using activated sludge at a loading rate of 0.116 kg of phenol/kg MLSS/day.
An influent phenol concentration of 1200 mg/1 was reduced by more than
99 percent in this year-long study. Similar phenol removal rates were
obtained by Reid and Janson (41), in treating wastewaters generated by
the washing and decarbonization of aircraft engine parts. Other examples
of biological treatment of phenolic wastes include work by Putilena (42),
Meissner (43) and Shukov, et. al. (44).
Of particular interest is a specific test on the biological treat-
ment of coke plant wastes containing phenols and various organics. In
22
-------
(O
a:
o
o
1 _
Slope = K = 0.30 day"1
Le =
La
1 + O.SOt
5 10 15
Aeration Time (Days)
i
20
FIGURE 8. Determination of Reaction Rate Constant for a
Creosote Wastewater
23
-------
a report of pilot scale and full scale studies performed by Kostenbader
and Flacksteiner (45), the complete mixed activated sludge process
achieved greater than 99.8 percent oxidation efficiency of phenols.
Successful results were achieved with phenol loadings of 0.86 kg phenol/
kg MLSS/day with an equivalent BOD loading of 2 kg BOD/kg MLSS/day. In
comparison, a typical activated sludge loading is 0.4 kg BOD/kg MLSS/
day. Effluent concentrations of phenol from the pilot plant were 0.2
mg/1 in contrast to influent concentrations of 3500 mg/1. Slight varia-
tions in process efficiency were encountered with varying temperatures
and loading rates. Phosphoric acid was added to achieve a phosphorus-to-
phenol ratio of 1:70. At the termination of pilot plant work, a similar
large scale treatment plant processing of 424 m3/day (112,000 gpd) was
installed and resulted in an effluent containing less than 0.1 mg/1 of
phenol.
Dust and Thompson (46) conducted bench-scale tests of complete-mixed,
activated sludge treatment of creosote and pentachlorophenol wastewaters
using 5-liter units and detention times of 5, 10, 15, and 20 days. The
operational data collected at steady-state conditions of substrate removal
for the creosote waste are shown in Table 6. A plot of these data showed
that the treatabUHy factor, K, was 0.30 days -1 (Figure 8). The
resulting design equation, with t expressed 1n days, is:
Lo
Le * -
+ 0.30*
A plot of percent COD removal versus detention time in the aerator
based on the above equation, shown 1n Figure 9, Indicates that an oxidation
efficiency of about 90 percent can be expected with a detention time of
20 days 1n units of this type.
TABLE 6. SUBSTRATE REMOVAL AT STEADY-STATE CONDITIONS IN ACTIVATED
SLUDGE UNITS CONTAINING CREOSOTE WASTEWATER
Aeration Time, Days 5.0 10.0 14.7 20.1
COD Raw, mg/1
COD Effluent, mg/1
% COD Removal
COD Raw/COD Effluent
447
178
60.1
2.5
447
103
76.9
4.3
442
79
82.2
5.6
444
67
84.8
6.6
Work was conducted to determine the degree of biodegradabillty of
pentachlorophenol waste. Cultures of bacteria prepared from soil removed
from a drainage ditch containing pentachlorophenol waste were used to
inoculate the treatment units. Feed to the units contained 10 mg/liter
24
-------
o
o
90
80
o 70
o
e
IN}
en
a
o
o
«
a.
60
2 50
Lo
0.30*
40
10
Aeration Time (Days)
15
20
FIGURE 9.
COD Removal from a Creosote Wastewater by Aerated lagoon without Sludge Return
-------
of pentachlorophenol and 2,400 mg/1iter COD. For the two 5-liter units
(A and B) the feed was 500 and 1000 ml/day and detention times were, in
order, 10 and 5 days. Removal rates for pentachlorophenol and COD are
given in Table 7. For the first 20 days. Unit A removed only 35 percent
of the pentachlorophenol added to the unit. However, removal increased
dramatically afterward and averaged 94 percent during the remaining 10
days of the study. Unit B consistently removed over 90 percent of the
pentachlorophenol added. Beginning on the 46th day and continuing through
the 51st day, pentachlorophenol loading was increased at two-day intervals
to a maximum of about 59 mg/liter. Removal rates for the three two-day
periods of increased loadings were 94, 97, and 99 percent. COD removal
for the two units averaged about 90 percent over the duration of the study.
Also working with the activated sludge process, Kirsh and Etzel (47)
obtained removal rates for pentachlorophenol in excess of 97 percent
using an 8-hour detention time and a feed concentration of 150 mg/liter.
The pentachlorophenol was supplied to the system in a mixture that included
100 mg/liter phenol. Essentially complete decomposition of the phenol
was obtained, along with a 92 percent reduction in COD,
TABLE 7. REDUCTION IN PENTACHLOROPHENOL AND COD IN WASTEWATER TREATED
IN ACTIVATED SLUDGE UNITS
RAW EFFLUENT FROM UNIT
WASTE (% Removal)
DAYS (rag/1) "A" "B"
COD
1-5
6-10
11-15
16-20
21-25
26-30
31-35
2350
2181
2735
2361
2288
2490
2407
78
79
76
82
90
—
83
78
79
75
68
86
84
80
PENTACHLOROPHENOL
1-5 7.9 20 77
6-10 10.2 55 95
11-15 7.4 33 94
16-20 6.6 30 79
21-25 7.0 - 87
26-30 12.5 94 94
31-35 5.8 94 91
36-40 10.3 -- 91
41-45 10.0 ~ 96
46-47 20.0 ~ 95
48-49 30.0 — 97
50-51 40.0 - 99
-26-
-------
Cooper and Catchpole (48) reported greater than 95 percent oxidation
of phenols using activated sludge units treating coke plant effluents
containing phenols, thiocyanates, and sulfides. Adequate^data were not
available on the detailed operating parameters of the activated sludge
plant.
Trickling Filters
Hsu, Yany, and Weng (49) reported successful treatment of coke plant
phenolic wastes with a trickling filter, removing over 80 percent of the
phenols. It was stated that influent phenol concentrations should not
exceed 100 mg/1.
Using a Surfpac trickling filter, Francingues (50) was able to remove
80 to 90 percent of the influent phenol from a wood preserving creosote
wastewater at a loading rate of about 16 kg/1000 m3/day (1 Ib phenol/
1000 ft3/day).
Sweets, Hamdy, and Weiser (51) studied the bacteria responsible for
phenol reductions in industrial waste and reported good phenol removal
from synthesized waste containing concentrations of 400 mg/1. Reductions
of 23 to 28 percent were achieved in a single pass of the wastewater
through a pilot trickling filter having a filter bed only 30 centimeters
(12 inches) deep.
Waters containing phenol concentrations of up to 7500 mg/1 were suc-
cessfully treated in laboratory tests conducted by Reid and Libby (52).
Phenol removals of 80 to 90 percent were obtained for concentrations on
the order of 400 mg/1. Their work confirmed that of Ross and Shepard
(531 who found that strains of bacteria isolated from a trickling filter
could survive phenol concentrations of 1600 mg/liter and were able to
oxidize phenols in concentrations of 450 mg/liter at better than 99 percent
efficiency. Reid, Wortman, and Walker (54) found that many pure cultures
of bacteria were able to live in phenol concentrations of up to 200 mg/1,
but few survived concentrations above 900 mg/1, although some were grown
in concentrations as high as 3700 mg/1.
Harlow, Shannon.and Sercu (55) described the operation of a
commercial-size trickling filter containing "Dowpac" filter medium that
was used to process wastewater containing 25 mg/1 phenol and 450 to
1900 mg/1 BOD. Reductions of 96 percent for phenols and 97 percent
for BOD were obtained in this unit. Their results compare favorably
-with those reported by Montes, Allen, and Schowell (56) who obtained BOD
reductions of 90 percent in a trickling filter using a 1:2 recycle
ratio, and Dickerson and Laffey (57), who obtained phenol and BOD reduc-
tions of 99.9 and 96.5 percent, respectively, in a trickling filter used
to process refinery wastewater.
A combination biological waste-treatment system employing a trickling
filter and an oxidation pond was reported on by Davies, Biehl, and
Smith (58). The filter, which was packed with a plastic medium, was
used for a roughing treatment of 10.6 million liters (2.8 million gallons)
of wastewater per day, with final treatment occurring in the oxidation
pond. Removal rates of 95 percent for phenols and 60 percent for BOD
-27-
-------
were obtained in the filter, notwithstanding the fact that the pH of
the influent averaged 9.5.
A study of biological treatment of refinery wastewaters by Austin,
Meehan, and Stockham (59) employed a series of four trickling filters
with each filter operating at a different recycle ratio. The waste
contained 22 to 125 mg/liter of oil and this adversely affected BOD
removal. However, phenol removal was unaffected by oil concentrations
within the range studies.
Prather and Gaudy (60) found that significant reductions of COD,
BOD, and phenol concentrations in refinery wastewater were achieved
by simple aeration treatments. They concluded that this phenomenon
accounted for the high allowable loading rates for biological treatments
such as trickling filtration.
The practicality of using trickling filters for secondary treatment
of wastewaters from the wood preserving industry was explored by Dust
and Thompson (46). Creosote wastewater was applied at BOD loading
rates of from 400 to 3050 kilograms/1000 m3 per day (25 to 190 pounds/
1000 ft3 per day) to a pilot unit containing a 6.4 meter (21 feet)
filter bed of plastic media. The corresponding phenol loadings were
1.6 to 54.6 kMograms/1000 m3 per day (0.1 to 3.4 pounds/1000 ft3 per
day). Raw feed-to-recycle ratios varied from 1:7 to 1:28. Daily
samples were analyzed over a period of seven months that included both
winter and summer operating conditions. Because of wastewater charac-
teristics at the particular plant cooperating in the study, the following
pretreatment steps were necessary: (a) equalization of wastes; (b) pri-
mary treatment by coagulation for partial solids removal; (c) dilution of
the wastewater to obtain BOD loading rates commensurate with the range
of raw flow levels provided by the equipment; and (d) addition to the
raw feed of supplementary nitrogen and phosphorus. Dilution ratios
of 0 to 14 were used.
The efficiency of the system was essentially stable for BOD
loadings of less than 1200 kilograms/1000 m3 per day (75 lbs/1000
ft3 per day). The best removal rate was achieved when the hydraulic
application rate was 2.85 Ipm/m2 (0.07 gpm/ft2) of raw waste and
40.7 Ipm/m2 (1.0 gpm/ft2) of recycled waste. The COD, BOD, and
phenol removals obtained under these conditions are given in Table 8.
Table 9 shows the relationship between BOD loading rate and removal
efficiency. BOD removal efficiency at loading rates of 1060 kilograms/
1000 m3 per day (66 pounds/1000 ft3 per day) was on the order of 92
percent, and was not improved at reduced loadings. Comparable values
for phenols at loading rates of 19.3 kilograms/1000 m3 per day (1.2 pounds/
1000 ft3 per day) were about 97 percent.
Since phenol concentrations were more readily reduced to levels
compatible with existing standards than were BOD concentrations, the
sizing of commercial units was based on BOD removal rates. Various
combinations of filter-bed depths, tower diameters, and volumes of
filter media that were calculated to provide a BOD removal rate of
90 percent for an Influent having a BOD of 1500 mg/liter are shown in
Table 10 for a plant with a flow rate of 75,700 Ipd (20,000 gpd).
-28-
-------
TABLE 8. BOD, COD, AND PHENOL LOADING AND REMOVAL RATES FOR PILOT
TRICKLING FILTER PROCESSING A CREOSOTE WASTEWATER
Measurement
BOD
Characteristics
TOD
Phenol
Raw Flow Rate Iprn/m2
(gpm/ft2)
Recycle Flow Rate 1 pro/in2
(gpm/ft2)
2.85
(0.07)
40.7
(1.0)
2.85
(0.07)
40.7
0.0)
2.85
(0.07)
40.7
(1*0)
Influent Concentration (mg/1)
1698
3105
31
Loading Rate gm/m3/day
Effluent Concentration (mg/1)
Removal (%}
1075
(66.3)
137
91.9
1967
(121.3)
709
77.0
19.5
(1.2)
<1.0
99+
29
-------
TABLE 9. RELATIONSHIP BETWEEN BOD LOADING AND TREATABILITY FOR
PILOT TRICKLING FILTER PROCESSING A CREOSOTE WASTEWATER
BOD Loading
kg/cu m
373
421
599
859
1069
1231
1377
1863
2527
a
Based
BOD Loading
(Ib/cu ft. /day)
(23)
(26)
(37)
(53)
(66)
(76)
(85)
(115)
(156)
on the equation:
E§ = eKD/
Removal Treatability a
(«) Factor
91
95
92
93
92
82
80
75
62
Q °'5 (Germain, 1966)
0.0301
0.0383
0.0458
0.0347
0.0312
0.0339
0.0286
0.0182
0.0130
in which Le = BOD concentration of settled effluent,
Lp = BOD of feed, Q = hydraulic application rate of
raw waste in gpm/ft^, D = depth of media in feet, and
K = treatability factor (rate coefficient).
30
-------
TABLE 10. SIZING OF TRICKLING FILTER FOR A WOOD PRESERVING PLANT
(NOTE: Data are based on a flow rate of 75,700 liters per
day (20,000 gallons per day), with filter influent
BOD of 1500 and effluent BOD of 150 mg/1).
Depth of
filter
bed
m
(ft)
Raw Flow
1 pm/m2
(gpm/ft2)
filter
surface)
Recycle flow
1 pm/m2
(gpm/ft2)
filter
surface)
Filter
Surface
area
(ft2)
Tower
dia
m
(ft)
Vol ume
of
media
uj3
(ft3)
3.26
(10.7)
3.81
(12.5)
4.36
(14.3)
4.91
(16.1)
5.46
(17.9)
5.97
(19.6)
6.52
(21.4)
0.774
(0.019)
1.059
(0.206)
1.385
(0.034)
1.793
(0.044)
2.200
(0.054)
2.648
(0.065)
3.178
(0.078)
29.7
(0.73)
29.3
(0.72)
28.9
(0.71)
28.5
(0.70)
28.1
(0.69)
27.7
(0.68)
27.3
(0.67)
65.8
(708)
48.3
(520)
37.0
(398)
29.3
(315)
23.7
(255)
19.5
(210)
16.4
(177)
9.14
(30.0)
7.83
(25.7)
6.86
(22.5)
6.10
(20.0)
5.49
(18.0)
4.97
(16.3)
4.57
(15.0)
213
(7617)
183
(6529)
160
(5724)
142
(5079)
128
(4572)
116
(4156)
107
(3810)
Oxidation Ponds
The American Petroleum Institute's "Manual on Disposal of Refinery
Wastes" (61) refers to several industries that have successfully used
oxidation ponds to treat phenolic wastes. Montes (62) reported on
results of field studies involving the treatment of petrochemical wastes
using oxidation ponds. He obtained BOD reductions of 90 to 95 percent in
ponds loaded at the rate of 84 kilograms of BOD per hectare per day
(75 pounds/acre/day).
31
-------
Phenol concentrations of 990 mg/liter in coke oven effluents
were reduced to about 7 mg/liter in field studies of oxidation ponds
conducted by Biczyski and Suschka (63). Similar results have been
reported by Skogen (64) for a refinery waste.
The literature contains operating data on only one pond used
for treating wastewater from wood preserving operations (65, 66, 67).
This is the oxidation pond used as part of a waste treatment system
by Weyerhaeuser Company at its DeQueen, Arkansas, wood preserving
plant. As originally designed and operated in the early 1960's,
the DeQueen waste treatment system consisted of holding tanks into
which water from the oil-recovery system flowed. From the holding
tanks the water was sprayed into a terraced hillside from which
it flowed into a mixing chamber adjacent to the pond. Here it was
diluted 1:1 with creek water, fortified with ammonia and phosphates,
and discharged into the pond proper. Retention time in the pond
was 45 days. The quality of the effluent was quite variable, with
phenol content ranging up to 40 mg/liter. In 1966, the system was
modified by installing a raceway containing a surface aerator and a
settling basin in a portion of the pond. The discharge from the
mixing chamber now enters a raceway where it is treated with a floc-
culating agent. The floe formed collects in the settling basin.
Detention time is 48 hours in the raceway and 18 hours in the settling
basin from which the wastewater enters the pond proper.
These modifications in effect changed the treating system from
an oxidation pond to a combination aerated lagoon and polishing pond.
The effect on the quality of the effluent was dramatic. Figure 10
shows the phenol content at the outfall of the pond before and after
installation of the aerator. As shown by these data, phenol content
decreased abruptly from an average of about 40 mg/liter to 5 mg/liter.
Even with the modifications described, the efficiency of the
system remains seasonally dependent. Table 11 give phenol and BOD
values for the pond effluent by month for 1968 and 1970. The smaller
fluctuations in these parameters in 1970 as compared with 1968 indicate
a gradual improvement in the system.
Soil Irrigation
The principal feature of the soil irrigation method of waste-
water treatment is its simplicity. Water that has been freed of
surface oils and, depending upon the presence of emulsified oils,
treated with flocculated chemicals and filtered through a sand bed
is simply sprayed onto a prepared field. Soil microorganisms decompose
the organic matter in the water in much the same fashion as occurs in
more conventional waste treatment systems.
In addition to its simplicity, soil irrigation has the advantage
of low capital investment (exclusive of land costs), low operating
and maintenance costs, requires a minimum of mechanical equipment,
32
-------
CO
co
45
40
35
30
25
Q>
o
o
1 15
0)
10
JAN FEB MAR APR MAY JUNE JULY AUG SEPT OCT NOV DEC
Month
Figure 10. Phenol Content in Oxidation Pond Effluent Before and After Installation in June 1966 of Aerator
-------
and produces a high-quality effluent in terms of color, oxygen demand,
and other pertinent parameters. Its chief disadvantage is that its
use requires a minimum of approximately one acre for an application
rate of 13,250 Ipd (3500 gpd). This limitation makes soil irrigation
practical only in areas where land is available and relatively in-
expensive.
TABLE 11. AVERAGE MONTHLY PHENOL AND BOD CONCENTRATIONS IN EFFLUENT
FROM OXIDATION POND
(mg/liter)
1968
Month
January
February
March
April
May
June
July
August
September
October
November
December
Phenol
26
27
25
11
6
5
7
7
7
16
7
11
BOD
290
235
190
150
100
70
90
70
110
150
155
205
1970
Phenol
7
9
6
3
1
1
1
1
1
-
-
-
BOD
95
140
155
95
80
60
35
45
25
-
-
-
Several applications of wastewaters containing high phenol con-
centrations to soil irrigation have been reported. One such report,
by Fisher (68) related the use of soil irrigation to treat wastewaters
from a chemical plant that had the following characteristics:
pH 9 to 10
Color 5,000 to 42,000 units
COD 1,600 to 5,000 mg/liter
BOD 800 to 2,000 mg/liter
-34-
-------
Operating data from a 0.81 hectare (2 acre) field, when irrigated
at a rate of 7570 liters (2,000 gal) per acre/day for a year, showed
color removal of 88 to 99 percent and COD removal of 85 to 99 percent.
The same author reported on the use of this method to treat
effluent from two tar plants that contained 7,000 to 15,000 mg/liter
phenol and 20,000 to 54,000 mg/liter COD. The waste was applied to
the field at a rate of about 9460 liters (2500 gal) per acre/day.
Water leaving the area had COD and phenol concentrations of 60 and
1 mg/liter, respectively. Based on the lower influent concentration
for each parameter, these values represent oxidation efficiencies
of well over 99 percent for both phenol and COD.
Bench-scale treatment of coke plant effluent by soil irrigation
v/as also studied by Fisher. Wastes containing BOD and phenol concen-
trations of 5,000 and 1,550 mg/liter, respectively, were reduced by
95+ and 99+ percent when percolated through 0.9 meters (36 inches) •
of soil. Fisher pointed out that less efficient removal was achieved
with coke-plant effluents using the activated sludge process, even
when the waste was diluted with high-quality water prior to treatment.
The effluent from the units had a color rating of 1,000 to 3,000 units,
compared to 150 units for water that had been treated by soil irrigation.
Both laboratory and pilot scale field tests of soil-irrigation
treatments of wood preserving wastewater were conducted by Dust and
Thompson (46). In the laboratory tests, 210-liter (55 gallon) drums
containing a heavy clay soil 60-centimeters (24 inches) deep were
loaded at rates of 32,8000, 49,260, and 82,000 liters/hectare/day
(3,500, 5,250, and 8,750 gallons/acre/day). Influent COD and phenol
concentrations were 11,500 and 150 mg/liter, respectively. Sufficient
nitrogen and phosphorus were added to the waste to provide a COD:N:P
ratio of 100:5:1. Weekly effluent samples collected at the bottom
of the drums were analyzed for COD and phenol.
Reductions of more than 99 percent in COD content of the wastewater
were attained from the first week in the case of the two highest
loadings and from the fourth week for the lowest loading. A break-
through occurred during the 22nd week for the lowest loading rate
and during the fourth week for the highest loading rate. The COD
removal steadily decreased thereafter for the duration of the test.
Phenol removal showed no such reduction, but instead remained high
throughout the test. The average test results for the three loading
rates are given in Table 12. Average phenol removal was 99+ percent.
Removal of COD exceeded 99 percent prior to breakthrough and averaged
over 85 percent during the last week of the test.
The field portion of Dust and Thompson's (46) study was carried
out on an 0.28-hectare (0.8 acre) plot prepared by grading to an
approximately uniform slope and seeded to native grasses. Wood
preserving wastewater from an equalization pond was applied to the
field at the rate of 32,800 liters/hectare/day (3,500 gallons/acre/day)
for a period of nine months. Average monthly influent COD and phenol
concentrations ranged from 2,000 to 3,800 mg/liter and 235 to 900
mg/liter, respectively. Supplementary nitrogen and phosphorus were
35
-------
not added. Samples for analyses were collected weekly at soil depths
of 0 (surface),30, 60, and 120 centimeters (1, 2, and 4 feet).
The major biological reduction in COD and phenol content occurped
at the surface and in the upper 30 centimeters (1 foot) of soil.
A COD reduction of 55.0 percent was attributed to overland flow.
The comparable reduction for phenol content was 55.4 percent (Table 13),
COD reductions at the three soil depths, based on raw waste to the
field, were 94.9, 95.3, and 97.4 percent, respectively, for the 30-,
60-, and 120 centimeter (1-, 2-, and 4-foot) depths. For phenols,
the reductions were, in order, 98.9, 99.2, and 99.6 percent.
TABLE 12. RESULTS OF LABORATORY TESTS OF SOIL IRRIGATION METHOD OF
WASTEWATER TREATMENT*
Loading Rate
(Liter/ha/day)
32,800
(3,500)
49,260
(5,250)
82,000
(8,750)
Length of
Test
(Week)
31
13
14
Avg. & COD
Removal to
Breakthrough
99.1 (22 wks)
99.6
99.0 (4 wks)
COD REMOVAL
Last Week
of Test
%
85.8
99.2
84.3
Phenol
Avg. %
Removal
(All Weeks)
98.5
99.7
99.7
Loading rates in parentheses in gallons/acre/day
Creosote wastewater containing 11,500 mg/liter of COD and 150 mg/Hter
of phenol was used.
Activated Carbon Filtration
Activated carbon is used commercially to treat petroleum (69) and
other types (70) of Industrial wastewaters. It can also be used
effectively to remove phenolic compounds from wood preserving waste
streams. Although carbon has a strong affinity for nonpolar compounds
such as phenols, adsorption is not limited to these materials. Other
organic materials in wastewater are also adsorbed, resulting in a
decrease in the total oxygen demand of the waste. Because the concen-
tration of the latter substances exceeds that of phenols in effluents
from wood preserving plants, the useful life of activated carbon is
determined by the concentration of these materials and the rate at
which they are adsorbed.
36
-------
TABLE 13. REDUCTION OF COD AND PHENOL CONTENT IN WASTEWATER TREATED
BY SOIL IRRIGATION
Soil Depth (centimeters)
Month Raw Waste
July
August
September
October
November
December
January
February
March
April
Average % Removal
(weighted)
July
August
September
October
November
December
January
February
March
April
2235
2030
2355
1780
2060
3810
2230
2420
2460
2980
235
512
923
310
234
327
236
246
277
236
0
COD (mg/1)
1400
1150
1410
960
1150
670
940
580
810
2410
55.0
Phenol (mq/1)
186
268
433
150
86
6
70
in
77
172
30
••» •
—
--
150
170
72
121
144
101
126
94.9
MM
—
«
4.6
7.7
1.8
1.9
4.9
2.3
1.9
60
M m.
—
—
—
170
91
127
92
102
—
95.3
..
—
~
_.
3.8
9.0
3.8
2.3
1.9
0.0
120
66
64
90
61
46
•58
64
64
68
76
97.4
1.8
0.0
0.0
2.8
0.0
3.8
0.0
1.8
1 .3
0.8
Average % Removal
(weighted)
55.4
98.9
99.2
99.6
37
-------
Results of carbon-adsorption studies conducted by Dust and Thompson
(46) on a creosote wastewater are shown in Figure 11. Granular carbon
was used and the contact time was 24 hours. The wastewater was floccu-
lated with ferric chloride and its pH adjusted to 4.0 prior to exposure
to the carbon. As shown in the figure, 96 percent of the phenols and
80 percent of the COD were removed from the wastewater at a carbon dosage
of 8 g/liter. The loading rate dropped off sharply at that point, and
no further increases in phenol removal and only small increases in COD
removal occurred by increasing carbon dosage to 50 gm/liter. Similar
results were obtained in tests using pentachlorophenol wastewater.
Results of adsorption isotherms that were run on pentachlorophenol
wastewater, and other samples of creosote wastewater followed a pattern
similar to that shown in Figure 11. In some instances a residual content
of phenolic compounds remained in wastewater after a contact period of
24 hours with the highest dosage of activated carbon employed, while in
other instances all of the phenols were removed. Loading rates of 0.16
kilograms of phenol and 1.2 kilograms of COD per kilogram of carbon were
typical, but much lower rates were obtained with some wastewaters.
Miscellaneous Treatment and Handling Methods
Wastes from wood preserving plants may also be handled by containment,
if adequate land is available, by spray evaporation, if a relatively
high operating cost can be tolerated, or by heat evaporation or incinera-
tion if the waste stream is small.
SUMMARY
It was concluded that previous laboratory and pilot work demonstrated
that chemical or biological action could be used to reduce wastewater
pentachlorophenol concentration. Pentachlorophenol is more toxic than
simple creosote but less soluble in water. High concentrations of
pentachlorophenol can be oxidized to harmless, biodegradable chloranyls.
Low concentration of pentachlorophenol, on the order of 10 to 30 mg/1,
can be degraded biologically in the presence of relatively numerous
nutrients. Some portion of the Carbondale plant's wastewater could,
therefore, be degraded in an activated sludge system, probably including
the pnetachlorophenol and creosote fractions.
Ample evidence was found in the literature to substantiate destruc-
tive chlorination and biological oxidation of phenolic compounds. Thus,
while there remained some ambiguity concerning the detailed operating
parameters for a treatment plant for these wastes, the basic processes
were sound. It was felt that early ambiguities arose from non-parametric
studies with varying feed waters, few of which were specifically wood
preserving wastewaters. It was the intent of the Carbondale study to
clarify the various operating parameters and provide a sound basis for
future design work.
33
-------
10CH
10 20 30
Activated Carbon (gm/liter)
FIGURE 11
Relationship Between Weight of Activated Carbon
Added and Removal of COD and Phenols from a Creosote Wastewater
39
-------
SECTION V
MATERIALS AND METHODS
Following acceptance of the grant application, laboratory and
field studies were begun in Carbondale to establish wastewater flow
and characteristics. A mobile laboratory was stationed on-site for
a five day period during which samples were collected and analyzed.
Flow measurements were initiated and continued for a two month period.
A discussion of data collection methods and of development of design
parameters are presented in this section.
PRE-DESIGN STUDIES
At the time of the pre-design wastewater studies, condensate
from the treating cylinders was pumped to primary separation tanks.
The pentachlorophenol condensate which is isolated from the creosote
waste stream receives polymer addition before going to the secondary
penta separator. Since penta-oil is lighter than water, skimming
allows good separation. The creosote condensate, after polymer
addition, was separated by settling the heavier creosote and skimming
the light oils. The two waste streams were then combined in a common
sump and pumped to Pond 2 or Pond 3. The effluents from Ponds 2 and 3
flowed to a Pond 4 by gravity. Pond 1 was maintained for emergency use
only. Previous to the present design, these ponds, together with the
primary oil removal and preservation recovery system and a 1.05 hectare
(2.58 acre) irrigation field constituted the waste treatment facilities
for the Carbondale plant.
The wastewater flow during the pre-design study averaged 27,055
1 pd (7,148 gpd) of which 36 percent was penta waste and 64 percent
creosote waste. The range and variability of the total wastestream and
the constituent flows is illustrated in Figure 12. Obviously, the flow-
rate was erratic, varying from less than one-fourth to nearly three
times the average daily flow. Of importance is the fact that penta flow
was non-existent for several consecutive days and then occurred in
slug flows.
The analytical data collected during the five day sampling period
is presented in Table 14. Each pond was sampled during this period;
however, due to inplant modifications, it was decided that the pond data
was of little value for design. The samples considered to be of value
were those from the creosote decantor effluent and the common sump.
During the period of sampling, there was no flow for at least two days
from the penta separator and, therefore, the concentrations determined
in the commom sump are not necessarily average concentrations. A
better estimate of average conditions is obtained by calculating con-
centrations based on the preparation of average flow from each waste
source. This calculated average is also shown in Table 14.
40
-------
20,250
10,160
COMBINED WASTE FLOW
O PENTACHLOROPHENOL WASTE
MISSING DATA
POINT
IS l« 17 18 19 20 21 22 23 24 25 26 27 29
Z9 30
FIGURE 12.
Time/Days
Flowrate Variation with Time
-------
TABLE 14. Analytical Data From Pre-Design Study
ro
Date
6-25
6-26
6-27
6-28
6-29
Sample
Point
Creosote
Effluent
Penta
Effluent
Common Sump
Creosote
Effluent
Penta
Effluent
Penta
Effluent
Creosote
Effluent
Penta
Effluent
Common Sump
Creosote
Effluent
Penta
Effluent
Common Sump
COD
(mg/1)
2,130
4,360
2,130
7,800
6,900
-
7,990
4,720
7,260
3,209
4,972
2,621
BOD5
(rag/T)
615
1,335
600
525
1,395
-
-
-
-
1,200
2,512
-
TS
(mg/1)
4,270
20,780
5,480
5,220
19,830
-
5,400
19,980
7,250
4,184
19,844
4,447
TSS
(mg/1)
147
156
181
70
138
-
58
143
56
142
158
174
Phenol
(mg/D
100
50
120
140
65
-
132
70
140
200
-
-
Oil and Grease NH3+-N Total
(mg/1) (mg/1) (mg/1) pH
89 550 3,200 5.6
4.9
5.6
96 500 3,050 5.6
178 1,750 10,200 4.7
263 1,650 11,200
5.6
4.9
5.4
275 500 2,050 5.7
4.8
5.7
-------
TABLE 14. ANALYTICAL DATA FROM PRE-DESIGN STUDY
Sample
Date Point
Average
creosote
effluent
Penta
Effluent
Common Sump
COD
(mg/1 )
5,282
5,238
4,004
BOD5
(mg/T)
780
1,747
600
TS
(mg/1)
4,769
20,109
5,726
TSS
(mg/1)
104
149
137
Phenol
(mg/1)
143
78
130
Oil and Grease
(mg/1)
153
221
_
NH3+-N
(mg/1)
517
1,700
_
Total
(mg/1)
2,767
10,700
_
pH
5.6
4.8
5.6
oo
CALCULATED
AVERAGE
CONCENTRATIONS
OF COMBINED
EFFLUENTS 5,266 1,126 10,291
121
120
178
943
5,623 5.3
-------
The ratio of BOD to COD for the calculated average data was
relatively low, possibly indicating some degree of biological inhibition.
Figure 13 shows the effluent dilution of the BOD test. When the dilution
factor was increased from 99.6 to 99.9 percent, the BOD of the penta
effluent increased from 1860 to 3500 mg/1. An increase in dilution
from 99.8 to 99.9 percent for the creosote effluent resulted in a BOD
increase from 1000 to 2000 mg/1. Assuming the samples were properly
seeded, the value of the BOD test becomes questionable. While a limited
amount of BOD data was collected during the study and is presented
in this report where appropriate; the limitations on its usefulness
should be noted in light of the above discussion.
The majority of the solids, as noted in Table 14, are composed
of dissolved material which resulted for the most part from salts in
fire retardant compounds which contained ammonium phosphate, ammonium
sulfate, sodium tetraborate and boric acid as their primary constituents.
Analyses performed later showed high boron levels. Also, the nutrient
levels were relatively high due to the use of the fire retardant. The
plant, subsequent to thepre-designed study, terminated the use of fire
retardant preservative although boron persisted in the effluent for a
period of time.
The phenol concentration averaged 120 mg/1 during the study while
the oil and grease concentration was 178 mg/1 and pH averaged 5.3. No
analytical data is given in Table 14 for penta because at the time of
the pre-design study no suitable analysis technique had been developed.
Later analyses by Koppers personnel indicated that the penta concentration
was less than 20 mg/1.
DEVELOPMENT OF PARAMETERS
The average conditions determined in the pre-design study were
chosen as the hydraulic basis for design. The average daily flow
used for design was 27,063 Ipd (7150 gpd) or 19 1pm (5 gpm). Further,
it was decided that by maintaining Pond 2 as a surge lagoon it would be
possible to operate the treatment facility at a constant feed rate and
minimize the problems associated with flowrate and quality variations.
The pre-design data indicated that primary and secondary preserva-
tive recovery was efficiently removing most of the separable oils from
the effluent. For this reason no modification of the existing oil re-
moval system was considered necessary.
Laboratory studies by Thompson (46) and others indicated that
biological oxidation of penta was possible. However, due to uncertainty
with regard to the degree of reduction possible, the maximum concentration
allowable, and the effects of penta on a biological system treating a
complex, heterogeneous wastewater, it was decided that pretreatment
with chlorine should be included in the design. Preliminary tests
indicated that several hours detention time would reduce the chlorine
residual to minimal levels. For this reason no chlorine removal facili-
ties were included in the design of the pre-chlorination section of
the treatment system.
44
-------
4000-
PENTACHLOROPHENOL
EFFLUENT
3000
2000'
a
o
m
LU
1000-
CREOSOTE
EFFLUENT
99.6
99.7
^DILUTION
99.8
99.9
100.0
FIGURE 13,
Percent Dilution vs. BOD
45
-------
On the basis of the limited information in the literature, recent
laboratory data, and the consultant's experience with biological treat-
ment, the system with the best potential for success was judged to be
complete mix activated sludge. This process, having a record of success
in many industrial applications, has the advantage of reducing the effects
of shock loadings. Additionally, it requires relatively little land area
and is a viable treatment alternative for wood preserving plants with
little available space.
The determination of design parameters was based on experience
with the activated sludge process and on the limited laboratory and
literature data relative to wood preserving wastes. It was felt that
the design should be based on the assumption that pre-chlorination
might not be necessary. Therefore, all loadings, detention times, and
capacities were based on the data shown in Table 14 of this section.
The factor considered most important with regard to organic loading
rates was the penta concentration in the mixed liquor. Laboratory
results had shown biological degradation of penta at loadings of 1.62
gm/m3 (0.1 lb/1000 cu ft) of aeration volume (71). Slug loads of 6.5
gm/nr (0.4 lb/1000 cu ft) had been tolerated in the same study. This
is equivalent to an average loading of 4.2 kg penta/kkg MLSS with shock
loadings up to 16.9 kg penta/kkg MLSS. Considering that this waste also
contains phenols in excess of 100 mg/1, a conservative loading rate of
2 kg penta/kkg MLSS was chosen. Assuming a penta concentration of 20
mg/1 and a mixed liquor concentration of 3000 mg/1 resulted in a required
aeration volume of about 83,270 liters (22,000 gallons) and a hydraulic
detention time exceeding three days, the corresponding BOD loading
(usinq the calculated average from Table 14 which was assumed to be
valid) was a conservative 0.1 kg BOD/kg MLSS. The phenol loading rate
was about 0.01 kg phenol/kg MLSS, which was considerably less that the
maximum loadings recorded in the literature for wastewaters not con-
taining penta. With these conservative design parameters and with the
further safeguard of pre-chlorination, it was felt that satisfactory
results could be obtained.
Due to the lack of field information on the necessary dosages of
chlorine for pre-chlorination and post-chlorination, precise design
parameters could not be defined. The pre-chlorination dosage capability
was therefore designed to range from 0 to 4000 mg/1 and the post-
chlorination from 0 to 400 mg/1.
DESIGN AND CONSTRUCTION
The basic units required for effective chemical and biological
treatment of the wastewater based on the parameters developed above and
with as much flexibility as possible due to the experimental nature of
the project, were considered to be as follows:
1. Surge or equalization basin. The existing Pond #2 was suitable
for this purpose.
2. Influent pump. A small centrifugal pump with a maximum
capacity of 37,850 Ipd (10,000 gpd) mounted on a floating
platform in Pond #2 was considered adequate.
46
-------
3. Flow measurement and control device. The small flow could be
easily measured with a rotameter and controlled with a valve.
4. Pre-chlorination unit. Total detention time equaling 12 hours
with baffling for varying detention times and by-pass capability.
5. Aeration tank. A total volume of at least 83,290 Ipd (22,000
gallons) should be divided into two or more sections for varying
loading rates.
6. Final clarifier. An overflow rate of 8150 to 12,200 Ipd/m2
(200 to 300 gpd/ft2) was considered necessary.
7. Post chlorination tank. A detention time of 8 to 10 hours was
provided.
8. Chlorine injector equipment. A variable feed rate up to 91
kg/day (200 Ib/day) was provided.
9. Aerobic digester. A retention period of 15 to 20 days was
allowed.
10. Final sludge disposal was to be by irrigation on an existing
field.
A package unit was delivered by Davco in January 1973. As illus-
trated in Figure 14, the treatment plant consisted of two rectangular
tanks and a separate circular clarifier. The first rectangular tank,
3.66 m (12 ft) wide by 9.75 m (32 ft) long, was divided into an aerobic
digestion tank and pre-chlorination tank, each approximately 1.83 m
(6 ft) in length, and the #1 aeration tank which was about 6.1 m (20 ft)
long. The secorvd tank was 2.44 (8 ft) wide by 11.6 m (38 ft) long and
was divided into two sections, the #2 aeration tank which was about
7.9 m (26 ft) long, and the post chlorination tank which was about
1.83 m (6 ft) long. The clarifier had a diameter of approximately 2.44 m
(8 ft). Flow entered either the pre-chlorination chamber or moved
directly to the aeration tank. At 19 1pm (5 gpm), the detention time
in the pre-chlorination tank was about 15 hours. This tank was later
baffled to provide variable detention times. The aeration time in the
#1 tank was about 50 hours. All activated sludge was returned to this
tank. The flow then entered aeration tank #2 which had a detention time
of 47 hours at a flow of 19 1pm (5 gpm). The mixed liquor from tank
#2 then settled in the clarifier which had a surface overflow rate
of less than 6100 Ipd/sq m 150 gpd/sq ft) at the average design flow of
27,250 Ipd (7200 gpd). The clarifier overflow could be post chlorinated
prior to final discharge.
Air was supplied to the aeration tanks, aerobic digester, and the
air lift sludge return line by a duplex blower driven by a 7.5 hp motor.
The total expected air requirement was 5.2 cu m/min at 1.34 atm (185 cfm
at 5 psig).
The entire plant was placed on a reinforced concrete slab above
ground. All extension surfaces were coated with insulating material to
protect against severe winter weather. Heater tape was placed on
exposed pipes and valves and electric immersion heaters were placed in
the aeration tanks.
47
-------
INFLUENT
00
RETURN SLUDGE
BLOWER
DUPLEX
AERATION TANK NO. 1
AERATION TANK NO. 2 BYPASS
CLARIFIER
AERATION TANK NO. 2
EFFLUENT
FIGURE 14.
Schematic of "Package" Treatment System
-------
Due to the high nutrient levels observed in the pre-design study,
no nutrient addition was provided in the final design. Control of pH,
was not included in the final design. It was found that manual addition
of lime to the aeration basins on an as needed basis would provide
satisfactory pH control.
In addition to the treatment plant itself, laboratory facilities
were also constructed on-site. A full time chemist was employed to
perform all analyses on-site with the exception of BOD tests which were
conducted by an outside laboratory. A treatment plant operator was
trained to maintain and operate the plant and also to assist in per-
forming daily sample collections and analyses.
PLAN OF OPERATION
The original operating schedule developed for the project was
based on the uncertainty of the effects of pentachlorophenol on the .
activated sludge process. The original schedule is as follows:
Month #1 - Chlorinate the effluent at 100 percent of chlorinator
capacity using full detention time in prechlorination
facility. With BOD loading equaling 0.1 kg BOD/day/kg
MLSS, maintain MLSS around 3,000 mg/1. Post-chlorinate
to produce an effluent phenol concentration of 0.1 mg/1.
Month #2 - Reduce pre-chlorination to 50% of capacity or chlorinate
only half of the influent stream at 100% capacity, other-
wise, maintain steady-state conditions.
Month #3 - Reduce pre-chlorination by 50% again, resulting in a total
decrease since initial operation of 75%. Maintain con-
stant conditions.
Month #4 - Based on the previous three months of operation, dis-
continue pre-chlorination entirely or operate at the miniumum
level apparently required. Determine this level by ex-
amining the condition of the biological process during the
first three months. Also, study the effect of detention time
on chlorination by collecting samples from each section
of the baffled pre-chlorination tank.
Month #5 - Maintain pre-chlorination at the minimum level determined
above or increase it as necessary while doubling BOD and
PCP loadings by halving the aeration tank volume. Also,
attempt a 20% reduction in MLSS concentration.
Month #6 - Pre-chlorinate as necessary while again reducing MLSS by
20%. After two weeks, if possible, reduce MLSS by another
20%.
Month #7 - Pre-chlorinate as necessary while again reducing MLSS by
20% with further reductions if possible.
Month #8 - Operate at steady state conditions utilizing the optimum
pre- and post- chlorination dosages determined during the
operating period, as well as the corresponding optimum
BOD and penta loading rates.
Although the package plant arrived in Carbondale in February 1973,
because of inclement weather it was not ready for startup until July.
49
-------
Due to the delay, it was decided to initiate operation without pre-
chlorination and thereby determine immediately whether chlorination
would be required.
On this basis, plant startup procedures were initiated on July
26, 1973. The aeration basins were filled with water from the emergency
lagoon, Pond #1, which had low concentrations of boron, phenols, and
penta. Bacterial inoculation was accomplished by placing horse manure
into the aeration tank and aeration was begun. One week later a 23 1pm
(6 gpm) feed mixture of emergency lagoon water and concentrated waste
from Pond #2 was begun. By the middle of August the proportion of the
mixture consisting of concentrated waste had been increased to 100
percent. Normal mechanical problems were encountered during the initial
startup period. During the latter part of August, a pin sheared in the
clarifier sludge rake mechanism and one pump failed. The sludge rake
malfunction resulted in low MLSS concentrations throughout August. After
the shear pin was replaced, the treatment plant was again placed in
operation and startup was continued through September 1973.
Because of the immediate success of the complete mix process with-
out pre-chlorination, the entire operating schedule was modified.
This revised schedule is shown in Table 15. Due to inclement weather
and later mechanical failures, this schedule could not be adhered to
exactly; however, all the desired objectives were accomplished during
the study period.
TESTING SCHEDULE
The on-site laboratory was equipped with the necessary materials
to perform basic gravimetric, colorimetric, and titrametric analyses
including COD, solids, nutrients, phenols, pentachlorophenol, oil and
grease, residual chlorine, pH, temperature, and dissolved oxygen.
BOD analyses were performed by an outside laboratory and any special
analyses required such as gas chromatography or metal analyses were
performed elsewhere.
Samples were collected daily for analysis. Batch samples were
used instead of composites because of the presence of the large surge
lagoon which minimized fluctuations and because of the large detention
time in the treatment plant itself which tended to smooth out variations
throughout the system.
Due to the large number of analyses needed and the limited staff
at Carbondale, a schedule of analyses based on the minimum requirements
for experimentation and the manpower limitations had to be developed.
The schedule shown in Table 16 was followed throughout the study period.
During periods when more information was desired in one unit of the
treatment system than another, more analyses were performed. For
instance, when the effects of post-chlorination were being closely
studied, more chlorine residual determinations were required. BOD,
COD, phenol, solids, and oil and grease analyses were performed ac-
cording to Standard Methods (13 edition) (72). Nutrients were analyzed
50
-------
TABLE 15. REVISED OPERATING SCHEDULE
# 2
# 3
# 4
# 5
# 6
i 7
Objective
Startup and shakedown
Hydraulic loading
variation
Organic loading
variation
Increased organic loading
Increased organic loading
Post-chlorination studies
Pre-chlorination studies
# 8 Optimization
Operation
Inoculate aeration tanks with activated
sludge or other bacteria source. Operate
plant with increasing proportion of con-
centrated waste and decreasing proportion
of dilution water. Shakedown mechanical
equipment, repairing and replacing as
necessary.
Increase the hydraulic loading to the
treatment system in increments up to the
limit of hydraulic capacity or organic
loading rate, whichever is reached first.
Restabilize the process at 4 to 6 gpm
using only one aeration basin.
Reduce the mixed liquor suspended solids
or increase the flow rate incrementally.
Continue reducing the MLSS or increasing
the flow rate incrementally.
Measure the effects of post-chlorination
on PCP, phenol, COD and BOD concentrations
at various dosages, increasing the dosage
incrementally over the month.
Operate the treatment plant at near constant
conditions while increasing the pre-chlori-
nation dosage incrementally and measuring
its effect on the activated sludge process.
Based on the previous months' experience,
operate the process at those conditions
which gave the best results including pre-
and post-chlorination as necessary.
51
-------
TABLE 16. SCHEDULE OF ANALYSES
Sampling Point and Number of Analyses Per Week
Parameter
BOD
COD
Phenol
Penta
TS
TSS
VSS
TDS
NH4+
P04=
Influent
2
2
2
2
2
2
-
2
1
1
Prechlorination
1
1
1
1
-
-
-
-
-
_
Aeration Basins
2
2
2
2
-
3
3
-
-
_
Clarifier Post Chlorination
1 2
1 2
1 2
1 2
2
2
-
2
1
1
SVI
Oil and grease
Temperature
D.O.
PH
Residual
5
5
5
0-5
0-5
52
-------
with colorimetric kits. The determination of penta proved to be
difficult and, in fact, no truly satisfactory method was found. The
method chosen at the beginning of the study after careful evaluation
of the two or three methods available was the Safram'n method which
is a distillation and color development technique.
53
-------
SECTION VI
RESULTS AND DISCUSSION
The experimentation phase of the project was begun in July 1973,
and was completed in May 1974. The raw data collected during the study
is contained in the Appendix.
PHASE 1 - START-UP AND STABILIZATION
The start-up of the treatment system was accomplished with rela-
tively little difficulty. Without the mechanical start-up problems
encountered, the activated sludge process could have been stabilized in
two weeks, but, with the mechanical problems, as previously discussed,
the start-up and stabilization phase took about five weeks. A significant
amount of data was not collected during the start-up period; however,
most of the data obtained is presented in Table 17. The average influent
and effluent concentrations of COD for the five week period were 1540
mg/1 and 410 mg/1, respectively, which is a reduction efficiency of
73 percent. The phenol reduction efficiency for the same period was
97 percent. The influent penta concentration was much less than expected
but a reduction through the treatment system of 79 percent was obtained.
PHASE 2 - STEADY STATE OPERATION
For a period of about four weeks (August 30 through October 5,
1973), the treatment plant was operated at constant flow and loading
to evaluate the performance of the activated sludge process under
controlled conditions. During this phase, flowrate was maintained
at 23 liters per minute (six gallons per minute), and influent COD
averaged 178 mg/1, influent phenols averaged 88 mg/1, and influent
penta averaged 1.7 mg/1. The average results of this period are pre-
sented in Table 18 and, as can be seen, the effluent quality varied
little during the four week period indicating a stable biological
process. Effluent COD averaged 404 mg/1 and never varied more than
10 percent from this value. Effluent phenols rarely varied from the
average value of 1 mg/1. The effluent PCP value never exceeded 0.6
mg/1 and averaged 0.4 mg/1. As it turned out, the loading rate was
not constant because of sludge buildup. However, in general, it can
be concluded from this data that a conservatively designed activated
sludge process treating creosote and pentachlorophenol wastewater
should be able to reduce COD by 75 to 80 percent, phenols by 95 to 99
percent, and PCP by 75 to 80 percent.
PHASE 3 - LOADING RATE VARIATION
Phase 2, Steady-State Operation, was terminated after the first
week in October 1973. From that time until mid-November, experimenta-
tion was directed primarily at examining the effects of loading rate
variations on the activated sludge process. Due to the conservative
design of the treatment system, a considerable degree of variation both
in organic and hydraulic loading rate was possible.
54
-------
TABLE 17. STARTUP AND STABILIZATION DATA
Date
1973
7-30
7-31
8-1
8-2
8-3
8-4
8-5
8-6
8-8
8-10
Flow, liters per minute
Dilution Concentrated Sampling
Water Waste Point
0 0 #1 Aeration
Dilution
Raw Waste
0 11,350 #1 Aeration
#2 Aeration
Effluent
0 0 #1 Aeration
#2 Aeration
Effluent
0 0 #1 Aeration
#2 Aeration
Effluent
17.0 1.89 Influent
#1 Aeration
#2 Aeration
Effluent
15.1 3.8 Influent
Effluent
13.2 5.7 Influent
Effluent
11.4 7.6 Influent
£1 Aeration
#2 Aeration
Effluent
3.8 15.1 Influent
#1 Aeration
#2 Aeration
Effluent
3.8 15.1 Influent
=1 Aeration
r2 Aeration
Effluent
Parameter
COD Phenols PCP
(mg/1) (mg/1) (mg/1 )
1
- 1
150
16
8
5
1 0.6
1 0.6
1 0.6
0.6
0.6
0.6
1
1
1
1
10
1 -
12
1
15
1
1 -
1
30
1
1
1
65
1.5
1.6
1.4
Sludge
(ml/1)
0
_
-
_
-
_
M
-
0.2
0.3
-
0.1
0.05
-
•*
-
.
-
fm
0.1
0.1
-
wm
0.1
0.1
-
_
0.3
0.4
_
55
-------
TABLE 17. STARTUP AND STABILIZATION DATA
Date
1973
8-16
8-17
8-20
Flow, liters per minute
Dilution
Water
3.8
1.9
0
Concentrated
Waste
15.1
15.1
11.4
(Pump Problems)
8-21
8-23
0
0
7.6
11.4
(Pumps Required)
8-24
8-27
8-28
8-29
8-30
8-31
0
0
Clarifier
Clarifier
0
0
15.1
22.7
paddles found
Sampling COD
Point (mg/1)
Influent
#1 Aeration
#2 Aeration
Effluent
Influent
#1 Aeration
#2 Aeration
Effluent
Influent
Effluent
Influent 1,260
#1 Aeration
#2 Aeration
Effluent 350
Influent
Effluent
Influent
Effluent
Influent
#1 Aeration
#2 Aeration
Effluent
Parameter
Phenols PCP
(mg/1) (mg/1)
70
2
2
2
70
3
2
2
70
1
70 3.4
1.5
1.5
1.5 0.6
70 3.4
1.5 0.3
70 2.6
1 0.3
80
3
2
2
Sludge
(ml/1)
0.7
0.6
-
mm
0.5
0.4
-
w
-
_
0.4
0.4
-
mm
-
_
-
—
2.0
1.7
-
to be not functioning
paddles repaired
22.7
22.7
Influent 1,820
#1 Aeration
$2 Aeration
Effluent 470
Influent
rl Aeration
#2 Aeration
Effluent
85 3.0
3
2
2 0.7
95
3
2
2
—
11.0
7.5
-
—
13.0
9.5
_
56
-------
TABLE 17. STARTUP AND STABILIZATION DATA
Flow, liters per minute Parameter
Date Dilution Concentrated Sampling CODPhenols PCPSludge
1973 Water Waste Point (mg/1) (mg/1 (mg/1) (ml/1)
AVERAGE OF ALL STARTUP PERIOD Influent 1,540 56 2.9 34
#1 Aeration - 2-30
DATA n Aeration - 2
Effluent 410 2 0.6 43
P04 NH4+
Influent
#1 Aeration
#2 Aeration
Effluent
TABLE 18. EFFECTS OF
Average Values from Steady
Flow Rate
Influent
22.7 1pm
(6 gpm) Effluent
Reduction
Result of Shock
Flow Rate
41.6 1pm
(11 gpm) Influent
Effluent
Reduction
SHOCK
State
COD
1784
404
77%
555 47.5
430 56.7
440 66.0
LOADING
Operation - mg/1
Phenols
88
1
99%
PCP
1.7
0.4
76%
Loading
COD
2650
710
73%
Phenols
90
10
88%
PCP
1.62
1.32
19%
57
-------
The effects of shock loading were observed during a three day
period. The flowrate, which had been maintained at a constant 21 liters
per minute (5.5 gpm) for over four weeks, was increased to 42 1pm (11 gpm)
on October 8 and maintained at this rate for three days. At this rate,
the nominal detention time in the aeration tanks was 44 hours, the BOD:
MLSS ratio was about 0.13 kg BOD/kg MLSS, and the COD:MLSS ratio ex-
ceeded 0.5 kg COD/kg MLSS. The penta loading was below 1 gm/cu m (0.06
Ib per 1000 cu ft) of aeration volume. While this is still far below
the shock loadings of Thompson (46) — 6.5 gm/cu m (0.4 Ib per 1000
cu ft), the detention time was less than one-half of the five day
detention used in his laboratory studies. The result of this increased
loading and decreased detention time was a noticeable decrease in treat-
ment efficiency as shown in Table 18. Phenol concentration increased
rapidly in both aeration tanks as well as in the effluent. Phenol
removal efficiency decreased from 99 percent to about 89 percent and
was decreasing rapidly with time. COD removal efficiency was less
affected but did show a decrease in efficiency from near 80 percent
to about 72 percent. BOD removal was apparently not affected but, as
noted previously, the value of the BOD test for this waste is questionable.
It is noteworthy that penta removal efficiency was apparently affected
by the shock loading. At a constant loading, the penta removal had
averaged 79 percent but, apparently because of the shock loading, this
was reduced to virtually zero removal of penta. Whether the decreased
removal efficiency was due to a decrease in the rate of oxidation of
penta or to the decreased hydraulic detention time was not determined.
In order to determine the effects of increased loading and decreased
detention time under more constant conditions, two series of loading var-
iation were initiated. The flowrate was increased incrementally from
20.8 1pm (5.5 gpm) to a maximum of 41.6 1 pm (11 gpm) for the first series
and to a maximum of 49 1 pm (13 gpm) for the second series. The first
series of incremental flow variation was conducted during the last two
weeks of October and the second series during the first two weeks of
November.
The activated sludge process was restabilized for a four day period
after the shock loading test. On October 15, the flow rate was increased
to 26.5 1pm (7 gpm), then 34 1pm (9 gpm) on the 16th, and finally to 41.6
1pm (11 gpm) by the 18th of October. The flowrate was maintained at 41.6
1pm (11 gpm) for about one week. The results of this phase of experi-
mentation are shown in Table 19. As the lo-ading was increased, the penta
removal efficiency again decreased until virtually no removal was obtained.
The phenol removal efficiency decreased slightly but the effluent
concentration of phenol never exceeded 3.0 mg/1. Apparently, as the
loading was increased, the capacity of the activated sludge in the first
aeration basin to oxidize phenols was approached and exceeded. As the
loading was increased the concentration of phenols in the first aeration
tank increased. This resulted in an increase in the loading on the second
tank and some increase in effluent phenol concentration. The increased
loading on the second aeration tank produced a rapid buildup of suspended
solids which indicated increased biological activity.
58
-------
TABLE 19. RESULTS OF LOADING RATE VARIATION
Date
1973
(FIRST
10-15
10-16
10-17
10-18
10-19
10-24
(SECOND
11-2
11-6
Flow Sampling
1pm Point
LOADING SERIES)
26.5 Influent
#1 Aeration
#2 Aeration
Effluent
35.1 Influent
#1 Aeration
#2 Aeration
Effluent
35.1 Influent
#1 Aeration
#2 Aeration
Effluent
41.6 Influent
#1 Aeration
#2 Aeration
Effluent
41.6 Influent
#1 Aeration
#2 Aeration
Effluent
41.6 Influent
#1 Aeration
#2 Aeration
Effluent
LOADING SERIES)
20.8 Influent
#1 Aeration
#2 Aeration
Effluent
20.8 Influent
#1 Aeration
#2 Aeration
Effluent
COD BOD
(mg/1) (mg/1)
_
-
-
-
_ _
-
-
-
2117
-
-
757
_ _
-
-
-
755
-
-
75
2117
-
-
846
1045
-
-
no
2290
-
-
730
Parameter
Phenol PCP
(mg/1) (mg/1)
75 2.15
2
1
1 1.62
75
3
2
1
80
3
2
1
90 2.15
5
3
2 2.15
75 2.28
5
2
1 1.78
70
6
4
3
90 2.3
3
2
1 2.4
90
3
2
1
Sludge
(ml/1)
400
305
-
.
430
330
-
•»
470
340
-
_
500
365
-
mt
500
380
-
—
560
440
-
_
600
425
-
—
680
490
_
59
-------
TABLE 19. RESULTS OF LOADING RATE VARIATION
Date
1973
(FIRST
11-7
11-8
11-9
11-12
11-13
11-14
Flow Sampling
1pm Point COD
LOADING SERIES) (mg/1 )
26.5 Influent
#1 Aeration
#2 Aeration
Effluent
36.0 Influent
#1 Aeration
#2 Aeration
Effluent
41.6 Influent
#1 Aeration
#2 Aeration
Effluent
49.2 Influent
#1 Aeration
#2 Aeration
Effluent
49.2 Influent 2650
#1 Aeration
#2 Aeration
Effluent 1040
49.2 Influent
#1 Aeration
#2 Aeration
Effluent
Parameter
BOD Phenol
(mg/1) (mg/1)
90
5
3
2
100
5
2
1
90
7
3
2
80
9
5
2
90
25
15
TO
90
25
20
20
PCP
(mg/1)
2.1
_
-
2.1
_
-
-
-
2.4
-
-
2.2
2.7
-
_
3.2
w
-
_
-
3.1
_
_
2.7
Sludge
(ml/1)
_
700
470
-
—
620
470
-
..
690
480
-
_
_
_
-
_
525
580
-
«•
500
500
-
11-15 0 Effluent 40
(Flowrate Variation Discontinued)
60
-------
The COD removal efficiency, which had decreased during the earlier
period of shock loading, continued to decrease during this period also.
By October 24, the COD removal efficiency had decreased to about 60
percent. During the same period, however, BOD analyses indicated good
BOD removal efficiency. On October 19, with the flowrate at 41.6 1pm
(11 gpm), the BOD removal was 93 percent.
The second series of loading variation was begun on November 7,
following a week-long period of stabilization at the design flowrate.
The flowrate was increased to 49 1pm (13 gpm) over a five day period,
the results of which are shown in Table 19. The results are quite
similar to those obtained in the October series of loading variation.
Virtually no penta removal occurred and the COD removal efficiency was
reduced to about 60 percent. The buildup of phenol in both aeration basins
occurred as before. However, at 49 1pm (13 gpm) the oxidation of phenols
decreased very rapidly and was accompanied by sludge bulking in the
clarifier. At this rate, detention time in the aeration tanks was
37 hours, the BODrMLSS ratio was approximately 0.12 kg BOD/day/kg
MLSS and the COD:MLSS ratio equalled 0.36 kg COD/day/kg MLSS. The
penta loading was nearly 1.8 gm/cu m (0.II lb/1000 cu ft) of aeration
volume and the phenol:MLSS ratio was 0.01 kg phenol/day/kg MLSS.
Because of the fact that the hydraulic capacity of the treatment
system was probably exceeded at 49 1pm (13 gpm) and because the de-
tention time in the aeration basins was less than 50 percent of the
design aeration time, the above loadings probably do not represent
the maximum organic loading conditions at which the complete mix
activated sludge process could effectively function. It was there-
fore decided to reduce the aeration volume by about 50 percent by
utilizing only one aeration tank. By then increasing the flowrate
or decreasing the MLSS, a comparatively large change In loading could
be obtained without hydraulically overloading any unit of the treatment
system. Before this phase of the experimentation could be commenced,
however, severe winter weather including snow, ice, and subzero tempera-
tures set in. At the same time, the immersion heaters which had been
placed in the aeration tanks failed. The result was a period from
December 8, 1973, through January 17, 1974, during which the treat-
ment plant was inoperative due to frozen and broken valves and pipes.
During this period the aeration tank contents were aerated to maintain
aerobic conditions. Following a period of a few warm days in mid-
January, the necessary repairs were completed and plant operations
resumed.
It should be noted that the activated sludge responded immediately
to the reintroduction of feed water and stability was soon apparent.
As noted above, it had been decided to utilize only one aeration
tank for the purpose of loading variation. Because of the continuing
cold weather, it was decided to postpone further loading variation
until spring. The main experimentation efforts for the period from
January 17, 1974, through March 4, 1974, were directed at observing
the effects of post-chlorination of effluent quality. In order to
maintain continuity, this period will be discussed out of chronological
61
-------
order so that the results of loading variation can be concluded.
Loading variation recommenced on March 5, 197^, following
the post-chlorination study. As mentioned previously, this portion
of the study was performed using only the first aeration basin which
had a volume of about 56,400 liters (14,900 gallons). The initial
flowrate was 15 1pm (4 gpm) and the detention time in the aeration
tank was 62 hours. The BOD:MLSS ratio was approximately 0.10 kg
BOD/day/kg MLSS, the CODrMLSS ratio was 0.27 kg COD/day/kg MLSS, the
ratio of phenol to MLSS equalled 0.007 phenol/day/kg MLSS, and the
penta loading reached 3.2 gm/cu m (0.2 lb/1000 cu ft) of aeration volume.
Using this configuration of treatment units at 15 1pm (4 gpm), a COD
reduction of 70 percent, a BOD reduction of 85 percent, and a phenol
reduction of 99 percent were obtained.
From March 4 through the end of April the flowrate was increased
in increments from 15 1pm to 30 1pm (4gpm to 8 gpm). At first, it
appeared that a flowrate of 19 to 23 1pm (5 to 6 gpm) was the maximum
rate which could be handled without upsetting the biological process.
As can be seen in Figure 15, on three different occasions as this
flowrate was reached, the phenolic reduction decreased rapidly. The
sludge settling characteristics also changed at this loading with the
sludge volume index (SVI) increasing from about 100 to over 200. On
the third occasion the flowrate was increased beyond this loading range
to a maximum of 30 1pm (8 gpm). At this loading, the activated sludge
appeared to restabilize considerably and the SVI decreased to approxi-
mately 100. The phenol reduction efficiency again returned to 99 percent
removal and BOD was removed at about 90 percent efficiency. COD re-
moval had decreased markedly at this loading, however, to about 57
percent. Also, the plant operator reported that after about five days
at 30 1pm (8 gpm), sludge was beginning to rise in the clarifier. At
this point loading variation was suspended. Thus, the maximum loadings
achieved with a 31 hour detention time were a CODrMLSS ratio of 0.50
kg COD/day/kg MLSS, a BODrMLSS ratio of 0.18 kg BOD/day/kg MLSS, a
phenol:MLSS ratio of 0.013 kg phenol/day/kg MLSS, and a penta loading
of 7.3 gm/cu m (0.45 Ib penta/1000 cu ft) of aeration volume. As can be
seen, these are relatively high loading rates. The detention time of
31 hours is much less than that reported for penta removal and the penta
loading exceeds the maximum loading attempted in previous laboratory
studies.
PHASE 4 - POST-CHLORINATION STUDIES
Post-chlorination studies were begun on February 6, 1974, with
the primary objective of determining the effects of chlorine on
effluent quality. During this period of the study, the activated
sludge process was operated with one aeration basin. The influent
flowrate was maintained at 15 1pm (4 gpm) and the MLSS concentration
was held constant at about 3500 mg/1 by wasting sludge as necessary.
All other operating parameters were maintained constant to minimize
as many variables as possible during the post-chlorination phase of
the study.
62
-------
CO
70-
63-
60-
83-
30-
45-
<
Z 40-
a" _,
O 33-
~Z.
LU
°- 30-
28-
20
15-
10-
3-
INFLUENT PHENOL CONCENTRATION
EFFLUENT PHENOL CONCENTRATION,
10
a.
o
-3
4
-3
I 2 3 4 5 6 7 8 9 10 II 12 13 14 B 16 17 18 19 2021 22 232423 2627 28 2930 I 2 3 4 5 6 7 8 9 10 II 12 13 14 18 16 17 IB 19 20 21 22232425 262728 293031
MARCH, 1974 APRIL.I974
FIGURE 15.
Influent and Effluent Phenol Concentration
-------
Prior to initiating full-scale post-chlorination, some labora-
tory scale studies were performed on the clarified effluent to determine
the range of post-chlorination which would be most effective. For
this purpose, sodium hypochlorite (clorox) was used at dosages ranging
from 15 mg/1 to 500 mg/1 as HOC1. As illustrated in Figure 16, the
residual chlorine stabilized within thirty minutes for all dosages and
then decreased slowly, if at all. The effect of increasing dosage
on COD, penta, and phenol is shown in Table 20. Minimal reduction in
COD occurred at even the 500 mg/1 chlorine dosage. The effluent
phenol was already below 1 mg/1 and the reduction due to chlorine was
not significant. As can be seen in Figure 17, the effect of chlorine
on penta was quite significant, producing a maximum apparent reduction
of 77 percent at a chlorine dosage of 250 mg/1. The normally brown
wastewater was considerably lightened in color with increasing chlorine
dose.
TABLE 20. LABORATORY POST-CHLORINATION STUDIES
C19 Dosage
*(mg/l)
15
30
45
250
500
Time
(min)
40
40
40
60
60
Penta Phenol
(percent reduction)
16
31
38
77
75
—
--
--
25
33
COD
--
—
—
7
12
In spite of the lack of beneficial results from the laboratory
study, full-scale post-chlorination studies were conducted to confirm
the laboratory results and to further study the effects of chlorine
on penta. Chlorine was injected into the post-chlorination tank at
concentrations varying from 7 mg/1 to 155 mg/1 as HOC1. The detention
time in the post-chlorination tank at 15 1pm 14 gpm) was about 10
hours. The MLSS concentration was maintained between 3500 and 4000
mg/1. The immersion heaters in the aeration tank limited temperature
variations while pH was held constant by lime additions. The dissolved
oxygen concentration was maintained at 2 mg/1.
As shown in Table 21, there was no reduction in COD even at the
highest chlorine dosage. Phenol concentrations in the effluent were
reduced by about 50 percent at chlorine residuals exceeding 11.1 mg/1.
There were apparent reductions in BOD ranging up to 64 percent. How-
ever, the validity of this reduction is questionable considering the
retardance of the BOD test and the fact that no COD reduction occurred.
The effect of chlorine on penta was either a reduction of penta or a
reduction of the concentration of substances which interfered with the
analysis for penta.
64
-------
500-
^400-
o>
E
"5
£300-
e
c
in
200
100
i
15
30
45
60
Time (min)
90
105
120
135
FIGURE 16.
Chlorine Residuals with Time
-------
5.0i
4.0-
o»
E
3.0-
2.0
1.0-
15
IS mg/| Chlorine
30 45
60
i
75
90
K)5
Time (min)
120
FIGURE 17.
Effects of Chlorine on Pentachlorophenol Concentrations as Measured bv Safranin Method
i
135
-------
CD
TABLE 21.
EFFECTS OF FULL SCALE POST CHLORINATION
Date
2/11/74
2/14/74
2/18/74
2/21/74
2/25/74
2/28/74
3/4/74
Chlorine
Feed
Ob/day)
0.75
0.75
1.0
3.0
5.0
7.0
10
Chlorine
Residual
(mg/1)
2
0
3
11
24
32
35
.0
.5
.3
.1
.4
.0
.7
Phenol ,
, 0)
0.6
0.5
0.4
0.9
1.2
0.8
1.1
mg/1
J2I
0.6
0.5
0.4
0.9
0.6
0.4
0.6
Penta,
Jll_
8.4
7.6
8.1
9.2
9.6
8.2
9.4
mg/1
J21
4.4
5.3
5.2
4.3
3.2
1.4
5.2
COD,
HI
595
645
755
700
855
835
805
mg/1
Jii
595
670
760
735
835
860
800
BOD,
HI
125
80
95
110
265
100
125
mg/1
Jil
95
75
80
85
95
80
65
(1) Before Chiorination
(2) After Chiorination
-------
It should be noted that the nutrient levels during this period,
as throughout the entire study, were quite elevated due to the previous
use of a fire retardant which contained ammonia and phosphorus com-
pounds. The presence of large concentrations of ammonium ions in the
wastestream may have caused the high residuals of chlorine and con-
tributed to the poor reaction of chlorine with the organics in the
treated effluent.
PHASE 5- PRE-CHLORINATION
As has been previously discussed, the primary purpose of pre-
chlorination was to reduce penta concentrations to a level that would
allow satisfactory biological activity in the activated sludge process.
It had been demonstrated during the previous phases of the project
that pre-chlorination was not required in order to treat the wastes
biologically. The need for pre-chlorination was therefore considered
limited. However, before abandoning the concept entirely, it was
decided to experiment on a laboratory scale with chlori nation of the
raw waste to determine if any measurable benefical effects occurred.
Initially, laboratory tests were conducted to determine chlorine
persistence. This was considered important due to the high dosages
which were expected to be required and because only small chlorine
residuals could be allowed to enter the aeration units without damage
to the activated sludge. Chlorine doses of approximately 600, 1200,
3400, and 6900 mg/1 were prepared in the laboratory using sodium
hypochlorite. Chlorine residual was measured with time over a period
of at least 10 hours for each sample. The resulting chlorine residual
curves are shown in Figure 18. It can be seen that the primary
reaction of chlorine with the raw wastewater occurred within two to
four hours and that the decrease in total residual occurred at a much
slower rate after this initial period. After 19 hours of reaction
time the sample initially treated with 600 mg/1. of chlorine still
contained a residual of over 200 mg/1. High initial doses resulted
in correspondingly higher total residuals. The 6900 mg/1 initial
doses, for instance, produced a residual after 10 hours of over
2600 mg/1. Obviously, if large chlorine doses were required, high
chlorine residuals would result and a substantial degree of dechlorina-
tion would be required before biological treatment would be possible.
.Subsequent laboratory studies were conducted to determine the
effects of chlorine on the raw waste at concentrations of chlorine
of 500 mg/1 and 1000 mg/1. As illustrated in Figure 19, oxidation of
phenols occurred rapidly and completely at chlorine levels of 500
mg/1 and 1000 mg/1. The reaction at pH 8 was somewhat more complete
after one hour than the reaction at pH 2. Figure 20 shows penta
removal with chlorine doses of 500 mg/1 and 1000 mg/1. The efficiency
of removal of penta was 40 percent using 500 mg/1 of chlorine at pH
8, 81 percent using 500 mg/1 of chlorine at pH 2 and about 80 percent
using 1000 mg/1 of chlorine at pH 8.
68
-------
1400-1
CT>
VO
1200 rag/1 chlorine dosage
A
600 mg/1 chlorine dosage
0
16
18
20
Time After Initial Dose
FIGURE 18 (a).
Chlorine Persistence
(hrs)
-------
7000
6900 mg/1 chlorine dosage
2000-
3400 mg/1 chlorine dosage
1000-
0
6 8 10 12
Time after Initial Dose (hrs)
FIGURE 18 (b). Chlorine Persistence
14
16
18
20
-------
60H
55
50
45-
40-
35
30-
x
f 25-
£ 20-
15-
10
5-
25Omg/l Clodded
500 mg/l
CMpH=8
1.0
1.5
2J5
3.0
Tim* (hrs)
Figure 19. Effect of Chlorination on Phenolic Concentration of Raw Wastewater with Activated Carbon
-------
ro
pH=8
mg/1 C12, pH=8
3.0
TIME (hrs)
FIGURE 20.
Effect of Chiorination on Penta Concentration of Raw Wastewater
with Activated Carbon
-------
Also shown in Figures 19 and 20 is the effect of adding powdered
activated carbon to the raw wastewater. As this was not part of the
project objectives, the use of activated carbon was not studied exten-
sively. However, the few tests performed indicated that activated
carbon at a concentration of 0.5 grams/liter can reduce phenol concen-
tration in the raw waste by 84 percent and penta by about 25 percent
At a concentration of 2.0 grams/liter, powdered activated carbon removed
about 61 percent of the phenols and 98 percent of the penta rem°ved
** H-iU wa? thought that the adsorbed phenol and penta might be more
readily oxidized either chemically or biologically while attached to
the carbon than when in solution. Therefore, Figures 19 and 20 also
show the results of a few experiments in which chlorine was added to a
solution of powdered activated carbon and raw wastewater. The effert
of the chlorine was apparently to attack the carbon preferentially
resulting in the desorption of the phenol and penta molecules!
Based on the above results, it was intended that a full-scale
pre-chlorination study be performed. A schedule of chlorine doses
and dechlorinating agent requirements was prepared and pre-chlorination
was begun on May 7, 1974. Due to the high chlorine residuals expected
it was decided to initiate pre-chlorination at 50 mg/1 and gradually
increase the dosage to a maximum of 500 mg/1. Dechlorination was to
be accomplished by the addition of sodium sulfite.
Pre-chlorination was continued for one month. Unfortunately, due
to several problems, the chlorine dosage never exceeded about 75 mg/1
and no significant reductions in phenol, penta, or COD were obtained.
Problems related to pre-chlorination were largely operational. De-
chlorination has not been anticipated to be a major problem in the
initial design and, consequently, no alternatives other than air
stripping were included in the treatment plant. Therefore, control
of chlorine residual was accomplished during the study by gravity
fed sodium sulfite, and the reliability of this system was poor.
Consequently, either due to the chlorine or to excess sodium sulfite
entering the aeration basin, the activated sludge process appeared
to be suffering rather than benefiting from pre-chlorination. As
can be seen by examination of the data contained in the Appendix,
on May 28, 1974, phenol reduction efficiency appeared to be decreasing
rapidly. Therefore, pre-chlorination was suspended on May 29.
DISCUSSION OF RESULTS
Based on the data developed during the study, the optimum
design and operating parameters for the treatment of the specific wood
preserving wastewater studied can be presented. As the characteristics
of the waste are dependent upon the wood preserving process from which
it comes, the design parameters for this waste may differ significantly
from those at any other plant. However, the results and conclusions
should allow generalizations for similar wood preserving plants.
73
-------
It was determined early in the study that the wastewater inhibited
the BOD test. While this fact precludes the use of the BOD test as a
precise method of analysis, it does not eliminate its usefulness as an
indicator. The average BOD/COD ratio of 0.35 was found to be rather
constant for the raw waste.
The result of loading the activated sludge at various rates is
summarized for COD in Figure 21. The percent reductions of COD when
plotted against the nominal hydraulic detention time produce a linear
relation as indicated. Increasing organic loading resulted in a
linear decrease in treatment efficiency up to a loading of about 0.35
kg COD/day/dg MLSS, while the decrease in removal efficiency became
much less rapid above the loading.
BOD and phenol concentration were readily reduced at practically
every loading level tested. A BOD reduction of 90 percent and a phenol
reduction of 99 percent were obtained.
The primary measurable effects of post-chlorination were to marked-
ly improve the color of the wastewater and to reduce the penta concen-
tration of the wastewater and/or the concentration of substances being
measured as penta. Slight reduction of phenol and no reductions of
organics were indicated under these operating conditions. At the
conclusion of the EPA sponsored program, Koppers Company conducted a
further investigation of post-chlorination. Preliminary results
indicated that at a pH of 7 to 8 and a flow of 5.5 gpm, penta was
reduced from about 5 mg/1 to less than 0.10 mg/1.
Pre-chlorination was found to be effective for reducing penta and
phenols in the raw waste. The ratio of chlorine to penta required to
produce an 80 percent reduction in penta concentration was found to be
in excess of 300:1 on a molar basis. In addition, the residual chlorine
was found to be high following pre-chlorination,. a condition which was
possibly aggravated by the presence of ammonia. The high residual
chlorine caused operational problems which were not overcome. Con-
sequently, whether pre-chlorination could be beneficial to the activated
sludge process was not clearly established.
Based on the results of this study, the following are design para-
meters for this particular waste:
Average COD loading =0.3 kg/day/kg MLSS
Maximum COD loading = 0.4 to 0.5 kg/day/kg MLSS
Average BOD loading = 0.1 kg/day/kg MLSS
Maximum BOD loading = 0.2 kg/day/kg MLSS
Average phenol loading =0.01 kg/day/kg MLSS
Average penta loading =1.62 gm/day/cu m (0.1 lb/day/1000 cu ft)
Maximum penta loading =6.5 gm/day/cu m (0.4 lb/day/1000 cu ft)
Average hydraulic detention time = 60 hours
Minimum hydraulic detention time = 40 hours
74
-------
Hydraulic Detention Time (hrs.)
10 20 30 40 50 60 70 80 90 100
en
80 .
>
O)
o
O
O
70 .
60 -
50
0
I 0.3 0.4
COD LOADING RATE, Ibs COD/day/1b MLSS
FIGURE 21,
COD Removal In The Activated Sludge Process
0.5
-------
At the Carbondale wood preserving facility, the pretreatment system
was adequate for recovering pentachlorophenol from the process waste
stream prior to biological treatment. A properly designed and operated
preservation recovery system in conjunction with equalization is impor-
tant for successful operation at the loadings listed above.
An activated sludge process designed on the basis of the above
should result in the following reduction efficiencies:
COD removal efficiency = 70 to 80 percent
BOD removal efficiency = 90 percent
Phenol removal efficiency = 99 percent
Penta removal efficiency = 99 percent
76
-------
SECTION VII
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-------
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Treating Plant Waste. In: Proceedings, Conference on Pollution
Abatement and Control in the Wood Preserving Industry.(W. S.
Thompson, Editor). Mississippi Forest Products Laboratory,
Mississippi State University, State College, Mississippi.
pp. 261-270. (1971).
66. Gaudy, A. F., Jr., R. Scudder, M. M. Neeley and J. J. Perot. Studies
on the Treatment of Wood Preserving Wastes. Paper presented at 55th
National Meeting, Amer. Insti. Chem. Eng., Houston, Texas. (1965).
81
-------
67. Gaudy, A. F., Jr. The Role of Oxidation Ponds in a Wood Treating
Plant Waste Abatement Program. In: Proceedings, Conference on Pollu-
tion Abatement and Control jiji the Wood Preserving Industry. (W. S.
Thompson, Editor).Mississippi Forest Products Laboratory, Mississippi
State Univ., State College, Mississippi, pp. 150-164. (1971).
68. Fisher, C. W. Koppers1 Experience Regarding Irrigation of Indus-
trial Effluent Waters and Especially Wood Treating Plant Effluents.
In: Proceedings, Conference on Pollution Abatement and Control in the
Wood Preserving Industry.(W. S. Thompson, Editor).Mississippi
Forest Products Laboratory, Mississippi State University, State
College, Mississippi, pp. 232-248. (1971).
69. Gloyna, E. F. and J. F. Malina, Jr. Petrochemical Waste Effects
on Water, Part 2. Physiological Characteristics. Industrial Water
and Wastes. (November-December, 1962).
70. Gould, M. and J. Taylor. Temporary Water Clarification System.
Chem. Eng. Progress 65(12). (1969).
71. Kirsch, Edwin J. and J. E. Etzel. Microbial Decomposition of PCP.
JWPCF 45(2). (February 1973).
72. American Public Health Association Standard Methods. American
Public Health Assoc., Inc., New York, New York.
82
-------
SECTION VIII
GLOSSARY
Activated Sludge - Sludge floe produced in raw or settled wastewater
by the growth of zoogleal bacteria and other organisms in the presence
of dissolved oxygen and accumulated in sufficient concentration by re-
turning floe previously formed.
Aerated Lagoon - A natural or artificial wastewater treatment pond in
which mechanical or diffused-air aeration is used to supplement the
oxygen supply.
Alum - A common name in the water and wastewater treatment field for-
commercial -grade aluminum sulfate.
Bentonite - An absorptive and colloidal clay used especially as a filler
(as in paper) or carrier (as of drugs).
BOD - Biological Oxygen Demand is a measure of biological decomposition
oTbrganic matter in a water sample. It is determined by measuring the
oxygen required by microorganisms to oxidize the organic contaminants
of a water sample under standard laboratory conditions. The standard
conditions include incubation for five days at 20°C.
COD - Chemical Oxygen Demand. Its determination provides a measure of
thT oxygen demand equivalent to that portion of matter in a sample which
is susceptible to oxidation by a strong chemical oxidant.
Creosote - A complex mixture of organic materials obtained as a by-product
from coking and petroleum refining operations that is used as a wood pre-
servative.
Cresol - Any of three poisonous colorless crystalline or liquid isomeric
phenols
Emulsion - A heterogeneous liquid mixture of two or more liquids not
normally dissolved in one another, but held in suspension one in the
other by forceful agitation or by emulsifiers which modify the surface
tension of the droplets to prevent coalescence.
Flocculation - In water and wastewater treatment, the agglomeration of
colloidal and finely divided suspended matter after coagulation by gentle
stirring by either mechanical or hydraulic means. In biological wastewater
treatment where coagulation is not used, agglomeration may be accomplished
biologically.
Lime - Any of a family of chemicals consisting essentially of calcium
fiydroxide made from limestone (calcite) which is composed almost wholly
of calcium carbonate or a mixture of calcium and magnesium carbonate.
83
-------
Mixed Liquor - A mixture of activated sludge and organic matter under
going activated sludge treatment in the aeration tank.
Pentachlorophenol - A crystalline compound CgClgOH used as a wood
preservative, fungicide and disinfectant.
Phenol - The simplest aromatic alcohol.
Polyelectrolyte - A nonmetallic electric conductor of high molecular
weight in which current is carried by the movement of ions.
Quinone - Either of two isomeric cyclic crystalline compounds
that are di-keto derivatives of dihydro-benzene.
Sludge Volume Index (SVI) - It is the volume in milliliters occupied
by 1 gm of activated sludge after settling of the aerated liquid for
thirty minutes.
Thiocyanate - A salt or ester of thiocyahic acid, a colorless unstable
liquid acid (HSCN) of strong odor.
Trickling Filter - A filter consisting of an artificial bed of coarse
material, such as broken stone, clinkers, slate, slats, brush, or plastic
materials, over which wastewater is distributed or applied in drops,
films, or spray from troughs, drippers, moving distributors, of fixed
nozzles, and through which it trickles to the underdrains, giving oppor-
tunity for the formation of zoogleal slimes which clarify and oxidize
the wastewater.
84
-------
SECTION IX
APPENDIX
OPERATIONS LOG
The treatment facilities at Carbondale were placed in operation
on July 26, 1973 and the testing program was terminated on May 31,
1974. Table A presents a summary of key data collected during the
study. Following is a condensation of the daily log maintained by
the treatment plant operators:
August 1973
The activated sludge plant was installed and filled with water
from the emergency lagoon. Horse manure was used as a seed and
aeration began on July 26. The reason for using water from the emergency
lagoon initially was that it had relatively low concentrations of
phenol, penta, and boron and its pH was near neutrality. Subsequently,
wastewater from Lagoon No. 1 was gradually added. Three thousand
gallons of water from Lagoon No. 1 were added on July 31. Until
August 20 the influent to the activated sludge system consisted of a
mixture of waters from the emergency lagoon and Lagoon No. 1, but
on that date the emergency lagoon pump broke down and problems de-
veloped with the pump on Lagoon No. 1. Although both pumps were
repaired on August 23, it was decided to continue use of only water
from Lagoon No. 1, and to increase the flow by one gallon per minute
each day until a flow of 6 gpm was obtained.
It was observed that almost no suspended solids were building up
in the aeration tanks. On August 13 floating sludge was observed in
the clarifier. Although sludge was returned to aeration at maximum
capacity, the problem continued. On August 28 it was discovered
that a pin had sheared in the clarifier paddle assembly preventing
aeration of the paddles. The clarifier was emptied into the aeration
tank and repairs were made.
Considerable amounts of protozoa were observed from initial start-
up until August 21 when the numbers began to drop drastically. Small
amounts of lime were added to Aeration Tank No. 1 to increase the
pH, and the protozoa count increased.
Due to lack of power at the on-site laboratory, penta analyses
were not begun until August 21.
September 1973
The month of September was intended as a sludge build-up period.
Settleable solids increased from 35 ml/1 at the beginning of September
to 180 ml/1 at the end of the month. By the end of the month the
MLSS was about 2000 mg/1.
85
-------
The water level in Lagoon No. 1 was getting low enough that the pump
began to pick up debris from the bottom, so water was added to Lagoon
No. 1 from Lagoon No. 3. This temporarily lowered the concentration
of penta and phenol entering the activated sludge system, but as raw
wastes continued to be added to Lagoon No. 1, these concentrations
began to rise.
October 1973
On October 8, by which time the MLSS of both aeration tanks
averaged about 2500 mg/1 and settleable solids about 270 ml/1, the
feed rate was set at 11 gpm and maintained at that rate through October
10. From October 11 through October 14 the feed was reduced to 5.5
gpm while the aeration tanks were being sprayed with an insulation
material and painted.
As indicated in Table A, the flow rate of 11 gpm resulted in a
reduced efficiency as phenol removal. So on October 15, when both
aeration tanks were back in operation it was decided to raise the feed
rate gradually while allowing the system to adjust and reduce phenol
levels prior to each increase. It took four days to again achieve a
flow of 11 gpm. The rate of 11 gpm was maintained from October 18
through October 25 with only a slight loss in phenol removal efficiency.
On October 26 the flow was reduced to 5.5 gpm to allow stabilization
in preparation for tripling the feed rate.
As can be seen in Table A, the pH of the influent to the activated
sludge system was consistently below 5.0. Prior to the feed increase
on October 8, only periodic additions of small amounts of lime were
necessary to maintain a pH in the aeration tank at above 6.0. How-
ever, after the flow was increased on October 8, considerably larger
lime dosages were necessary nearly every day.
November 1973
On November 7 the feed rate was increased from 5.5 to 7 gpm and
then gradually increased to 13 gpm by November 12. This rate was
maintained for three days, at which time drastically reduced phenol
removal necessitated a feed reduction. Six gallons per minute were
fed until the holiday weekend of November 22 during which time the
flow was cut off and the air supply decreased.
The reason for shutting off the flow was that many wood preserving
plants do not have the lagoon capacity that the Carbondale facility
does and no flow on a long weekend would be normal. Also, in an
effort to conserve electricity (the winter of 1973 found the United
States in an "Energy Crisis"), the metabolism of the sludge was
reduced by timing the air pumps to run for one hour and be off for
five hours.
Large quantities of lime were necessary to maintain the pH in
the aeration basins near neutrality. This was especially true during
the period of high feed rate.
-------
Protozoa were easily visible until the system upset of November.
15. On November 16 horse manure was added to replace protozoa.
December 1973
The stabilization period of the last week in November was maintain-
ed into December. On December 3 heaters were installed in the aeration
tanks and these were expected to maintain a water temperature of at
least 20°C.
On December 3 the water temperature was 15°C. By the next day the
heaters had increased it to 17°C; however, the temperature then dropped
until by December 7 it was at 11°C.
During the weekend of December 8 and 9 the flow was cut off and the
air pumps were operated for one hour of each six hours. This did not
allow adequate water circulation over the immersion heaters; they'
developed a sludge layer and burned out. The lack of circulation also
led to freezing of several lines and both pumps in Lagoon No. 1. There
was a thin layer of ice on all tanks.
By December 13 the system had thawed enough that repairs could be
begun.
More cold weather appeared on December 19 and from that date until
December 25 there was at least a four inch layer of ice on all tanks.
All operations were suspended.
The plant was back in operation on December 26. Then, on December
29, a line became clogged with ice and the system became frozen again.
January 1974
It was decided that for the remainder of the study only Aeration
Tank No. 1 would be used in order to allow better operational control.
On January 8 new heaters were installed in the aeration tank by chopping
through five inches of ice. By January 10 the aeration tank had thawed,
but the external valves and lines were still frozen. On January 17 the
system was placed in operation with a flow of 1.5 gpm. Also on January
17, heaters were installed in the pre-chlorination unit. The temperature
in the aeration basin gradually increased but did not rise above 20°C
until January 21.
The flow was gradually increased until it reached 4 gpm on January
28 (it would be maintained at this rate until March 11).
On January 23 a program of wasting small amounts of sludge to the
digester was initiated. The MLSS at this time was 4650 mg/1, and it was
intended to eventually reduce it to 3500 mg/1.
February 1974
By the beginning of February the activated sludge system was
operated as designed and as soon as the ,MLSS became stationary it was
-87-
-------
planned to begin post-chlorination.
By February 7 the MLSS was below 3800 mg/1 and post-chlorination
was initiated at 7 pounds of chlorine per day. This resulted in a
chlorine residual of 35 mg/1.
It was decided to determine what chlorine feed rate would yield a
residual of near 1 mg/1. February 10 through 14 results on Table B
show a feed of 0.75 ppd would achieve a residual of about 1 mg/1.
It was also intended to increase the chlorine feed gradually to
a maximum of 10 ppd to determine effects of BOD, COD, penta, and
phenols. This was done from February 15 through March 4. From February
22 through March 4 the pH of the post-chlorinated water began to drop
drastically as the chlorine feed approached 10 ppd.
March and April 1974
The objective during March and April was to determine the effects
of increased flow rates while maintaining other factors constant.
Throughout the two-month period it was necessary to add large amounts
of lime (12 to 16 pounds every second or third day) in order to control
pH in the aeration basin.
On March 7 the line between the aeration basin and the clarifier
became clogged. This caused the aeration basin to overflow and lose
solids.
Beginning March 9 flow rates were increased until March 17. On
March 16 the sludge return line became clogged and large amounts of
sludge had to be wasted in order to unclog the line. Horse manure was
added to the aeration basin on March 13 to increase the protozoa count.
Beginning on March 19 the flow rate was again increased until it
reached 6.5 gpm on March 22. At this point the phenol concentration
in the effluent had risen to such a high level that the flow was
reduced to 3 gpm to allow system stabilization.
Sludge had to be wasted almost daily in order to maintain a MLSS
of approximately 3500 mg/1. On March 21 phenols and penta concentrations
were observed to be low in the digester. It was decided to incorporate
a sludge contact chamber. On March 26 all return sludge was pumped to
the digester for two hours detention before being returned to the aeration
basin. Using the contact tank, the flow was gradually increased until
April 8 when the submersible pumps went out. The system was immediately
converted back to straight activated sludge.
The feed rate was continually increased, despite increased phenol
concentrations in the effluent, until April 29 when sludge began to
float in the clarifier.
On April 11 the penta oil separation system malfunctioned and penta
was spilled into Lagoon No. 1. On April 15 the spill began to appear
in the treatment system.
88
-------
May 1974
The primary objective during May was to determine the effects and
operating parameters of pre-chlorination. The flow rate was set at
6 gprru It was intended to maintain a MLSS of 3500 mg/1, but, as shown
in Table A, the MLSS varied from 2790 to 4320 mg/1.
Pre-chlorination began at 50 mg/1 and was scheduled to be increased
to 500 mg/1 during the month. Sodium sulfite was used for de-chlorination
prior to aeration. Sodium hydroxide was used to maintain a pH of 7 to
8 in the aeration basin.
Pre-chlorination was initiated on May 7 at 50 mg/1. No residual
resulted. On May 9 the chlorine feed rate was increased to 75 mg/1 and
a residual of 1 to 2 mg/1 resulted.
Due to the fact that extreme difficulties were encountered in
controlling the sodium sulfite addition by the gravity feed system, 'it
was decided to install a feed pump. The pre-chlorination feed rate
was maintained at 75 mg/1 until the pump could be installed.
The feed pump was received on May 22 and prepared for installation.
However, on May 28 it became apparent from increasing phenol levels in
the effluent that the activated sludge system was breaking down. The
pre-chlorination schedule was discontinued.
89
-------
TABLE A.
10
O
DAILY LOG SUMMARY
DO in
Phenol Penta BOD COD PO* NH4 SS Aeration MLSS
Flow (mg/1) (mg/1) (mg/1) (mg/1) (mg/1) (mg/1) (mg/1) (mg/1) (mg/1)
pH
7/26/73
7/31/73
8/2/73
8/31/73
8/4/73
8/5/73
8/6/73
8/7/73
8/8/73
a/9/73
8/10/73
8/13/73
8/14/73
8/15/73
8/16/73
8/17/73
8/21/73
8/22/73
8/23/73
8/24/73
8/25/73
8/26/73
8/27/73
8/28/73
8/30/73
8/31/73
9/4/73
9/5/73
9/6/73
9/7/73
Aeration Basin
Wastewater
Added
Rising Sludge
Pump Problems
Pumps
Corrected
Lime Added
Clarifier
Paddles
Corrected
Lime Added
AHfl-Lf
5
5
5
5
5
5
5
5
5
5
5
5
4.5
2
2
3
4
5
5
6
6
6
6
6
6
6
6
5.9
5.8
5.8
5.8
5.5
5.4
5.5
5.5
5.4
5.5
5.5
5.4
5.5
5.5
5.4
-
-
5.2
5.3
5.0
5.1
5.0
4.9
3.9
5.0
6.1
6.4
6.3
6.4
6.4
6.5
6.5
6.5
6.5
6.5
6.5
6.2
6.1
6.2
6.2
6.2
6.2
6.5
6.3
6.6
6.6
6.5
6.7
6.6
6.4
0.4
12
15
27
30
65
65
65
75
65
70
70
70
70
70
70
-
-
80
85
95
90
90
95
95
0.6
<1
<1
<1
<1
1
1.4
1.6
1.5
1.5
2.0
2.0
1.5 3.4 0.6
1,5 3.4 0.3
2.0 2.3 0.86
1.0 2.6 0.3
2.0
3.0
2.0
2.0
2.0
1
2 2.2 0.6
1 2.7 0.5
2
40
1 260 350
- 440 - 67
1820 470
1960 440
- 380 - 67
-------
DATE
REMARKS
TABLE A.
DAILY LOG SUMMARY
DO in
pH Phenol Penta BOD COD P04 NH4 SS Aeration MLSS
How (mg/1) (mg/1) (mg/1) (mg/1) (mg/l) (mg/1) {mg/1) (mg/1) (mg/1)
(gpm) Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. #1 #2 #1 #2
9/10/73
9/12/73
9/13/73
9/14/73
9/17/73
9/18/73
9/19/73
9/20/73
9/21/73
9/24/73
9/25/73
9/27/73
9/28/73
10/1/73
10/2/73
10/3/73
10/4/73
10/5/73
10/8/73
10/9/73
10/10/73
10/11/73
10/12/73
10/15/73
10/16/73
10/17/73
10/18/73
10/19/73
Added Lime
Added Line
Tank
Maintenance
Added Lime
Added Lime
Added Lime
(10/19-10/22)
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
11
11
11
5.5
5.5
7
9
9
11
11
5.2
5.5
5.1
5.0
5.0
5.0
5.0
4.9
4.9
4.9
4.9
4.9
4.8
4.7
4.7
4.7
4.7
4.5
4.7
4.7
4.6
4.7
4.7
4.8
4.8
4.8
4.8
4.7
6.6
6.5
6.5
6.5
6.5
6.6
6.4
6.4
6.3
6.2
6.4
6.2
6.1
6.0
6.2
6.2
6.2
6.2
6.0
6.1
6.3
6.2
6.3
6.2
6.4
6.2
6.1
6.2
70
70
70
95
90
90
90
90
90
90
90
100
100
100
110
100
100
100
110
no
120
90
100
75
75
80
90
75
<1
<1
1
1
<1
1
1
<
2
2
1
1
1
1
3
9
10
7
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
.7
.8
.6
.5
.5
.2
.7
.53
.73
.82
.35
.62
.36
.15
.15
.28
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1.
1.
2.
1.
6
1550 400
3 - 430 - 57
1
1700 400 - 400 - 67
3
2
3
1925 375
5 - 360 - 55
64 - 106
2272 612
64 - 350 - 50
97
57
2647 708
32 415 40
62
62
2117 757
15
78 755 75 - 340
2426 1751
4050 3690
3650 2640
-------
TABLE A.
DAILY LOG SUWARY
10
ro
DATE
10/23/73
10/24/73
1 0/25/73
10/26/73
10/29/73
10/30/73
10/31/73
11/1/73
11/2/73
11/5/73
11/6/73
11/7/73
11/8/73
11/9/73
11/12/73
11/13/73
11/14/73
11/18/73
11/19/73
11/20/73
11/21/73
11/26/73
11/27/73
11/28/73
11/29/73
REMARKS
Added Lime
Added Lime
Added Lime
Began Regular
Lime Addition
Poor Sludge
Separation
No Feed
(11/15,11/16)
No Feed
(11/22-11/25)
Flow
(gpm)
11
11
11
5.5
5.
5.
5.
5.
5.
5.
5.
7
9.
11
13
13
13
6
6
6
6
6
6
6
6
5
5
5
5
5
5
5
5
pH
Inf. Eff.
4.8
4.8
4.8
4.9
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.9
4.7
4.7
4.8
4.7
-
4.7
4.7
4.7
4.8
4.8
4.8
6.4
6.3
6.4
6.4
6.4
6.4
6.7
6.7
6.7
6.6
6.6
6.6
6.6
6.6
6.6
6.8
6.7
6.9
6.9
6.7
6.8
6.8
6.9
6.8
Phenol
("9/1 )
Inf. Eff.
75
70
70
70
90
80
90
80
90
90
90
90
100
90
80
90
90
-
90
90
90
70
3
3
2
3
2
1
1
1
1
1
1
2
1
2
2
10
20-
4
4
2
1
2
Penta BOD COD P04 NH4
(mg/1) (mg/1) (mg/1) (mg/1) (mg/l)
Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff.
1.68
2.22
1.93
2
2
2
2
2
2
3
4
4
4
.30
.3
.1
.1
.4
.7
.1
.4
.4
.6
2.02
2117 846
- 460 - 45
2.56 860 63
2.15
3.13
2217 803
- 320 - 55
2.4 1045 110
2.3
2290 730
2.1
- 300 - 52
2.2
3.3
2650 1040
2.7
3.8
2910 1090
3.5 - 260 - 40
- 260 - 45
4.3 2240 1030
DO in
SS Aeration MLSS
(mg/1) (mg/1) (mg/1)
Inf. Eff. #1 #2 #1 #2
4280 3500
2.5 7.8
3.0 9.5
4940 3800
2C A C
.5 4.5
1115
1 . O 1 . J
5250 '4930
5340 4970
1.0 3.5
120 270 1.5 1.5
2.0 6.0 5110 4660
2.3 7.5
-------
TABLE A
DAILY LOG SUMMARY
U3
DATE REMARKS
11/30/73
12/3/73 Heaters
Installed
12/4/73
12/5/73
12/6/73
12/7/73
12/10/73 Lagoon Pump
Frozen
12/12/73
12/13/73
12/14/73 #1 Tank
Repair Begun
12/17/73
12/18/73
12/19/73
12/26/73
12/27/73
12/28/73 Both Tanks
in Operation
1/15/74 No Row
1/18/74 Flow Into
#1 Only
1/21/74
1/22/74 Increased Air
1/23/74
1/24/74
1/25/74
1/28/74 Air Pump
Break Down
1/29/74
Flow
(gpm)
6
6
6
6
6
6
0
6
6
3
3
3
3
3
3
1.5
0
1.5
2.5
3
3
3
3
4
4
pH
Inf. Eff.
4.8
4.7
4.7
4.9
4.8
4.8
4.8
4.8
4.7
4.8
4.7
4.8
4.8
4.9
4.8
4.8
4.8
4.9
4.8
4.9
4.8
4.8
4.9
6.9
6.9
7.0
7.1
6.9
6.9
7.2
7.0
6.9
6.7
6.9
6.9
7.0
7.1
6.9
7.4
7.1
7.2
7.0
7.1
6.7
6.6
Phenol
(mg/l )
Inf. Eff.
54
55
56
54
55
55
56
35
44
42
38
43
43
44
0.7
0.5
0.4
0.9
0.7
5.1
13
1.5
0.7
0.4
0.1
0.2
0.1
0.4
Penta
(mg/l)
Inf. Eff.
4.1
4.5
4.1
3.8
4.9
4.2
4.1
3.7
3.4
4.0
4.2
3.0
3.6
3.0
4.1
4.9
4.0
4.3
5.9
4.8
5.2
4.5
.4.9
4.6
5.0
4.3
4.2
3.8
BOD COD P04
(mg/l) (mg/l) (mg/l)
Inf. Eff. Inf. Eff. Inf. Eff.
780 100
2100
2110
985 103 2040
2150
1065 125 2180
2170
821 - 2110
1620
540 85 1610
1730
1730
695 100 1730
790 135 1640
1000
220 200
940
200 200
820
360
300 260
880
910
240 240
1060
990
690
690
200 200
690
200 200
610
710
260 200
DO in
NH4 SS Aeration MLSS
(mg/l) (mg/l) (rag/1) (mg/l)
Inf. Eff. Inf. Eff. #1 #2 #1 12
110 200 2.2
2.0
60 40 90 200 1.5
2.2
60 42 100 160 2.9
2.8
3.2
60 35 60 120 5.0
_
.
65 55 100 160
3.0
2.0
55 55 80 110 0.5
2.2
60 45 100 150 1.6
2.0
0.5
55 45 130 170 0.5
9.0 5180
8.5
6.5 5000
7.5
5.5 5040
7.8
5.0
7.5 5190
5.8
7.5
9.5 3570
4900
3810
_
j,
- 4650
- 4620
4610
4090
3940
4420
4540
4860
4080
4880
_
—
-------
TABLE A.
DAILY LOG SUMMARY
DATE REMARKS
1/30/74
1/31/74
2/1/74
2/4/74
2/6/74
2/8/74
2/11/74
2/12/74
2/13/74
2/14/74
2/15/74
2/18/74
2/19/74
2/20/74
2/21/74
2/22/74
2/25/74
2/26/74
2/27/74
2/28/74
3/1/74
3/4/74
3/5/74
3/6/74
3/7/74
3/8/74
3/11/74
3/12/74
3/13/74 Added Horse
Manure
3/14/74
Flow
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
Inf.
4.8
4.8
4.8
4.8
-
4.9
4.8
4.8
4.8
4.8
4.8
4.9
4.8
4.9
4.9
4.9
5.3
5.0
5.0
5.1
5.0
5.1
5.1
5.0
4.7
4.9
4.7
4.7
PH
Eff.
6.5
6.8
6.7
6.8
5.8
6.4
6.8
6.6
6.6
6.5
6.6
6.0
5.7
6.2
5.6
4.2
4.7
3.7
4.6
3.3
3.0
6.9
6.9
6.9
6.5
6.7
6.8
6.7
Phenol
(mg/1)
Inf. Eff.
52 0.2
56 0.4
62 0.6
59 0.5
58 0.4
62 0.9
64 0.6
63 0.4
,
70 0.6
66 0.2
60 0.6
Inf
3.5
4.0
5.1
3.9
5.2
7.4
Penta
(mg/1)
. Eff.
4.9
5.7
4.4
5.3
5.2
4.3
6.0 3.2
3.2
5.4
7.8
8.6
7.5
1.4
5.2
7.4
8.6
8.1
BOD COD P0a
(mg/1) (mg/1) (mg/1)
Inf. Eff. Inf. Eff. Inf. Eff.
515
1040
520
465
565
630
730
1070
740
920
860
770
1015
85 1830 570
220 2110 605
55
95 2340 595
220 180
75 2450 570
80 2390 760
200 160
85 2420 735
95 2500 835
220 180
80 2630 860
65 2800 800
200 200
85 2965 722
95 2620 855
180 180
135 2715 985
DO In
NHd SS Aeration
(mg/1) (mg/1) (mg/1)
Inf. Eff. Inf. Eff. #1 #2
90
55 30 115
no
60 40 175
160
70 50 140
160
65 40 850
60 25 175
1.0
1.0
100 1.0 -
1.0 -
2.5 -
2.4 -
3.0
100 2.1 -
2.0 -
1.5 -
90 1.5
0.5 -
110 1.9 -
2.5 -
0.4 -
115 0.5 -
3.5 -
110 2.5 -
1.5 -
2.2 -
135 0.5 -
0.5 -
700 1.7 -
2.2 -
1.0 -
2.0 -
1.5 -
165 1.7 -
1.2 -
1.2 -
MLSS
(mg/D
#1 #2
4340 -
4125 -
3375 -
3860 -
3620 -
3880 -
3780 -
3660 -
3760 -
3390 -
3610 -
3765 -
3585 -
4155 -
3930 -
2750 -
3445 -
4290 -
4395 -
3775 -
-------
TABLE A.
DAILY LOG SUfWARY
in
DATE
REMARKS
DO in
pH Phenol Penta BOD COD P04 NH4 SS Aeration MLSS
Flow (mg/1) (rag/1) (mg/1) (mg/1) (mg/1) (mg/1) (mg/1) (mg/1) (mg/1)
(gpro) Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. 11 K 11 #2
3/15/74
3/16/74
3/17/74
3/18/74
3/19/74
3/20/74
3/21/74
3/22/74
3/25/74
3/26/74
3/27/74
3/28/74
3/29/74
4/1/74
4/2/74
4/3/74
4/4/74
4/5/74
4/8/74
4/9/74
4/10/74
4/11/74
4/12/74
4/15/74
Sludge Return
Line Clogged
Started
Returning
Sludge
To Contact
Tank For 2 hr
Then to 11
Tank
Stop Use of
Contact Tank
5
5.5
5.5
4
5
5.5
6
6.5
4
4
4
4
4
4
5
5
5
5.5
5.5
5.5
6
6
6
6
4.7
4.7
.8
.7
.8
.8
.8
4.9
4.8
4.8
4.8
4.9
4.8
4.8
4.8
4.8
4.7
4.7
4.7
4.7
4.7
6.9
6.9
6.9
6.9
6.7
6.9
6.8
6.7
6.8
6.8
6.8
6.8
6.8
6.8
6.8
6.6
6.8
6.7
6.7
6.6
6.8
65
59
60
63
60
64
60
58
59
0.5
1.2
5.0
0.3
0.2
0.2
0.2
9.5
0.3
7.2
8.1
7.4
6.6
6.1
6.4
6.7
7.1
8.6
9.1
9.9
7.0
6.2
6.5
6.8
6.4
7.2
10.4
830
910
875
750
865
945
995
845
100
115
95
120
100
115
135
120
2245
2455
2400
2365
2375
2285
2580
2640
700
160 160
725
720
710
160 140
.
650
125 125
790
1070
180 65
160 100
50 35
80 120
145 145
140 135
60 40
105 155
65 60 110 135
320 155
1.0
2.7
3.0
1.4
3.0
3.5
3.0
4.0
4.0
2.8
2.2
3.5
2.5
2.5
3.0
3.5
4.0
4.0
2.7
2.0
3.0
- 3805
- 1645
- 3530
_
- 3605
-
- 3350
-
3785
- 2920
_
- 3315
- 3040
-
- 3320
- 2910
- 3355
- 3780
- 4220
- 3980
- 4385
- 4880
-
_
.
_
_
_
_
_
-
_
-
_
.
_
_
-
-------
TABLE A.
DAILY LOG SUWARY
10
DATE
4/16/74
4/17/74
4/22/74
4/23/74
4/24/74
4/25/74
4/26/74
4/29/74-
4/30/74
5/1/74
5/2/74
5/3/74
5/6/74
5/7/74
5/8/74
5/9/74
5/10/74
5/11/74
5/12/74
5/13/74
5/15/74
5/16/74
5/17/74
5/20/74
5/21/74
5/22/74
5/23/74
5/24/74
5/28/74
5/29/74
5/30/74
5/31/74
REMARKS
Rising Sludge
Started Pre-
Chlori nation
Excessive
Foam
Began NaOH for
pH Control
Stop Free
Chi ori nation
Flow
(gpm)
6.5
6.5
7.5
7.5
8
8
8
8
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
5
6
6
6
0
0
pH
Inf. Eff.
4.9
4.7
4.7
4.8
4.7
4.7
4.7
4.8
4.7
4.8
4.7
4.7
4.9
4.7
4.7
4.7
4.7
4.7
6.6
6.7
6.9
6.6
6.8
6.7
6.8
7.0
6.8
6.8
7.2
7.0
7.2
7.2
7.2
6.9
7.0
6.8
Phenol
(mg/1)
Inf. Eff.
56
65
64
68
70
72
80
74
82
74
2.3
0.5
0.4
0.4
0.4
0.5
0.5
0.2
0.2
8
DO in
Penta BOD COD P04 NH. SS Aeration MLSS
(mg/1) (mg/1) (rng/1) (mg/1) (mg/1) (mg/1 ) (mg/1) (mg/1)
Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. #1 #2 #1 #2
15.8
11.2
7.6
8.9
8.9
8.0
9.2
2.8
6.6
5.4
17.2
22.4
15.2
19.2
14.5
7.2
12.0
9.6
6.2
5.0
885 100 2595
935 95 2465
2565
835 102 2465
680 90 2580
740 85 2320
660 85 2225
720 90 2070
695 85 2105
120 120
1155
1100
120 120
930
780
895
970
685
740
655
225 210 3.5
5.0
3.5
60 40 1.2
1.3
180 90 0.5
3.0
70 40 150 280 1.0
1.5
0.7
130 110 2.0
2.0
1.8
130 140
1.0
1.0
135 210 1.0
1.7
2.1
3.0
1.5
1.5
1.5
3.0
0.8
0.6
- 5070 -
- 3710 -
4225 -
- 4050 -
-
- 4260 -
- 3285 -
-
- 3515 -
- 3715 -
- 3865 -
-
- 4150
- 4180 -
- 4320 -
- 3725 -
-
- 3495
3410
2790
2940
3470
3670
3630
3040
-------
TABLE B,
POST-CHLORINATION
Date
2/7/74
2/8/74
2/9/74
2/10/74
2/11/74
2/12/74
2/13/74
2/14/74
2/15/74
2/18/74
2/19/74
2/20/74
2/21/74
2/22/74
2/25/74
2/26/74
2/27/74
2/28/74
3/1/74
3/4/74
cr
OJ
? Feed
3/day)
7
0.5
1.5
1
0.75
0.75
0.75
0.75
1
1
3
3
3
5
5
7
7
7
10
10
7
1
g Residual
(mg/1)
35
0
4.4
6.6
2.0
1
1
0.5
3.3
2.4
11.6
13.9
11.1
22.4
24.4
33.4
35.2
32.0
47,4
35.7
97
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-76-231
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Treating Wood Preserving Plant Wastewater by
Chemical and Biological Methods
5. REPORT DATE
September 1976 (Issue Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
John T. White, T. A. Bursztynsky, John D,
and Richard H. Jones
8. PERFORMING ORGANIZATION REPORT NO,
Crane
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Koppers Company
Forest Products Division
10. PROGRAM ELEMENT NO.
1BB610
11. CONTRACT/GRANT NO.
12100 HIG
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory - Cin., OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
Performed for the Koppers Company by ENVIRONMENTAL SCIENCE AND ENGINEERING, INC,
P. 0. Box 13454, University Station, Gainesville, Florida 32604
16. ABSTRACT
A completely mixed activated sludge system was designed for a wood pre-
serving plant with an average daily wastewater flow of 27,000 I/day
(7,150 gal/day), a BOD concentration of 1,100 mg/1, and a phenol concen-
tration of 120 mg/1. Included in the design were capabilities for pre- and
post-chlorination. The activated sludge system alone was capable of re-
moving 90 percent BOD, 75 percent COD, 99 percent phenol, and 76 percent
pentachlorophenol. Post chlorination dosages of over 50 mg/1 resulted in
50 and 52 percent reductions of phenol and pentachlorophenol, respectively.
Laboratory pre-chlorination studies showed removal of phenol and penta-
chlorophenol at chlorine dosages in excess of 250 mg/1.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
*Wood preservatives, *Activated
sludge, *0xidation, Phenol, Creosote
^Completely mixed,
*Chlorination, pentachloro
phenol.
13/B
8. DISTRIBUTION STATEMENT
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
108
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
98
ftUSGPO: 1977 - 757-056/5479 Region 5-11
------- |