MIDWEST RESEARCH INSTITUTE
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EPA-440/9-76-013
WASTEWATER TREATMENT TECHNOLOGY DOCUMENTATION FOR TOXAPHENE
MANUFACTURE
FINAL REPORT
February 6, 1976
Contract No. 68-01-3524
MRI Project No. 4127-C
EPA Project Officer
Mr. Ralph H. Holtje
For
Office of Water Planning and Standards
U.S. Environmental Protection Agency
Waterside Mall, Room 2834
Mail Stop WH595
401 M Street, S.W.
« Washington, D.C. 20460
MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD, KANSAS CITY. MISSOURI 64110 • 816561-02^
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^
WASTEWATER TREATMENT TECHNOLOGY DOCUMENTATION FOR TOXAPHENE
MANUFACTURE I
5
I
Midwest Research Institute i
425 Volker Boulevard
Kansas City, Missouri 64110
U.S. En'/Srsiiirsjnta! Pieisdion Agency
Rt^ifi III inioiination Resource
841 Cteinut Street
Philact^hia, PA 19107
FINAL REPORT
February 6, 1976 |
Contract No. 68-01-3524
MRI Project No. 4127-C
EPA Project Officer
Mr. Ralph H. Holtje
For
Office of Water Planning and Standards
U.S. Environmental Protection Agency
Waterside Mall, Room 2834
Mail Stop WK595
401 M Street, S.W.
Washington, D.C. 20460
s
MIDWEST RESEARCH INSTITUTE 425 VCLKER BOULEVARD, KANSAS CITY. MISSOURI 6-311 0 * SIS 531-0202
-------
PREFACE
This is one of four reports on pesticide-containing wastewaters pre-
pared by Midwest Research Institute for the Office of Water Planning and
Standards. These reports concern the wastewater treatment technology in-
volved in the manufacture of aldrin/dieldrin, endrin,
toxaphene, and DDT. This report is concerned with toxaphene.
These reports were prepared by Dr. Alfred F. Meiners, Mr. Charles E.
Mumma, Mr. Thomas L. Ferguson, and Mr. Gary L. Kelso. This program (MRI
Project No. 4127-C) has been under the general supervision of Dr. Edward W.
Lawless, Head, Technology Assessment Section. Dr. Frank C. Fowler, President,
Research Engineers, Inc., and Mr. William L. Bell, President, Arlington
Blending and Packaging, acted as consultants to the program.
Approved for:
MIDWEST RESEARCH INSITUTE
. J./
hysic<
L
Phys
hannon, Assistant Director
1 Sciences Division
.February 6, 1976
ii
-------
INTRODUCTION
Midwest Research Institute (MRI) has performed a comprehensive exami-
nation of the wastewater treatment technology applicable to aldrin/dieldrin,
endrin, DDT, and toxaphene. The work was performed for the Environmental
Protection Agency (EPA) under Contract No. 68-01-3524.
The basic objectives of the program were: (a) to perform an examina-
tion of the wastewater management practices currently employed in the manu-
facture of the specified pesticide; (b) to examine the state
of the art of potential wastewater treatment processes that might be appli-
cable to this industry; and (c) to select those processes that would be
applicable to EPA toxic pollutant control technology requirements. Of
special interest was the cost of existing and proposed wastewater treatment
methods.
This report concerns the wastewater treatment technology for
toxaphene manufacture.
iii
-------
CONTENTS
Page
List of Tables vi
List of Figures vii
TOXAPHENE MANUFACTURE
Sections
I Summary 1
II Characterization of Industry 7
Hercules, Inc 7
Tenneco Chemicals, Inc 24
Riverside Chemical Company . 32
Vicksburg Chemical Company 38
III Alternate Systems for Removing Toxaphene from
Wastewater , 45
Present Status of Alternate Systems for Treating
Toxaphene Wastewaters 45
The Feasibility of Alternate Systems for Removing
Toxaphene from Wastewater 48
Flow Diagrams of Alternate Systems for Removing
Toxaphene from Wastewater. 54
Possibilities for Zero Discharge in Toxaphene
Manufacture 65
Comparison of Effluents Produced by Alternate Treatment
Systems with Effluent Limitations Guidelines 67
iv
-------
CONTENTS (continued)
IV Wastewater Treatment Coat Estimates V . . . 70
Estimated Cost of Presently Used Wastewater Treatment
Systems 70
Estimated Cost of Alternate Toxaphene Wastewater
Treatment Systems 71
References
Appendix A - Engineering Information Pertinent to Toxaphene Waste
Treatment at the Hercules, Inc., Plant at
Brunswick, Georgia.
Appendix B - Definition of Terms and Discussion of Conventional
Engineering Practices Used in Estimating Costs of
Pesticide Wastewater Treatment Processes.
-------
TABLES
No. Title
TOXAPHENE MANUFACTURE
1 Summary of Production Rates and Wastewater Characteristics
For Toxaphene Manufacture 8
2 Toxaphene Wastewater Effluent Data, Hercules, Inc.,
Brunswick, Georgia • 18
3 Data From Hercules' Monthly Discharge.Reports for NPDES
Permit No. GA 0003735 at Brunswick, Georgia, Plant-
June 29 to August 28, 1975 (Outfall No. 001) 19
4 Chemical and Physical Properties of Endrin and
Toxaphene 50
5 Summary of Cumulative Pesticide Removal at 10-PPB Load . . 64
6 Effluent Limitations Guidelines for Halogenated Organic
Pesticides (Tentative Recommendations) 69
7 Installed Capital Equipment Cost for the XAD-4 Resin
System, The Reductive Degradation System, and the XAD-4
Resin System and Reductive Degradation System in
Series 85
8 Total Investment Cost and Annual Operating Cost for Three
Toxaphene Wastewater Treatment Systems Treating Either
200 or 300 Gal/Min Wastewater Effluent 93
9 Installed Capital Equipment Cost for the 300 GPM Carbon
Adsorption System 103
10 Estimated Total Investment and Annual Operating Costs
For Granular Activated Carbon Adsorption Systems .... 110
vi
-------
FIGURES
No. Title Page
TOXAPHENE MANUFACTURE
1 Hercules' Production and Waste Schematic for Toxaphene . . 11
2 Hercules' Toxaphene Treatment System at Brunswick,
Georgia 15
3 Schematic Flow Diagram—Manufacture of Toxaphene
(Strobane®-T) by Tenneco Chemicals, Fords, New Jersey. . 26
4 Schematic of Water Flow—Riverside Chemical Company,
Port Neches, Texas 36
5 Toxaphene Production Schematic--Vicksburg Chemical
Company, Vicksburg, Mississippi 40
6 Effluent Treatment Process—Vicksburg Chemical Company,
7
8
9
10
11
12
Liquid Waste Disposal System — Vicksburg Chemical Company,
Design Flow Diagram of Amberlite XAD-4 Resin System, . . .
Design Flow Diagram of Reductive Degradation System. . . .
Design Flow Diagram of Amberlite XAD-4 Resin System and
Design Flow Diagram for a Carbon Adsorption System ....
44
53
56
57
58
59
vii
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TOXAPHENE MANUFACTURE
-------
SECTION I
SUMMARY
Toxaphene (chlorinated camphene) is produced in the United States by four
companies: Hercules, Inc. (at Brunswick, Georgia); Tenneco Chemicals, Inc.
(at Fords, New Jersey); Riverside Chemical Company (at Groves, Texas) and
Vicksburg Chemical Company (at Vicksburg, Mississippi). Actual toxaphene
production rates are not available; however, total production in the United
States is estimated to be 80 to 110 million pounds.
Toxaphene is produced in essentially the same manner by all domestic
producers, that is, by the chlorination of camphene. This production
method results in the formation of relatively large quantities of by-
product hydrogen chloride (about 0.5 Ib/lb toxaphene). The hydrogen
chloride is absorbed in water, generating hydrochloric acid. The genera-
tion of the acid creates a major disposal problem. Tenneco, Riverside, and
Vicksburg have reported that they sell practically all of the acid generated.
Hercules neutralizes and discharges a large portion of the acid generated.
A summary of toxaphene production and wastewater characteristics is pre-
sented below.
-------
Estimated 1975
toxaphene production
Average wastewater
flow from toxaphene
production
Average
daily toxaphene
discharge in
plant effluent
(millions of pounds) gpm
Hercules
Tenneco
Riverside
Vicksburg
50-80
9-11
8-10
9-11
167
0.07
5.8
10
gal/lb product
1.1-1.8
0.003-0.004
0.30-0.38
0.48-0.58
Ib/day
0.27
<0.05
0.032
Unknown
ppb
114
< 6
320
Unknown
Information sources and methods for calculating the above data are de-
tailed in the report.
The above data show that Hercules produces a relatively large quantity
of wastewater compared to the other producers. Hercules employs a toxaphene
wastewater system which includes neutralization of by-product hydrogen chloride
followed by adsorption and sedimentation processes. The other manufacturers
sell practically all of the by-product hydrogen chloride as hydrochloric
(muriatic) acid. The wastewaters generated by Tenneco, Riverside, and
Vicksburg are primarily spent caustic liquor from scrubbers used to absorb
excess hydrogen chloride in the hydrochloric acid production process. The
volume of spent caustic liquor is very small compared to the volume of neu-
tralized hydrochloric acid produced by Hercules.
Because of the relatively large quantity of water produced by Hercules,
and also because of the relatively high concentration of toxaphene in this
wastewater, alternate methods may be required for treating the Hercules ef-
fluent. Four treatment systems appear to be the most promising for this
purpose: (a) a resin adsorption system, (b) a reductive degradation system,
-------
(c) the resin adsorption and reductive degradation systems .in series, and
(d) an activated carbon adsorption system. These systems have been examined
in this report for their potential usefulness in the treatment of wastewater
from the Hercules manufacturing process. The characteristics of this waste-
water have been examined and estimates have been made of the expected quality
of the effluents produced by the application of each alternate treatment
system to this wastewater.
Only laboratory-scale data are available concerning the applicability
of these alternate systems to toxaphene wastewaters. None of the alternate
systems have been operated under conditions which approximate actual use,
nor have they been developed to the point where a determination of operat-
ing conditions or costs can be made with a high level of confidence. How-
ever, MRI believes that these treatment systems would be technically feasible
based upon (a) the limited available experimental data concerning the ef-
fectiveness of these treatment systems in removing toxaphene and related
compounds from water, (b) the opinions of experienced research personnel, and
(c) a consideration of the similar chemical and physical properties of toxa-
phene compared to those of other chlorinated pesticides which have been
demonstratably removed from wastewater.
The wastewater treatment system at Hercules has been examined in some
detail. The cost of the existing system at Hercules and the costs of the
four alternate wastewater treatment systems have been estimated. Cost esti-
mates have been made for two flow rates, 200 and 300 gpm; these flow rates
-------
are (a) the approximate average effluent flow rate to the present treatment
system, and (b) the design flow capacity of that system. The quality of
the present effluent has been compared to the expected quality of the ef-
fluent from each alternate system. This information concerning effluent
quality and costs is summarized on the following page.
The cost estimates were based upon conceptual systems which required
initial sedimentation and filtration steps. Since the present Hercules
system employs sedimentation, a question arises concerning whether or not
the estimated costs of the alternate systems would be add-on costs for
Hercules. If the alternate systems were added to the present Hercules sys-
tem, no additional sedimentation step would probably be required because of
the extensive sedimentation system in place at Hercules. However, because
of the nature of the alternate systems, an additional filtration step would
probably be required to remove suspended solids. (The average concentra-
tion of suspended solids was 57 ppm between September 1974 and March 1975.)
Furthermore, because these solids remained after an extensive sedimentation
step, a sophisticated and costly filtration system might be required in
order to achieve a substantial reduction of suspended solids.
Sedimentation and filtration represent a significant portion (25 to
45%) of the estimated capital equipment costs for the alternate systems,
and the filtration step is four or five times more costly than the sedimenta-
tion step. Thus, even though the sedimentation step might be eliminated,
the total capital equipment cost would probably not be greatly reduced.
-------
SUMMARY OF ESTIMATED COSTS FOR TOXAPHENE WASTEWATER TREATMENT SYSTEMS
Hercules' system
Resin adsorption
Reductive degradation
Resin adsorption plus
reductive degradation
30 min contact time
60 min contact
(Hercules Plant
, Brunswick, Georgia)
Installed
Tbxaphene in
Wastewater
flow rate (gpm)
181 (8/74)
146 (2/75)
200
300
.on 200
300
us 200
tion 300
sorption
me 300
me 300
treated
Ppb
203
58
1.4
1.4
< 3
< 3
0.1
0.1
< 5
< 5
effluent
Ib/day
0.44
0.10
0.0034
0.0050
< 0.0072
< 0.0108
0.0002
0.0004
< 0.018
< 0.018
capital
equipment
cost
$800,000
800,000
586,200
790,400
350,700
433,700
731,600
955,900
617,000
794,000
Annual
operating
cost
$300,000
300,000
324,300
433,200
154,100
181,800
410,300
537,500
194,200
232,500
Cost per pound
of toxaphene
product.3.'
$0.0060 '
0.0060
0.0065
0.0087
0.0031
0.0036
0.0082
0.0108
0.0039
0.0047
aj Based upon an annual production of 50 million pounds of toxaphene.
-------
Furthermore, if a sophisticated filtration step was required, there might
even be an increase in costs. Therefore, we conclude that the estimated
costs of each of the alternate systems would be approximately equal to the
cost of adding that system to the existing Hercules system.
The effluent from the present Hercules system contains an average of
57 ppm suspended solids and 114 ppb toxaphene (the solubility of toxaphene
has been reported to be 400 to 3,000 ppb). Estimates indicate that the
concentration of toxaphene in the precipitated sludge is approximately 0.02%.
If it is presumed that the amount of toxaphene adsorbed on the suspended
solids is about the same as the amount adsorbed on the sludge, a 10% re-
duction in the amount of toxaphene in the effluent would be achievable if
the suspended solids could be completely removed from the effluent stream.
Very few data are available upon which to base the design of a fil-
tration system which would accomplish the removal of the suspended solids.
If a simple sand filtration system is sufficient, the estimated capital
equipment cost would be $130,000 to $160,000. If fine filtration is re-
quired, the estimated capital equipment cost would be about $225,000, but
a sand filtration system would probably also be required as an initial step.
Operating costs for each of these systems would be approximately 15% of the
capital equipment cost.
-------
SECTION II
CHARACTERIZATION OF INDUSTRY
Toxaphene (chlorinated camphene) is produced at four plants in the
United States which differ considerably in their operating characteristics.
A summary of production rates, average wastewater flows and average daily
toxaphene discharges is presented in Table 1. Detailed descriptions of
these plants and their wastewater operations are presented in the following
four sections.
HERCULES, INC.
General
The Hercules, Inc., chemical plant at Brunswick, Georgia, is about
50 years old (Ferguson and Mumma, August 1975). The plant produces about
120 products (SIC 2861 and SIC 2879-secondary) and the principal raw mate-
rial is pine stumps (Ferguson and Mumma, August 1975).
The Hercules plant produces resin, terpenes and their derivatives
from pine stumps. The plant uses^from 1,000 to 1,900 tons of stumps per
day. The stumps are washed, ground into chips and stored. The chips are
then extracted with a solvent (methyl isobutyl ketone) under heat and
pressure. The mixture of solvent and dissolved resin is drained from the
-------
Table 1. SUMMARY OF PRODUCTION RATES AND WASTEWATER CHARACTERISTICS
FOR TOXAPHENE MANUFACTURERS
Estimated 1975
toxaphene production
(millions of pounds)
Average wastewater
flow from toxaphene
production
gpm gal/lb of product
Hercules
Tenneco
Riverside
Vicksburg
50-802-
9-113.
3/
a/
9-11^
167k/
10.
1.10-1.75-'
0.003-0.004£/
0.30-0.38£/
0.48-0.58^
Average
daily toxaphene
discharge in
plant effluent
Ib/day ppb
0.27^ 114k/
< 0.05k/ < &J
0.032-/ 320k/
Unknown Unknown
a/ MRI estimate.
b/ Hicks (1975). See Table 2.
c/ Calculated from production estimates and wastewater flow rate.
I/ Calculated from data of Hicks (1975). See Table 2.
e_/ Worley (1975).
f/ Calculated from "Commingled" waste stream (003) flow rate (1.01 million
gallons per day) and average toxaphene concentration < 6 ppb (Worley, 1975).
£/ NPDES, TX0062448 (1975).
h/ The NPDES discharge limitation (TX0062448) is 0.04 Ib/day. September 1975
analytical data supplied by a Riverside representative indicates an average
monthly discharge of 0.032 Ib/day. On the basis of a 12,000 gal/day (5.8 gpm)
discharge, the calculated toxaphene concentration is 320 ppb.
i/ Enviro-Labs (1975). See text concerning Vicksburg wastewater characteristics.
-------
extractors and pumped to the refinery. The spent chips are burned in the
power plant boilers. Solvent, turpentine, and pine oil are removed from
the mixture by distillation. The crude rosin is subsequently refined
further into rosin derivatives. The solvent is recovered and returned to
the extractor. Mixed turpentine and pine oil are routed to the still
house for further separating and fractionating. Toxaphene insecticide is
manufactured from a-pinene in a separate process (Lair and Bruner, 1975).
Normally, the plant operates 7 days/week, 24 hr/day. However, since
the latter part of February 1975, the plant has been operating on a split
10-day-on 4-day-off schedule as follows (Lair and Bruner, 1975):
Primary operations (wood milling, extraction, and main portion of
the power hours) continuous until February 28, then the 10 day work-
ing schedule commencing March 5, 1975.
Secondary operations (toxaphene plant, and other conversion opera-
tions) continuous until February 23, then the 10 day working sched-
ule commencing February 26, 1975.
Toxaphene Manufacture
Hercules, Inc., has produced toxaphene at the Brunswick, Georgia,
plant since 1948 and was its first manufacturer. Hercules' patents on
toxaphene expired in the late 1960's.
The estimated annual production of toxaphene at the Hercules plant
in 1975 is 50 to 80 million pounds (MRI estimate).
-------
Toxaphene is produced in a series of steps beginning with the raw
material a-pinene, which is extracted from pulverized resinous southern
pine stumps. Alpha pinene is heated over a catalyst of benzoyl peroxide
to form camphene plus bornylene and some or-terpineol which are then chlor-
inated by liquid chlorine in carbon tetrachloride to produce yellow waxy
toxaphene. About two thirds of the final weight of toxaphene is chlorine.
Approximately 7 moles of chlorine gas are required per mole of camphene
to produce a mole of toxaphene and 6 moles of hydrochloric acid (Ferguson
and Meiners, 1974).
The production chemistry for toxaphene manufacture is shown in the
following equation (Ferguson and Meiners, 1974):
- Ci°Hi°cl8 + 6 HC1
_. _ . Toxaphene (mixed isomers
cr-Pinene • Camphene ,
and related compounds
67-697. Cl)
A production and waste schematic for Hercules' toxaphene process is
shown in Figure 1.
Jett (1975) has reported that Hercules' hydrochloric acid (muriatic
acid) by-product is either sold or neutralized. Hicks (1975) has reported
that the sources of the process water are deep wells.
Other information concerning toxaphene manufacture at Hercules is
shown as follows (Ferguson and Meiners, 1974).
10
-------
Southe
Pine St
Chi
Sol
H2O— »*
Lime . -MI
NaOH — »•
Lime-
Stone
Surface
Waters
rn —I
umps 1 £ 1 % „ _. Main Plant
' — ~ftp> a Pmene ... . e.
\ Waste Stream
J ~A
Reactor
^ NA/rfsVps * . ,. ,
» vvasres — Mixed
I Xylenes
Camphene j
• ... _ . .. 1 ^ Of> O^ Tnvnnliniin
orine »•
vent'- ' i " »•
Chlorinator
^..ioxaphene^^. p.|ter _^ Stripper -«*• Toxaphene — ^Solution
t J, 1 _ 1
r-HCI
Absorber
4
Scrubbers
(2)
t
Neutralizer
*
Primary
Waste
Treatment
Plant
Discharge to
Tidal Creek
J
<
Reco
Muri
Cake^ U^
1 — — L r^
— __ \ r
Dust
Formulation
\
— Baahouse Dust
Collector
vered 1
aticAcid t • . »
^ To Solid Atmosphere
^ Waste
Source: Ferguson and Metners (1974)
Figure 1. Hercules' production and waste schematic for toxaphene
-------
Material
1. Camphene
Material
1. HC1
Raw Materials (Ferguson and Meiners, 1974)
Received From Received By Storage
On site from
a-pinene
2.
3.
4.
5.
6.
7.
ci2
Solvent
Clay
NaOH
Limestone
Slaked lime
Six loc,
Georgia
Georgia
Georgia
Georgia
Tank cars
Tank cars
Rail
Tank truck
Rail
Rail
Tanks
Silo
Tanks
Silo
Warehouse
Reaction By-Products (Ferguson and Meiners, 1974)
Form
Solution in
water
Amount Produced
(Ib/lb AI)
0.53
Disposition
Sold or neutralized
Materials
Other Process Wastes and Losses
(Ferguson and Meiners, 1974)
1. Active ingredient
2. Solvents
3. Camphene production Liquid
4. Waste from scrubbers
Form
Liquid or solid
Disposition
Waste treatment system
Discharge to tidal creek
Waste treatment system
Disposition of Technical and Formulated Products
(Ferguson and Meiners, 1974)
^___ Shipments
Warehouse Technical Product Formulated Products
Elsewhere Container Transportation Formulation Container Transportation
% Small Exported via
amount, East coast
250 gal.
galvanized
drums
% Most, 907, Tanks,
concentrate; 55 gal.,
10% xylene 50-Ib
bags
pellet-
ized
Rail and truck
exports '
12
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Wastewater Treatment System*
On March 15, 1974, Richard E. Chaddock stated that the Hercules' waste
treatment system was based upon the principle that toxaphene in aqueous
medi? adsorbs very strongly to particulates, especially those of soil. In
this system, the waste stream to the treatment lagoon is neutralized and
the pH carefully controlled (Chaddock, 1974). The inert solids were re-
ported "to consist chiefly of sand, clay and insoluble hydroxides and car-
bonates." The toxaphene, "strongly adhering to the inert solids, settles
out in several lagoons connected in series" (Chaddock, 1974). Data on the
"irreversibility" of toxaphene adsorption has been reported by Wisconsin
scientists in a study of fish poisoning (Hughes et al., 1970).
On June 24, 1975, Hicks reported that the toxaphene waste treatment
system is a physical/chemical system (Hicks, 1975). Hicks (1975) also
reported that residual toxaphene is removed from the wastewater by adsorp-
tion on inorganic particulate matter and neutralized. Hicks reported that
"this process was selected as the best for toxaphene removal and imple-
mented following extensive testing of other methods such as heat treatment,
solvent extraction, and the use of other adsorptive media" (Hicks, 1975).
* Additional information concerning the Hercules' waste treatment system
is provided in Appendix A. The information contained in Appendix A
was obtained from an engineering report supplied by Mr. C. L. Dunn,
Manager, Ecological Research, Hercules, Inc., to Mr. Richard K.
Ballentine, Toxic Substances Branch, EPA, on December 16, 1975. This
information was not received in time to be incorporated into the
toxaphene manufacture report.
13
-------
A schematic diagram of the Hercules toxaphene wastewater treatment
system at Brunswick, Georgia, is shown in Figure 2. Hicks (1975) has re-
ported that these treatment facilities were built during 1971 to 1974.
Hercules uses a separate treatment system exclusively for wastewater
from its toxaphene plant (Ferguson and Mumma, August 1975). Wastewaters
from the toxaphene plant are neutralized with caustic and limestone and
then pumped into the treatment system shown in Figure 2. This treatment
system consists of a distribution pond, four settling ponds (each pond is
about 200 ft x 400 ft x 3 ft deep) and a pond used to collect storm water
from the toxaphene manufacturing area. A Parshall flume and automatic sam-
pler are used to monitor the effluent from the toxaphene treatment system.
Lair and Bruner (1975) have reported that'the Brunswick plant dis-
charges cooling waters, effluent from the toxaphene treatment system, and
effluent from the milling powerhouse area treatment system. Discharge is
into two ditches, designated by the company as the north and south ditches
(Figure 2). These ditches join to form the plant's main outfall (desig-
nated 001 on the NPDES Permit No. GA 0003735 (1974)). The combined dis-
charge is into Dupree Creek. Sanitary wastewaters from approximately 950
employees and process wastewaters from the plant's pretreatment facility
are discharged into the Brunswick, Georgia, municipal sewerage system
(Lair and Bruner, 1975).
14
-------
Toxophene Process
Wostewafer
Toxophene
Sludge
Drying
Bed
Sludge
7.5T/DC/
0.02% c/
Toxaphene,
Landfill
Wafer
Neutralization
Process
Toxaphene: 2200 ppb a/
140 gpm b/
Ph 4.2 a/
S.S. 9000 ppm _c/
Settling
Ponds
Distribution
'Pond
Settling
Ponds
(Not in
Use)
Storm water
Pond
Stormwoter
>unoff
Watery ^
Sludge
i i
X
167 gpm _b/
pH 6.0JB/
Toxaphene : 1 1 4 ppb jo/
S.S. 57 ppm b/
North Ditch
Into Dupree Creek
After Dilution with Cooling Waters
South Ditch
Milling Area ond Powerhouse
Wastewater Treatment System Effluent
References
aj Ferguson and Meiners (1974)
b/ Hicks (1975).
c/ MRI estimate.
Source: Adapted from Lair and Bruner (1975).
Ferguson and Meiners (1974).
Figure 2. Hercules' toxaphene treatment system at Brunswick, Georgia
-------
Lair and Bruner (1975) have reported that wastewaters from the toxa-
phene area floor drains and product loading area drains are pumped into
the distribution pond along with the toxaphene plant process wastes.
Storm water from the toxaphene production area is pumped to the spe-
cial storm water pond. Storm waters are pumped slowly from the toxaphene
storm water pond into the distribution pond and ultimately into the set-
tling ponds. As indicated in Figure 2, effluent from the settling pond
is discharged into the north ditch.
The cooling waters from the toxaphene production area are discharged
separately into the north ditch. Jett (1975) has reported that all cool-
ing water is noncontact.
Steam and electricity are generated in a separate remote area so
there is no boiler blowdown in the toxaphene area (Hicks, 1975).
Only two of the four settling ponds are used at any one time. When-
ever the settling ponds fill up with solids and treatment efficiency de-
creases, the ponds are taken out of service and the remaining two ponds
are placed in service. The ponds that are out of service are allowed to
dewater and the solids are dredged into a separate sludge drying bed and
air dried. Any drainage from the sludge drying bed is sent to the settling
ponds in service. All of the solids recovered from the toxaphene wastewater
are retained in the lagoon system or related drying beds; the estimated
total accumulation rate of solids is 5 to 10 tons/day (Hicks, 1975).
16
-------
Wastewater Characteristics
Hicks (1975) has reported that the average influent flow rate to the
Hercules' toxaphene wastewater treatment systems at Brunswick, Georgia,
is 200 gpm and that the treatment system has a design flow capacity of
300 gpm. Effluent data obtained between April 1974 and March 1975 is pre-
sented in Table 2.
Daily samples taken by Hercules between April 1974 and March 1975,
when the flow averaged 167 gpm, showed that the treated effluent discharged
into the north ditch had the following average characteristics: (a) pH,
6.0; (b) suspended solids, 57 pptn; and (c) toxaphene concentration, 114
ppb (Hicks, 1975). These statistics are shown in Figure 2 and are the
most recent information available.
Under the NPDES Permit No. GA 0003735 (NPDES, 1974), Hercules, Inc.,
issues monthly discharge reports (Outfall No. 001) to the Environmental
Protection Agency, Water Enforcement Branch in Atlanta, Georgia. Jett
(1975) has reported that the waste in the 001 outfall includes (a) the
treated toxaphene waste stream, (b) unprocessed pine stump wash water
which has been clarified, and (c) noncontact cooling water. Data taken
from monthly discharge reports, presented in Table 3 show the quantity and
and quality of the discharged effluent from Outfall No. 001 for the period
of June 29 to August 28, 1975. The average daily discharge of toxaphene
during this period ranged from 0.045 to 0.35 Ib/day.
17
-------
, Table 2. TOXAPHENE WASTEWATER EFFLUENT DATA
HERCULES, INC., BRUNSWICK, GEORGIA
Average
Average treated Average of suspended
effluent flow daily pH solids
readings (ppm)
6.4
4.4
4.9
5.0
6.2
6.5
6.9
Month
April 1974
May 1974
June 1974
July 1974
August 1974
September 1974
October 1974
November 1974
December 1974
January 1975
February 1975
March 1975
Overall average
(gpm)
-
181
181
-
181
194
181
167
139
153
146
167
167
6.9
6.5
6.4
6.9
5.3
6.0
83
71
81
71
47
32
12
57
Average
toxaphene
concentration
(ppb)
104
93
81
176
203
125
99
109
90
58
114
Source: Hicks (1975).
Note: The toxaphene plant was operated continuously from January 1
to February 23, 1975; then on an intermittent schedule (10
days on-stream and 4 days off) commencing February 26, 1975
(Lair and Bruner, 1975).
18
-------
Table 3. DATA FROM HERCULES' MONTHLY DISCHARGE REPORTS FOR NPDES PERMIT NO. GA 0003735
AT BRUNSWICK, GEORGIA, PLANT—JUNE 29 TO AUGUST 28, 1975 (Outfall No. 001)
Reporting period:
Parameter Units
Flow MGD
Toxaphene Lb/day
Suspended Lb/day
solids
PH
Reported
Permit
condition
Reported
Permit
condition
Reported
Permit
condition
Reported
Permit
condition
June 29-July 28, 1975 July 29-August 28, 1975
Minimum Average Maximum Minimum Average Maximum
3.6 - 3.6
0.45 1.06 - 0.35 0.99
1.0 - - 1.0
422 960 - 405 900
9,000 27,000 - 9,000 27,000
6.6 7.1 7.5 6.6 7.4 8.1
6.0 - 9.0 6.0 - 9.0
-------
Further tests during March 3 to March 6, 1975 (Lair, 1975) showed
that the effluent into Dupree Creek had a flow of 16.5 million gpd, a pH
of 7.5 and a toxaphene concentration of 4 ppb after dilution in the ditches
with 16.3 million gallons per day of cooling water.
The Hercules' treatment facilities are reported to have been con-
structed to reduce the toxaphene content of the plant discharge to less
than 1 Ib/day (Hicks, 1975). Information provided in the NPDES permit
application for the Brunswick plant (NPDES for Permit No. GA 0003735,
1974) indicate that the effluent from the treatment facility has averaged
0.51 Ib/day of toxaphene, but the mean toxaphene content of the total plant
discharge (Outfall No. 001) has been about 2 Ib/day. Hercules states that
"the discrepancy is believed to be due in part to runoff from contaminated
areas outside the collection system and problems in sampling and analysis.
Efforts are being made to minimize the discrepancy and to reduce the toxa-
phene content of the total plant discharge" (NPDES, 1974).
The concentration of suspended solids in the effluent discharged from
the Hercules' neutralization process (see Figure 2) is unknown and no
information on this subject could be obtained from the company. On the
basis of the data shown in Figure 2, the loading of suspended solids can be
estimated as follows.
Given: Wastewater from neutralization process has a flow rate of
140 gpm which is equivalent to 1,683,000 Ib/day (Hicks, 1975).
Average daily generations of waste sludge is 7.5 tons or
15,000 Ib/day (Ferguson and Mumma, 1975)—all derived from
solids contained in neutralization wastewater.
20
-------
Hicks (1975) has reported that the average concentration of suspended
solids in the treated toxaphene effluent (discharged to north ditch) dur-
ing the period of September 1974 to March 1975 was:
57 ppm or 1,683,000 x 57 = 96 ib/day
106
Then, estimated concentrations of suspended solids in effluent from neu-
tralization process is:
—15?000 + 96 = ~ 9,000 ppm suspended solids in effluent
1,683,000 x 10"^ from neutralization process
The estimated values developed above are included in Figure 2, the
schematic for Hercules' toxaphene wastewater treatment system at Brunswick,
Georgia.
Sludge Characteristics
In the Hercules' toxaphene wastewater treatment system, a significant
amount (average of 7.5 tons/day) of waste sludge or settled solids is gen-
erated (Ferguson and Mumma, 1975). However, no information was obtained
from Hercules concerning the toxaphene content in the waste sludge.
On the basis of the available data, shown in Table 2, the approximate
toxaphene content in this sludge can be estimated as follows:
Given: Wastewater from neutralization process has a- flow rate of
140 gpm and contains ~ 2,200 ppb toxaphene. Treated efflu-
ent has a flow rate of 169 gpm and contains 114 ppb toxaphene.
21
-------
For neutralization wastewater:
Flow = 140 x 60 x 24 = 201,600 gpd or
201,600 x 8.35 Ib/gal = 1,683,000 Ib/day
2,200 ppb x 1.683.000 , _ .. . .. .
rrtj— = ~ J.7 lb toxaphene/day in
wastewater
For treated effluent (discharged to north ditch):
Flow = 167 x 60 x 24 = 240,000 gpd or
240,000 x 8.35 Ib/gal = 2,000,000 Ib/day
114 ppb x 2,000,000 = ^ o.23 lb toxaphene/day
For waste sludge (7.5 tons/day),
The toxaphene content is estimated to be:
(3.7 - 0.23) x 100 = ~ 0.02% toxaphene in sludge
7.5 x 2,000
In-Plant Controls
The toxaphene production area at Hercules is diked so that all liquid
wastes (e.g., leaks or spills) are contained and are eventually processed
through the wastewater treatment system. All liquid wastes from the toxa-
phene unit go to a large holding pond and waste treatment system (Ferguson
and Meiners, 1974).
At Hercules, process vents are water, caustic, or lye scrubbed before
venting to the atmosphere; waste from these scrubbers also goes to the hold-
ing pond. Baghouses are used in the dust concentrate unit, which is located
in the toxaphene production area. Dust from the collection system is re-
cycled. Short scheduled shutdowns for maintenance are made as needed
(Ferguson and Meiners, 1974).
22
-------
The tank cars, whether owned by the company or by the railroad, are
dedicated to toxaphene and are cleaned yearly at the Hercules plant, with
the washings going to the toxaphene recycle system and aqueous wastes
through the waste treatment systems. Tank trucks are customer- or truck
line-owned and are cleaned by the owner (Ferguson and Meiners, 1974).
Effluent Disposal Method
As shown in Figure 2, effluent from the toxaphene wastewater treat-
ment system is discharged to the north ditch along with cooling waters
from the Hercules plant. Effluent from the Hercules' milling area and
powerhouse wastewater treatment system is discharged along with plant
cooling waters to the south ditch. The outflow from these two ditches is
joined into a common plant discharge (Outfall No. 001) which enters Dupree
Creek.
The final disposal of treated- toxaphene wastewater into municipal
sewage treatment plants is an option which may be useful in some locations.
Hercules has plans to verify the efficacy of this procedure by plant-scale
trials at the Brunswick, Georgia, municipal sewage treatment facility.
Hercules has funded a research study on the effect of toxaphene on sewage
^
treatment (Black et al., 1971); the report shows that toxaphene can be
added to a sewage treatment plant without adverse effects upon normal
treatment processes.
23
-------
Plant Visit
On August 20, 1975, T. L. Ferguson and C. E. Mumma visited the chem-
ical plant of Hercules, Inc., at Brunswick, Georgia, to discuss toxaphene
wastewater treatment. The toxaphene wastewater treatment facilities were
examined during this visit (Ferguson and Mumma, 1975).
TENNECO CHEMICALS, INC.
General
The Fords New Jersey Plant, of the Organics and Polymers Division, of
Tenneco Chemicals, has its origin in the early 1900's. Since that time,
it has changed hands and changed names several times.
In 1963, following a series of mergers with Newport Chemical Company
and Nuodex the total assets were acquired by Tennessee Gas Transmission
Company. In 1965, the name of Tenneco Chemicals was born.
At present, more than 40 chemicals are produced at Fords. Some of
. the items are bulk chemicals and are produced at rates of 200 million pounds
per year. Some are produced at rates of only 200 pounds per day. The final
uses for these chemicals vary from flame retardants for children's sleep-
wear and intermediates for the paint, dye and plastics industry to food
preservatives, agricultural sprays and materials for the cosmetic industry.
The current product line (SIC 2818) includes chlorinated aromatics and air
oxidation products.
Toxaphene is produced, but is not formulated (Meiners and Mumma, 1975a).
The toxaphene products at the Fords plant have the Tenneco trade names of
24
-------
Strobane® T-90 (907o active ingredient) and Strobane®-T (1007» active in-
gredient) . Product quantities are considered by Tenneco to be proprietary
information and actual production data were not obtained from the company.
On the basis of a communication with a Tenneco representative, the esti-
mated annual production of toxaphene at the Fords, New Jersey, plant is
about 9 to 11 million pounds per year (Meiners and Mumma, 1975a). The
process equipment which is dedicated to production of toxaphene has been
operated since 1965; major revisions were made to the plant in 1969.
Tenneco operates the toxaphene plant at least 10 months each year.
Manufacturing Process (Worley, 1975)
The toxaphene manufacturing unit is part of a chlorination complex
in which several processes are integrated by sharing parts of a larger
equipment train.
All plant chlorination processes receive chlorine from a common tank
car storage-feed system. In addition, all of the processes also direct
by-product HC1 off-gas to a centrally located acid plant for eventual
recovery.
A process schematic for production of Strobane®-T at the Ford's plant
is shown in Figure 3. Points where common ties to other processes are
made are indicated in this figure.
XR\
Strobanew-T is manufactured by a batch process in which chlorine gas
is reacted with a camphene liquid to form a waxy solid containing 67 to 697o
chlorine content. The camphene is purchased.
25
-------
N>
Chlorine and
HCL from all
Chlorinatlon
Proceuei
Stack
HCL+CL2(Unreacred)
HCL
*7 Blender ^
I T>^ )
Spent Caustic
to Chemical Sewer
Middlesex Count/ Authority
~-1009Pd
Crude Mono-
Chloro Toluene
Dike
— "tJ Strobone®-T
Product
>
r
Storage
Strobone^-T
90
*
Drumming Tank -Q—t (
7i
^\ • Drums
StrobonAT
Strobone*-T
Tank Car or Truck
o o
StrobonAT 90
90
100
-Wafer
Muriatic
Acid
Source: Tenneco Chemicals, Letter from J. W. Worley, Works Manager to
Mr. W. J. Hunt, Effluent Guidelines Division, EPA, August 13, 1975.
<$>.
Figure 3. Schematic flow diagram—manufacture of toxaphene (Strobanew-T)
by Tenneco Chemicals, Fords, New Jersey
-------
The chlorination reaction is exothermic. Noncontact cooling is pro-
vided with an intermediate oil medium, which in turn is water-cooled in
a noncontact heat exchanger.
The chlorination by-product HC1 and unreacted chlorine gas are vented
from the reactor to an acid plant by an off-gas header, which also receives
chlorine and HCl from other processes. Both of these off-gases are recov-
ered as by-products by means of gas scrubbers.
When chlorination is completed, the batch is dropped from the reactor
to a blend tank where further physical processing occurs. The residual
entrapped gases (of HCl and chlorine) are air-sparged for removal. These
gases are subsequently neutralized in a common caustic scrubber which is
also used for treatment of gases from other (unrelated) operations in the
same plant. All of the reactor contents are collected as the final pro-
duct. By-product muriatic acid (20° Be") is sold as commercial product.
Crude monochlorotoluene, a by-product of other operations, is also recov-
ered and is consumed internally as an intermediate for other chlorine
derivatives.
(R)
For the preparation of Strobanew-T-90, xylene is added as a diluent
(S)
to Strobane -T in a blending operation. Vent gases from the blender, con-
sisting of air and HCl, are scrubbed by contact with a caustic solution.
The scrubbed gas is discharged to a vent stack and the spent caustic li-
quor (~ 100 gpd) is discharged to a chemical sewer.
27
-------
The product is drummed, charged into tank cars or tank trucks, or
placed in storage tanks. The storage tank areas are diked to contain any
spilled or leaked material. About 20% of the product is shipped in 50-gal.
drums and the balance is usually shipped in railroad tank cars. Tank
trucks are used occasionally to ship product.
Tenneco uses a "dry" production process. The process does not use
any contact process water and does not have any washing step. Any water
in the vicinity of the manufacturing process equipment does not come in
contact with the toxaphene itself which is a "bottoms" product. No dis-
tillation operations are conducted.
The primary source of noncontact cooling water is a natural ground-
fed stream within the plant boundary. This stream is impounded in a man-
made pond which overflows to the Raritan River at an approximate rate of
500,000 gal/day (NPDES, 1972). The pond serves as an evaporation heat
sink as the noncontact cooling water is drawn from and returned to this
pond at a maximum rate of approximately 3,600 gal/min.
The water used for processing is obtained from the Middlesex Water
Company of Edison, New Jersey. Water usage in the toxaphene production
unit includes makeup water in the cooling water system and water supplied
to the caustic scrubber system which treats vent gases.
Wastewater Characteristics (Worley, 1975)
A representative of Tenneco, Inc. (Worley, 1975), has indicated that
there is no process wastewater from the Strobane®-T process.
28
-------
Process wastewaters from all plant processes are collected and di-
rected to common sewer headers which, in turn, flow to a centrally located
in-plant collection sump. These wastes are then neutralized with lime and
subsequently discharged to the Middlesex County Sewerage Authority (MCSA).
These wastes are then collectively analyzed by the MCSA for the parameters
of flow gallons, BOD, suspended solids, and chlorine demand.
The "commingled" waste stream (labeled Stream 003) has an average
analysis as follows (Worley, 1975):
Flow million gal/day 1.01
BOD" mg/liter 1,153
S.S. mg/liter 382
Chlorine demand mg/liter 8.89
Runoff water flows to either of two discharge streams labeled 001
and 002 located at opposite ends of the plant. Stream 001 includes both
ground-fed water as well as natural runoff. Stream 002 contains runoff
water only, and its average flow rate is approximately 30,000 gpd. The
flow rate of both of these streams vary, depending on the amount of rain-
fall.
Discharge streams 001 and 002 are covered by the current NPDES Permit
No. N.J. 0000116 (1972). The NPDES permit describes the discharge to the
Raritan River. Both Streams 001 and 002 have been checked for toxaphene
analyses and the results were negative. Therefore, it appears that fugi-
tive losses to the effluent streams are extremely low, if any. The NPDES
29
-------
Permit Application No. 2SDOXW2000021 (NPDES, 1972) contains information
concerning Stream 003. However, Stream 003 is not included in the NPDES
permits because the discharge does not flow to a navigable waterway.
The Middlesex Authority provides a monthly composite sample of the
total Tenneco plant waste effluent, discharge Stream 003. This composite
represents 20 or more individual samples taken by the MCSA as part of
their waste monitoring program.
The monthly composite sample is then sent to an outside concern for
their individual analysis for toxaphene content.
A recent history of toxaphene analysis in the total Tenneco plant
waste discharge (Stream 003) is presented below.
Monthly
Composite
May 1974
June 1974
July 1974
August 1974
September 1974
October 1974
Toxaphene
Analyses
< 5.0 ppb
< 10.0 ppb
< 5.0 ppb
< 5.0 ppb
< 5.0 ppb
< 5.0 ppb
Monthly
Composite
November 1974*
December 1974*
January 1975
' February 1975
March 1975*
April 1975
Toxaphene
Analysis
-
< 10 ppb
< 5 ppb
-
< 5 ppb
* Samples were not sent out for analyses during these months.
Source: Worley (1975).
These data show that the toxaphene content in the wastewater was-
always less than 10 ppb and usually less than 5 ppb. The monthly average
toxaphene content was less than 6 ppb. Tenneco representatives have pointed
out that the analyses represented the limit of detectability and that it is
possible that there was no toxaphene in the discharge stream. The analytical
30
-------
samples included suspended solids, since there is no settling of solids
prior to discharge.
Spent caustic is discharged at a rate of about 100 gpd from the
caustic scrubber unit used in the toxaphene process. No data are avail-
able on the composition of this caustic liquor, but Tenneco representatives
have indicated that this stream contains little or no toxaphene (Meiners
and Mumma, 1975a).
In-Plant Controls
In-plant pollution controls include the noncontact heat exchange used
in the toxaphene process and the use of xylene instead of water to clean
out the equipment. The xylene cleaning liquor is recovered and used in
•
the plant.
In the event of on-site product spills, the spill is cleaned up im-
mediately and the incident is reported to the state office of EPA.
A water cooling tower is used in conjunction with the noncontact heat
exchange system (see Figure 3) to conserve water and permit water recycling.
Containment dikes are provided in the toxaphene production area and
around the product storage tanks to prevent loss of pesticide to the en-
vironment. All exhaust gases from processing are treated in gas scrubbers
before being vented to the atmosphere.
Wastewater Treatment
No wastewater treatment methods are used by Tenneco for the toxaphene
manufacturing operation since no wastewater is discharged from the process.
31
-------
For the total plant effluent, the type of waste treatment employed
consists of segregation of streams, collection, neutralization with lime,
and discharge (without settling) to the Middlesex County Sewage Authority
(Stream 003). The solids generated are discharged along with the effluent
stream; no sludge is accumulated.
The Tenneco waste treatment system is designed for a flow of 2 mil-
lion gallons per day. The annual operating cost is approximately $240,000
which includes the MCSA treatment costs of $100,000/year. The capital
value is approximately $290,000, which includes the most recent upgrading
expenditure of $85,000 in 1968. The waste treatment system was originally
built in 1958 (Worley, 1975).
Plant Visit
On October 13, 1975, Dr. A. F. Meiners and Mr. C. E. Mumma of MRI
visited the toxaphene plant site of Tenneco Chemical, Inc., in Fords, New
Jersey. Mr. Stephen J. Jelich, Technical Superintendent, and Mr. W. P.
Anderson, Director of Environmental Sciences, were interviewed concerning
the toxaphene operations. The manufacturing process and waste treatment
facilities were examined during the visit (Meiners and Mumma, 1975a).
RIVERSIDE CHEMICAL COMPANY
General
The original chemical plant at Groves, Texas, was built by Sonford
Products Company under government contract for production of chlorinated
benzene. Later the plant was used to produce chlorinated phenols. Beginning
32
-------
about 1967, the plant was used to manufacture toxaphene (Meiners and Mumma,
1975b). It was later assumed and operated by Bison Chemical Company.
On February 5, 1974, this plant was purchased from Bison by Riverside
Chemical Company, a subsidiary of Cook Industries, Inc. This company is
now in the process of extensive renewal and modernization of the entire
production facility, including precautions to prevent accidental discharge
of toxaphene.
The Riverside Chemical Company's toxaphene plant at Port Neches,
Texas, currently produces about 8 to 10 million pounds per year of toxa-
phene (the address of the plant is a post office box in Groves, Texas).
The production capacity of this toxaphene plant has recently been increased
and is now about 12 to 14 million pounds per year. The company also pro-
duces chlorinated paraffins (about 6 to 7 million pounds per year) at this
plant. Hydrochloric acid, a by-product of these chlorination processes,
is also recovered and sold. The plant operates 24 hr/day, 7 days/week
(Meiners and Mumma, 1975b).
Manufacturing Process
No detailed information on the process technology was obtained (or
requested) by project investigators (Meiners and Mumma, 1975b).
Basically, the process consists of reacting chlorine gas with camphene
(maximum chlorination temperature is 350°F) and separating out the by-
product HC1 and excess chlorine in an off-gas stream which is scrubbed to
33
-------
recover the by-product acid. Heat generated in the exothermic chlorina-
tion reaction is removed by noncontact heat exchangers using cooling water.
A cooling water tower is provided. Cooling water is recirculated to the
toxaphene plant heat exchanger from this cooling water tower. The by-
products of the toxaphene process are hydrochloric acid and probably sodium
chlorite from the scrubbers (Meiners and Mumma, 1975b).
Well water is used in the toxaphene plant. About 9,500 gpd are con-
sumed in the toxaphene process. In the recovery process for by-product
hydrochloric acid (muriatic acid), 3,500 gpd of water are used. The hydro-
chloric acid process produces 3,000 gpd of product (NPDES, TX0062448, 1975),
Wastewater Characteristics
According to their NPDES Permit No. TX0062448 (NPDES, 1975), the com-
pany has the effluent limitations shown below.
EFFLUENT LIMITATIONS
RIVERSIDE CHEMICAL COMPANY TOXAPHENE PLANT
GROVES, TEXAS
Discharge Limitations
kg/day (Ib/day)
Effluent Characteristic
Toxaphene
Biochemical Oxygen Demand
(5 day)
Chemical Oxygen Demand
Total Suspended Solids
Oil and Grease
Daily Average
0.02 (0.04)
4.5 (10)
27 (60)
4.5 (10)
2 (5)
Daily Maximum
0.03 (0.06)
9 (20)
45 (100)
9 (20)
NA
Source: NPDES (1975)
In addition, the permit specifies a 3.0 mg/liter (as CC14) discharge
of chlorinated hydrocarbons.
34
-------
According to the NPDES permit (NPDES, 1975) the plant intake of water
is 19,000 gpd. This amount of water is accounted for as follows:
Discharges (gpd)
Surface Water 2,000
Sanitary Water 500
Evaporation 2,000
Consumption 3,000
Boiler and Cooling Tower
Blow Down and Condensate 11,500
Total 19,000
In their NPDES permit (NPDES, 1975), Riverside Chemical Company pre-
sented a schematic of water flow as shown in Figure 4. Well water is em-
ployed in three processes: (a) 9,500 gpd is used in the toxaphene process;
of this, 1,200 gpd is evaporated to the atmosphere, and 8,300 gpd is waste-
water which is conducted to a holding pond; (b) 5,500 gpd of well water is
used in the paraffin chlorination process; 600 gpd is evaporated to the
atmosphere; 4,900 gpd is wastewater which is also conducted to the holding
pond; (c) 500 gpd of well water and 3,000 gpd of process water are employed
in the hydrochloric acid.process which produces 3,000 gpd of product and
300 gpd of wastewater. The total indicated amount of wastewater from the
three processes is 13,500 gpd. This plant currently generates 12,000 gpd
of wastewater (Meiners and Mumma, 1975b).
The by-product hydrochloric acid is sold to Reagent Chemicals Company
which is located near the Riverside plant (Meiners and Mumma, 1975b).
35
-------
to Atmosphere
1200 gpd
t
Row
Mat.
Wastewate
8300 gpd
Toxaphene
Process
r
i
i
On-Site yyt
. Holding w
*rlds Pond
Wastewate
4900 gpd
i
•r
i
1
9500
gpd
•1!
iter
5500
gpd
— » Product
to Atmosphere
200 gpd
Process Water *
3000 gpd 1 T
500 Muriatic
n Arid
9Pd Process
Product
^ 3000 gpd
1
Wastewater
^ tn Atmosohere 300 gpd
i 600 gpd
Chlorinated
Paraffin
Process
^ Product
Adapted from information provided by Riverside Chemical Company
Source: NPDES Permit No. TX 0062448 (1975)
Figure 4. Schematic of water flow—Riverside Chemical Company,
Port Neches, Texas
36
-------
Analytical data concerning any contaminants in this by-product, hydro-
chloric acid, were not obtained by project investigators. However, a
Riverside Chemical Company official has indicated that there is little,
if any, toxaphene contained in this acid (Meiners and Mumma, 1975b).
In-Plant Controls
For in-plant toxaphene operations, pollution control is accomplished
by dikes around all process equipment to contain all spills and leaks. A
pit is provided for containment of massive spills. Also, a drainage system
and collection sump for rainwater runoff has been provided; runoff col-
lected in the sump is pumped to an unlined holding pond. Riverside has
had the soil near this pond analyzed for porosity and had found that the
soil is nearly impervious to transfer by seepage (Meiners and Mumma, 1975b).
The off-gases from production of by-product hydrochloric acid are
neutralized in a gas scrubber before being vented to the atmosphere. At
present, there is a small discharge flow (~ 12,000 gpd, see below) from the
plant holding pond overflow, cooling tower blowdown, and boiler blowdown
to the Jefferson County canal which adjoins the property. In addition, the
neutralized caustic solution used to adsorb fugitive hydrogen chloride and
chlorine gases from the scrubber goes into the Jefferson County Canal.
Wastewater Treatment
At present, no wastewater treatment method is used by Riverside Chemi-
cal Company at their Port Neches, Texas, plant. All wastewater from the
diked chlorinating area is collected in a common holding pond (about
37
-------
75 ft x 150 ft x 10 ft deep) located cm-site (see Figure 4). Riverside is
meeting the NPDES discharge limitation of 0.04 Ib/day of toxaphene (daily
average). The average daily volume of wastewater from three processes operated
on-site is 12,000 gpd.
A Riverside official has stated that, theoretically, "no discharge"
could be achieved. However, in ordinary plant operations, some water dis-
charge will inevitably be required. The "no discharge" achievement would
mean that all leaks can be controlled; all by-product hydrochloric acid is
sold and the fugitive hydrogen chloride and chlorine gases from the scrub-
ber converted into bleach (Meiners and Mumma, 1975b).
Plant Visit
On August 7, 1975, Dr. A. F. Meiners and Mr. C. E. Mumma visited the
toxaphene plant of the Riverside Chemical Company at Port Neches, Texas. Toxa-
phene production was discussed with Mr. Robert C. Harnden, Senior Vice-
President of Riverside Chemical Company. The manufacturing process and
waste treatment facilities were examined during this visit.
VICKSBURG CHEMICAL COMPANY
General
The Vicksburg Chemical Company plant at Vicksburg, Mississippi, manu-
factures organic and inorganic chemicals including toxaphene, potassium
nitrate, ammonium nitrate, dinitrobutylphenol (DNBP), methyl parathion,
substituted triazines, nitric acid, and chlorine.
38
-------
The toxaphene production unit is about 2 years old; the process equip-
ment in this unit is used only for toxaphene manufacture. No toxaphene
formulation operations are conducted at this plant. Production of this
pesticide product (Vicksaphene®) is carried out on a seasonal basis accord-
ing to market demand (Meiners and Mumma, 1975c).
Manufacturing Process
A batch type production process is used as shown in Figure 5. Pur-
chased camphene is reacted with chlorine gas; the chlorination is conducted
using four reactors connected in series. Chlorine is introduced into these
reactors from a vaporizer. The exothermic heat of reaction is removed by
noncontact heat exchangers. No solvents are used in the process, but the
toxaphene is diluted with 107., xylene and sold as a 907, product.
Effluent hydrogen chloride gas is passed through a falling film ab-
sorber, and recovered by-product hydrochloric acid is removed from the
bottom of the absorber and sent to storage. All of the by-product acid
produced in this process is sold. Data obtained from the State of
Mississippi (NPDES Application No. MS0027995, 1975) shows that the daily
production of acid amounts to 48,000 Ib/day during operating periods.
Off-gases leaving the acid absorber are contacted in a gas scrubber
with caustic soda solution to neutralize any unabsorbed HCl or chlorine.
The scrubbed gas is then vented to the atmosphere. Neutralized HCl waste
(containing water and sodium chloride) is discharged at a flow rate of
about 10 gpm to a settling pond.
39
-------
VICKSAPHENE (Toxophene)
PRIMARY EFFLUENT TREATMENT
Effluent
Hydrochloric
Acid
f S,
Process
Reactor
\^_^S
Unabsorbed
Acid
Falling
Film
Absorber
1
-*- Inert
Caustic
Neutralizer
Neutralized Hydrochloric Acid Waste Containing
Sodium Chloride and Water to Settling Pond.
Efficiency of Hydrochloric Acid Removal: 99+%
Recovered Acid
to Tanks Process
Source: Vicksburg Chemical Company, Fact Sheet, Application for National Pollutant Discharge
Elimination System Permit to Discharge Wastewater to Waters of the State of
Mississippi, February 25, 1975.
Figure 5. Toxaphene production schematic—Vicksburg Chemical Company, Vicksburg, Mississippi
-------
During the seasonal operating periods, the process is operated 24
hr/day.
Wastewater Characteristics
The only liquid waste produced in the toxaphene process at the
Vicksburg, Mississippi, plant is the neutralized HC1 waste discharged at
a rate of about 10 gpm from the caustic scrubber (Meiners and Mumma, 1975c).
Chemical analyses performed by independent testing laboratories on samples
of this effluent have not detected any toxaphene. (The analytical methods
used were not stated.)
An engineering report was recently prepared for the Vicksburg Chemical
Company by Enviro-Labs, Inc. (Enviro-Labs, 1975) as part of the requirement
for the NPDES permit. The information concerning toxaphene in this report
is quoted below.
"Toxaphene produces no liquid wastewater; however, there is a scrubber
of high pH content to remove any chlorine that may escape from the reactor.
The flow rate from the scrubber is approximately 10 gpm."
In-Plant Controls
The use of a noncontact cooling procedure for the chlorination reac-
tion serves to reduce greatly the quantity of wastewater.
The entire toxaphene production facility is built on a concrete pad
and is diked to contain any spills, leaks and rainwater runoff in the pro-
duction area.
41
-------
Wastewater Treatment
The only effluent from the toxaphene process is spent caustic solution
discharged from the off-gas scrubber at a rate of approximately 10 gpm
(Enviro-Labs, 1975). A Vicksburg Chemical Company official has stated
that independent analysis of this effluent has failed to detect the pres-
ence of toxaphene (Meiners and Mumma, 1975c). This effluent is discharged
to a final neutralization and settling pond located on-site as shown in
Figure 6. Waste liquor is pumped from this pond to the city treatment
plant (Figure 7).
A Vicksburg Chemical Company official has pointed out that zero dis-
charge of effluent is not considered to be feasible, since it is probably
impossible to avoid the small discharge (10 gpm) of effluent from the off-
gas caustic scrubber (Meiners and Mumma, 1975c).
Plant Visit
On October 14, 1975, A. F. Meiners and C. E. Mumma visited the pro-
duction plant of the Vicksburg Chemical Company in Vicksburg, Mississippi.
Toxaphene production was discussed with Mr. Silvan B. Lutkewitte, President,
and Mr. Jerry W. McAdams, Environmental Engineer. The manufacturing pro-
cess and waste treatment facilities were examined during this visit.
42
-------
PRODUCT TYPE
Woste
Primary
Treatmen t
U>
Secondary
Treatment
Vicksaphene (Toxaphene)
HCL: 48,000 Ib./da.
Acid Absorption
Caustic Neutralizing
Acid Removed: 47,500Ib.
% Efficiency: 99%
Dinoseb
Phenol: 252 Ib./da.
H2SO4-HNO3]89lb./da.
Activated Carbon
Chemical Removal
Phenol Removed: 250Ib.
% Efficiency: 99%
Potassium Nitrate/
Ammonium Nitrate/
Nitric Acid
Chlorides: 650Ib./da.
Ammonia: 1159 Ib./da.
Nitrates: 5816Ib./da.
Chemical Premix and
Precipitation
Effect i Complete
Neutralization and
Approximate 5%
Precipitation
Final Neutralization and Settling Pond
Inlet Solids: 12000ppm-Out 2754ppm (avg)
% Efficiency: 70%
Discharge ph Range: 8- 10
Effluent Volume: 700.OOOgal./do.
River Volume: Over 50 Billion gal ./da.
Methylphosphate
Organo-
Phosphate: 1000 Ib./da.
H2S04 450 Ib./da.
Caustic Regeneration
Process to Produce
Sodium Phosphate,
H2S, Sodium Chloride
Organophosphate
Removed: 980Ib./da.
% Efficiency: 98%
Overall System Efficiency
for Contaminents Removal :
Approximately 80%
Source: Vicksburg Chemical Company, Fact Sheet, Application for National Pollutant Discharge
Elimination System Permit to Discharge Wastewater to Waters of the State of
Mississippi, February 25, 1975
Figure 6. Effluent treatment process—Vicksburg Chemical Company,
Vicksburg, Mississippi
-------
To City Treatment Plant
H
Degradation Pond
City Manhole
Sampling
Inspection
Holding
Pond
Neutralization
i
1 i
i
1
Pi
CH
Scrubbers
Potassium Nitrate -
Chlorine Plant
Secondary Treatment
2.53 Acre
Surface Area
Source: Vicksburg Chemical Company, Fact Sheet, Application for National Pollutant Discharge
Elimination System Permit to Discharge Wastewater to Waters of the State of
Mississippi, February 25, 1975
Figure 7. Liquid waste disposal system—Vicksburg Chemical Company, Vicksburg, Mississippi
-------
SECTION III
ALTERNATE SYSTEMS FOR REMOVING TOXAPHENE FROM WASTEWATER
A number of wastewater treatment methods have been investigated for
the removal of toxaphene from wastewater. The methods which have received
the most attention in past and current research, and which appear to be
the most promising are (a) adsorption on synthetic resins, (b) reductive
degradation, and (c) carbon adsorption. None of these systems have been
operated under conditions which approximate actual use for toxaphene re-
moval, nor have they been developed to a point where an accurate deter-
mination of operating conditions or costs can be made with confidence. In
this section of the report, each of these systems is described, the probable
effluent quality which can be achieved by each system is estimated, and the
cost of each system is estimated based on its application to the toxaphene
wastewater generated at the Hercules plant.
PRESENT STATUS OF ALTERNATE SYSTEMS FOR TREATING TOXAPHENE WASTEWATERS
Presented below are brief discussions of the present status of alter-
nate systems for the treatment of toxaphene wastewater.
45
-------
Adsorption on Synthetic Resin
The Rohm and Haas Company has developed a synthetic, polymeric adsorbent
which shows excellent promise for the removal of pesticides from wastewater.
According to this process, pesticides are adsorbed on Amberlite XAD-4, a syn-
thetic, polymeric adsorbent processing high porosity (0.50 to 0.55 ml of pore
2
per milliliter of bead) , high surface area (850 m /g) and an inert, hydropho-
bic surface (Kennedy, 1973). The adsorbent is regenerated with an organic sol-
vent, and the adsorbed pesticides are recovered in a concentrated form.
The process appears to have important advantages over carbon adsorp-
tions. For example, the XAD-4 resin has been shown to be superior to ac-
tivated carbon both in terms of pesticide leakage and in overall operating
capacity (Kennedy, 1973).
Although the laboratory data look promising, many problems must be
worked out before a practical process can be operational. To the best of
our knowledge as of November 18, 1975, pilot-scale tests of the efficiency
of treating toxaphene wastewater by this process have not been performed.
Reductive Degradation
Promising laboratory results have been shown by a degradation process
involving the catalyzed reduction of chlorinated pesticides to relatively
nontoxic products which do not contain chlorine. The process consists of
a copper-catalyzed reduction of the pesticide in water by iron. The pesti-
cide containing wastewater is passed through a packed column with the re-
ductant suitably diluted with inert particles to obtain good flow properties.
46
-------
Sweeny and Fischer (1970) and Sweeny et al. (1973) have reported that
this process appears to be attractive for the destruction of a wide range
of chlorinated hydrocarbon pesticides, including the cyclodiene pesticides:
aldrin, dieldrin, chlordane, endrin and heptachlor. In laboratory studies,
the process was found to proceed smoothly at ambient temperatures to remove
all or a substantial amount of the chlorine from dissolved pesticides.
Applicability of the technique to toxaphene waste has been reviewed
(Ferguson and Meiners, 1974). In one test, toxaphene waste was passed
through a column at neutral pH. There was no deviation from the gas chro-
matograph baseline indicative of any of the seven principal peaks of toxa-
phene in the effluent (< 0.1 ppb); the solutions before treatment ranged
as high as 5.5 mg/liter toxaphene (probably indicating the presence of some
suspended toxaphene).
Activated Carbon
Limited laboratory data are available concerning the adsorption of
toxaphene on activated carbon.
Hager and Rizzo (1974) have prepared limited isotherm data for the
adsorption of toxaphene on carbon. The adsorption isotherm is the relation-
ship, at a given temperature and other conditions, between the amount of a
substance adsorbed and its concentration in the surrounding solution. A
reading taken at any point on an isotherm gives the amount of material
47
-------
adsorbed per unit weight of carbon. In very dilute solutions, such as
wastewater, a logarithmic isotherm plotting usually yields a straight line.
From adsorption isotherm data, a determination can be made of whether
or not a particular degree of organic removal can be effected by adsorption
alone. Isotherm data will also show the approximate adsorptive capacity
of the carbon for the application. Isotherm data represent a large amount
of information condensed into concise form for ready evaluation and inter-
pretation.
The data of Hager and Rizzo (1974) were obtained using granular carbon
and toxaphene in distilled water. These studies were performed at toxaphene
concentrations between about 11 and 175 ppm.
THE FEASIBILITY OF ALTERNATE SYSTEMS FOR REMOVING TOXAPHENE FROM WASTEWATER
Considerable information is available concerning the treatment of
endrin wastewaters by means of reductive degradation and by adsorption on
carbon and on Amberlite resin. However, very little information is available
concerning the application of these processes to toxaphene. A careful con-
sideration of (a) the available experimental data, (b) the similar chemical
and physical properties of the two products, and (c) an evaluation of the
opinions of researchers knowledgeable of the processes, leads to the con-
clusion that these processes should have practical application to toxaphene
as well as endrin. These topics are discussed below.
48
-------
A Comparison of the Chemical and Physical Properties of Endrln and
Toxaphene
An examination of the chemical and physical properties of endrin and
toxaphene (Table 4) reveals that they are similar in regard to properties
that are important to the phenomenon of adsorption, such as affinity for
water, polarity, and solubility. The chemical natures of the two pesti-
cides are also similar; both are highly-chlorinated products containing
over 56% chlorine by weight. It could be predicted that these products
would behave similarly in many chemical reactions, such as oxidation or
reduction, and in fact both products have been shown to be resistant to
oxidation and susceptible to the reductive degradation reaction.
The resistance of endrin to oxidation is indicated by the experiments
of Robeck et al. (1965) which show that highly chlorinated hydrocarbons
such as endrin, lindane, and dieldrin, are not further oxidized by chlorine.
Robeck et al. (1965) state that "It was not anticipated that chlorination
would have much effect on the chlorinated hydrocarbons." Further experi-
mental work is cited by Marks (1974a) which shows that the chemical oxida-
tion of endrin in water by the oxidant potassium permanganate is "ineffective."
The resistance of toxaphene to oxidation is exemplified by the work
of Cohen et al. (1960), which showed, that, as expected, toxaphene in water
was not affected by chlorine.
The susceptibility of both endrin and toxaphene to reductive degra-
dation is discussed below.
49
-------
Table 4. CHEMICAL AND PHYSICAL PROPERTIES
OF ENDRIN AND TOXAPHENE^
Chemical Class
Description
Empirical formula
Molecular weight
Chlorine content
Carbon content
Hydrogen content
Melting point
Affinity for water
Polarity
Flammability
Solubility
Water
Petroleum oils
Acetone
Benzene
Endrin
Chlorinated hydrocarbon
Crystalline solid
C12H8C16°
381
567.
387.
27.
> 200°C
(with decomposition)
Hydrophobic
Nonpolar
Nonflammable
Very slightly soluble
(0.23 ppm at 25°C)£-/
Slightly soluble
Solub le
Soluble
Toxaphene
Chlorinated hydrocarbon
Waxy solid
~ r H r\y
L10H10 8
67-697.
28-317.
~ 2.5%
~ 84° C
Hydrophobic
Nonpolar
Nonflammable
Very slightly soluble
(0.4-3.0 ppm)£/
Soluble
Soluble
Soluble
a/ The information presented in this table was obtained from multiple
sources which are in general agreement.
b/ Toxaphene has the approximate composition c10HioCl8* Tt consists of
a mixture of 20 to 30 major compounds resulting from the chlorination
of camphene, but is predominantly a mixture of the octachlorocamphene
isomers.
c/ Gunther, F. A., "Reported Solubilities of 738 Pesticide Chemicals in
Water," Residue Reviews, 20j 1-145 (1968).
50
-------
Reductive Degradation
Considerable development work has been performed on the reductive
degradation process applied to wastewaters containing endrin (Sweeny et al.,
December 1973; Sweeny, May 1974; Sweeny, September 1974). Relatively little
work has been done concerning the application of this process to toxaphene.
However, the Envirogenics Company has demonstrated in the laboratory that
the reductive degradation system using copper-catalyzed iron can reduce the
concentration of toxaphene to less than 3 ppb from a concentration of 1,000
ppb (Sweeny et al., December 1973). Also, Sweeny in a patent owned by the
U.S. government (Sweeny, June 1973) describes a series of tests using the
process for the reduction of toxaphene, chlordane, dieldrin, aldrin, hepta-
chlor, and polychlorinated polyphenyls. Substantial conversion of these
compounds (which are all highly-chlorinated organics) was confirmed by gas
chromatography and by chloride ion determinations.
Dr. Robert Swank, Acting Chief, Industrial Pollution Branch, Environ-
mental Protection Agency, Athens, Georgia, is project monitor for the cur-
rent project study (EPA Contract No. 68-01-0083) involving the reductive
degradation of endrin and other highly-chlorinated hydrocarbons. Dr. Swank
is convinced that the reductive degradation system would be practical for
toxaphene as well as for other chlorinated pesticides t(Swank, 1975).
Dr. K. H. Sweeny is program manager for a current study of the appli-
cation of the reductive degradation system for the removal of chlorinated
hydrocarbon pesticides from wastewater (EPA Contract No. 68-01-0083,
51
-------
Envirogenics Systems Company). Dr. Sweeny believes that the reductive
degradation process is very promising for the removal of toxaphene from
wastewater (Sweeny, 1975).
Adsorption of Toxaphene on Carbon and on Amberlite Resin
In the candidate systems for resin adsorption and carbon adsorption
dilute aqueous solutions of endrin and toxaphene, 300 and 500 ppb, respec-
tively, are contacted with the adsorbent. The phenomenon responsible for
the removal of the contaminant from water involves physical adsorption of
the contaminant on the surface of the adsorbent. There is strong evidence
that carbon will effectively adsorb both of these products. Figure 8 pre-
sents the data obtained by the Calgon Corporation (Hager and Rizzo, 1974).
This figure shows that carbon is effective in removing both contaminants
from water at concentrations of about 20 ppb; the weight pickups are ap-
proximately 27. for toxaphene, 37. for endrin. The concentration of endrin
can be reduced to about 0.2 ppb. A linear extrapolation of the toxaphene
isotherm indicates that the weight percent pickup by carbon would be even
greater for toxaphene than for endrin at concentrations below about 5 ppb.
The extrapolation of the toxaphene isotherm to lower concentrations is
reasonable because, according to the Process Design Manual for Carbon Ad-
sorption published by EPA (Cornell, 1973), "In very dilute solutions, such
as wastewater, a logarithmic isotherm plotting usually yields a straight
line."
52
-------
Ul
10.0i=-
y
a.
i—
o
uu
0.1
0.01
,1
I I I I 1111 I I I I 11
in
0.1 1.0 10.0 100.0 1000.0
CONTAMINANT CONCENTRATION (Parts Per Billion)
Source: Hager and Rizzo (1974).
Figure 8. Simplified adsorption summary - toxaphene
-------
For several years the Rohm and Haas Company has been investigating
the adsorptive properties of its proprietary resin, Amberlite XAD-4, for
the removal of contaminants from water. The properties of the resin have
been described by Rohm and Haas (Rohm and Haas, 1971). The resin has been
shown to be very effective compared to carbon for the removal of "chlori-
nated pesticides from actual manufacturing waste effluents" (Kennedy, 1973).
In our recent contacts with Rohm and Haas Company, personnel restated
the usefulness of the resin for wastewater treatment. Rohm and Haas states
that it has evaluated this resin compared to carbon, and that in all tests
to date the resin has been superior to carbon in reducing the contaminant
concentration (Huritz, 1975). Although Rohm and Haas has not tested its
resin on endrin or toxaphene,.it has performed confidential studies for
various industrial clients; for one "chlorinated pesticide," the wastewater
concentration was reduced from 300 to 500 ppb to 1 to 3 ppb (Borenstein,
1975).
Thus, the available evidence indicates that the Amberlite XAD-4 resin
would be feasible for use in a practical system for the removal of toxaphene
from water.
FLOW DIAGRAMS OF ALTERNATE SYSTEMS FOR REMOVING TOXAPHENE FROM WASTEWATER
Although the alternate treatment systems have been operated on only a
laboratory scale, not on a pilot scale, it is possible for the purpose of
cost estimation to prepare flow diagrams showing the approximate design of
the systems. Also, as pointed out earlier in this section of the report,
54
-------
the alternate systems would be expected to be approximately as effective
in treating toxaphene wastewater as they are in treating endrin wastewater.
On this basis, an estimate of effluent quality can be made. Discussed be-
low are (a) flow diagrams of alternate systems for the treatment of toxaphene
wastewater and (b) the expected quality of the effluent produced when the
alternate systems are used to treat the toxaphene wastewater. The systems
are applied to wastes generated at the Hercules, Inc., plant at Brunswick,
Georgia, since the other manufacturers produce substantially smaller waste
streams.
The Amberlite XAD-4 Resin and Reductive Degradation Systems
The Amberlite XAD-4 resin system and reductive degradation system are
being studied for treatment of chlorinated pesticide wastes by Velsicol
Chemical Corporation and Envirogenics Systems Company, respectively. En-
virogenics has tested the capability of the reductive degradation system
to remove toxaphene from wastewater. No information is available on treat-
ment of toxaphene wastes with the resin system. A general description of
these systems was presented earlier in this section.
Design flow diagrams of these alternate treatment systems are presented
in Figures 9 through 12. In each system, the plant process wastewater con-
taining toxaphene is passed through a sedimentation process and a filtra-
tion process (a) to remove the suspended solids that would otherwise pass
through the XAD-4 resin system or overburden the reductive degradation sys-
tem, and (b) to allow destruction of the free chlorine by sunlight (requir-
ing 8 hr of exposure). The figures show the quality of the treated effluent
discharged and the sludge disposal operations.
55
-------
Untreated Toxaphene
Wastewater (200 gpm)
Toxaphene Concentration: 2200 ppb
PH:4.2
Neutralization
— » & Sedimentation — *
Process
1 |
1
Incinerate
or Landfill
Filtration
Process
XA
Pro
i J
Filter
Backwash
^
1
Effluent C
( 1 .4 ppb
pH: 7
D-4
in
cess
\] Monitoring Point
)ischarge
Toxaphene
200 gpm )
Figure 9. Design flow diagram of Amberlite XAD-4 resin system
-------
Untreated Toxaphene
Wastewater (200 gpm)
Toxaphene Concentration: 2200 ppb
pH:4.2
Sedimentation
Process
Filtration
Process
Sludge -•*
Reductive
Degradation
Process
Monitoring Point
Landfill or
Incinerate
Effluent Discharge
(<3 ppb Toxaphene
pH 7
200 gpm)
Figure 10. Design flow diagram of reductive degradation system
-------
Ul
CO
Untreated Toxaphene
Wastewater ( 200 gpm )
Toxaphene Concentration: 2200 ppb
pH:4.2
Sedimentation
Process
Reductive
Degradation
Process
Monitoring
Point
Effluent Discharge
(0.1 ppb Toxaphene
pH 7 200 gpm)
Incinerate
or Landfill
Figure 11. Design flow diagram of Amberlite XAD-4 resin system and reductive
degradation system in series
-------
-~500 ppb
Toxaphene I
VO
Untreated Toxaphene
Wastewater (300 gpm)
Toxaphene Concentration: 2200 ppb
PH: 4.2
Neutralization
& Sedimentation
Process
Sludge
1
1
Spent Carbon
to Incineration
Monitoring
Point
Incinerate
or Landfill
Effluent Discharge
<5 ppb Toxaphene
pH: 7 gpm: 300
Figure 12. Design flow diagram for a carbon adsorption system
-------
Figure 9 shows the design flow diagram of Amberlite XAD-4 resin ad-
sorbent system. In the XAD-4 system, the wastewater is passed through
vertical columns packed with resin that adsorbs the toxaphene. The resin
is periodically regenerated by flushing the resin beds with isopropyl al-
cohol to remove accumulated toxaphene. The treated wastewater passes
through a monitoring point and is then discharged.
Figure 10 shows the design flow diagram of the reductive degradation
system. The reductive degradation process operates by first neutralizing
»
(to pH 7) the acid wastewater with sodium carbonate in a pH adjustment
tank. After neutralization, the wastewater passes through parallel reduc-
tant columns that are packed with copper-catalyzed iron and sand. The
toxaphene is destroyed by reductive degradation in the columns. Subse-
quently, the treated wastewater is monitored and discharged..
Figure 11 shows the two systems in series. The wastewater is pro-
cessed through the XAD-4 resin system, the reductive degradation system,
and then discharged.
The process equipment involved in each system is given in greater
detail in the cost estimates discussed subsequently.
The Quality of the Treated Effluent
The quality of the toxaphene wastewater after treatment by the reduc-
tive degradation system has been determined in laboratory studies conducted
by Envirogehics. However, the tests conducted by Velsicol (Marks, March
1974) using the XAD-4 resin system involved only endrin wastewater. The
60
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transfer of endrin treatment technology to treatment of toxaphene waste-
water appears to be feasible as discussed earlier in this report. Based
upon the information to date, the probable quality of the treated effluent
from each of the three systems is as follows.
Amberlite XAD-4 Resin System - Velsicol has demonstrated in the laboratory
that the XAD-4 resin adsorbent system can reduce the concentration of endrin
in wastewater down to an average of 1.36 ppb (Marks, March 1974). For rea-
sons described earlier in this report, we believe that the resin system
would be approximately as effective for toxaphene as it is for endrin.
The Reductive Degradation System - Envirogenics Systems Company has demon-
strated in the laboratory that the reductive degradation system using copper-
catalyzed iron can reduce the concentration of toxaphene down to less than
3 ppb from a concentration of 1,000 ppb (Sweeny et al., July 1973).
Amberlite XAD-4 Resin System and Reductive Degradation System in Series -
This system treats the toxaphene wastewater with the XAD-4 resin system
first, and reduces the toxaphene concentration down to about 1.4 ppb prior
to treatment by the reductive degradation system. The reductive degrada-
tion system has not been tested for treating this low concentration of
toxaphene, but it is reasonable to assume a ten-fold decrease in toxaphene
levels in this case (since the higher concentration of 1,000 ppb was reduced
over 300-fold). Therefore, the amount of toxaphene in the effluent of these
two systems acting in series is estimated to be about 0.1 ppb.
61
-------
Carbon Adsorption System
A conceptual flow diagram for a carbon adsorption process (Hutchins,
1975a) is shown in Figure 12. The portions of this process which deal
with removal of suspended solids and pH adjustment in the wastewater are
taken to be identical to the process steps of sedimentation, filtration
and neutralization, which are used in the reductive degradation system.
After removal of suspended solids from the wastewater, it is con-
ducted through a two-stage carbon adsorption system consisting essentially
of (a) two on-streatn carbon adsorption units operating in series and one
standby adsorption unit packed with granular activated carbon, and (b) the
required auxiliary equipment (pump, piping, process instrumentation, etc.).
When the concentration of toxaphene in the effluent from the first
unit is equivalent to the feed concentration, the carbon in the unit is
exhausted and the unit is taken off stream (Hutchins, 1975a). The second
unit then becomes the lead unit and the standby column is put on stream
as the second column in the series. The exhausted unit is discharged,
refilled with fresh carbon, and used as standby. Because of the small
requirement for activated carbon, regeneration of the carbon is not eco-
nomically justified (Hutchins, 1975b). The exhausted carbon is disposed
of by incineration; the costs for incineration are not included in this
study.
62
-------
Robeck (1965) has reported test data (Table 5) for carbon adsorption
of endrin from wastewater; the influent contained 10 ppb endrin and the
endrin removal was over 99%. Similar results were reported for wastewaters
containing other chlorinated hydrocarbon pesticides. In this study, it was
considered that a similar adsorption efficiency would apply for toxaphene
vastewater; on this basis the estimated endrin content in the treated ef-
fluent would be less than 5 ppb.
63
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Table 5. SUMMARY OF CUMULATIVE PESTICIDE REMOVAL AT 10-PPB LOAD
Pesticide removed (%)
Process
Chlorination (5 ppm)
Coagulation and
Filtration
Carbon: Slurry
5 ppm
10 ppm
20 ppm
Carbon: Bed
0.5 gpm/cu ft
DDT Lindane
< 10 < 10
98 < 10
30
55
80
> 99 > 99
Parathion
75
80
> 99
> 99
> 99
> 99
Dieldrin
< 10
55
75
85
92
> 99
2,4,5-T Ester
< 10
65
80
90
95
> 99
Endrin
< 10
35
80
90
94
> 99
Source: Robeck, 1965 (p. 198).
-------
POSSIBILITIES FOR ZERO DISCHARGE IN TOXAPHENE MANUFACTURE
There is no apparent potential for zero discharge of effluent for the
Hercules, Inc., toxaphene wastewater treatment process currently used at
the Brunswick, Georgia, plant. Major equipment changes and modifications
in the existing treatment facility would be .required to even approach a
65
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condition of zero discharge at this site. The presently used treatment
process does not appear to be amenable to operation with zero discharge.
At present the discharge of wastewater is estimated to be about 3.5 gal/lb
of toxaphene product.
According to data obtained during site visits to Tenneco, Inc., at
Fords, New Jersey, to Vicksburg Chemical Company, Vicksburg, Mississippi,
and to Riverside Chemical, at Groves, Texas, the other three domestic toxa-
phene plants are in a much more favorable position than Hercules for either
closely approaching or achieving a no discharge type of operation. (See
references: Meiners and Mumma, 1975a; Meiners and Mumma, 1975b; and Meiners
and Mumma, 1975c.) According to data furnished by the producing companies,
the Tenneco, Inc., plant and the Vicksburg Chemical Company plant presently
have no discharge of process wastewater; both of these plants do have a
discharge of caustic waste liquid from off-gas scrubbing operations, i.e.,
about 100 gpd spent caustic liquid for Tenneco and 14,400 gpd of spent
caustic at Vicksburg plant. The Riverside plant currently discharges about
12,000 gpd of toxaphene contaminated wastewaters containing an average of
about 0.04 Ib of toxaphene (i.e., an average concentration of about 0.4 ppm
toxaphene in discharge wastewater).
A plant official at the Riverside Chemical Company has stated (Meiners,
August 1975) that "for practical purposes no discharge can be achieved by
toxaphene plants." However, this official believes that in ordinary plant
operations some water discharge will inevitably be required and that the
66
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no discharge achievement would mean that practically all of the by-product
hydrochloric acid from the toxaphene process would be sold as product.
COMPARISON OF EFFLUENTS PRODUCED BY ALTERNATE TREATMENT SYSTEMS WITH
EFFLUENT LIMITATIONS GUIDELINES
The Environmental Protection Agency in their "general instructions"
to contractors (Part II) describes effluent limitations guidelines in terms
of Levels I, II, and III technology. These levels of technology are briefly
defined below and replace the terms "best practicable control technology cur-
rently available" (BPCTCA), "best available technology economically achiev-
able" (BATEA) and "best available demonstrated control technology" (BADCT).
Level I - Control and Treatment Technology
This level must be achieved by all plants in each industry not later
than July 1, 1977. "Level I technology should be based upon the average
of the best existing performance by plants of various sizes, ages and unit
processes within each industrial category or subcategory. This average
shall not be based upon a broad range of plants within an industrial
category or subcategory, but shall be based upon performance levels
achieved by exemplary plants."
Level II - Control and Treatment Technology
This level is to be achieved not later than July 1, 1983. "Level II
technology is not based upon an average of the best performance within an
industrial category, but is to be determined by identifying the very best
67
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control and treatment technology employed by a specific point source within
the industrial category or subcategory, or where it is readily transferable
from one industry process to another, such technology may be identified as
Level II technology."
Level III - Control and Treatment Technology
This level is to be achieved by new sources. "Level III technology
shall be evaluated by adding to the consideration underlying the identifi-
cation of Level II technology a determination of what higher levels of pol-
lution control are available through the use of improved production processes
and/or treatment techniques."
The effluent limitations tentatively recommended for the "Halogenated
Organic Pesticides" subcategory of the "Pesticides and Agricultural Chemi-
cals Industry" category are presented in Table 6.
Except for one plant, the Hercules plant (Brunswick, Georgia), the
effluent limitations guidelines cannot' be compared with the quality of
effluents from toxaphene production units. In general, no data concern-
ing BOD, suspended solids, or phenol concentration are available for the
effluent from the toxaphene processes. Although data of this kind are
reported for the total plant effluent, the total effluent consists of
discharges from a number of other processes.
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SECTION IV
WASTEWATER TREATMENT COST ESTIMATES
In this portion of the report, capital investment costs and annual
operating costs are estimated (a) for presently used toxaphene wastewater
treatment systems and (b) for alternate wastewater treatment systems.
ESTIMATED COST OF PRESENTLY USED WASTEWATER TREATMENT SYSTEMS
Presented below are estimates of the capital investment costs and
operating costs for wastewater treatment systems currently in operation
at the four toxaphene production plants in the United States.
The Hercules Plant (Brunswick, Georgia)
A description of the wastewater treatment system used at the Hercules
plant has been presented in Section III. Lair and Bruner (1975) have re-
ported that the treatment facilities were built by Hercules during the
period 1971 to 1974. The design flow capacity of this treatment system
is reported to be 300 gpm, and the design toxaphene content in treated
effluent is 1 Ib/day (Hicks, 1975).
The capital cost of the toxaphene wastewater treatment system is re-
ported by Hicks (1975) to be about $800,000. The annual operating cost of
the treatment facility in 1974 was reported to be about $300,000, including
70
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monitoring costs and technical services (Hicks, 1975). These costs do not
include a solid waste disposal procedure.
The Tenneco, Riverside, and Vicksburg Plants
None of these three plants operate a toxaphene wastewater treatment
system. Therefore, no treatment cost data are available for these plants.
A detailed description of the waste disposal systems used by these plants
is presented in Section II.
ESTIMATED COST OF ALTERNATE TOXAPHENE WASTEWATER TREATMENT SYSTEMS
Investment and operating cost estimates have been prepared for four
potential alternate systems. The costs have been estimated based upon the
application of the treatment systems to the toxaphene wastewater generated
at the Hercules plant (Brunswick, Georgia). Costs have been estimated for
the following systems: (a) adsorption on synthetic resins, (b) reductive
degradation, (c) adsorption on synthetic resins followed by reductive
degradation, and (d) adsorption on granular activated carbon.
One alternative, in addition to those above, would be to reduce the
wastewater flow rate and quantity. However, no information is available
concerning the cost of achieving a reduced wastewater flow; therefore, no
cost estimate is made for this alternative.
Cost estimates have been made for two flow rates, 200 gpm and 300 gpm.
According to Hicks (1975), the present treatment system has a design flow
capacity of 300 gpin and the average influent flow rate is about 200 gpm.
A discussion of the methodology and the results of the cost estimates
is presented below.
71
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Estimated Capital Investment Costs for the Resin Adsorption System and th
Reductive Degradation System
e
Information concerning the alternate treatment systems and their asso-
ciated costs is derived in part from information submitted by Velsicol
Chemical Corporation (Marks, September 1974) and in part from reports by
Envirogenics Systems Company (Sweeny, May 1974 and September 1974) con-
cerning the pilot plant demonstration units. Where the costs of required
process equipment or labor were not stated by the two above companies,
these costs are estimated. In addition, the treatment systems are scaled
up from the proposed demonstration units (100 gpm flow) to 200 and 300 gpm,
and the costs are given in April 1975 dollars.
Since all of the alternate systems require both a sedimentation and
filtration process, and the costs of these two processes are identical for
each system, these processes are examined first. Following the treatment
and filtration processes, each of the alternate systems are discussed sep-
arately. The cost estimates for the system are then summarized and totaled.
Sedimentation Process Costs - The sedimentation process will allow large
solid undissolved particles to settle out of the wastewater prior to fil-
tration. The installed capital cost for a system to handle 200 gpm
(288,000 gpd) and 300 gpm (432,000 gpd) is estimated from a report by
Sleeker and Nichols (1973). The graph on page 126 of their report shows
that the installed cost (1972 dollars) of a sedimentation system to handle
1 million gallons per day is $65,000. The installed costs for the systems
to handle 200 and 300 gpm flows are extrapolated from the graph and are
72
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$20,000 and $25,000, respectively. These installed systems for the sedi-
mentation process include the purchased cost of tanks, motors and drives,
pumps, piping, concrete, structural steel, instrumentation, electrical,
paint, and indirect costs.
'Since these installed costs are given in 1972 dollars, the costs must
be escalated to April 1975 prices. To do this, the Chemical Engineering
(CE) Plant Cost Index is used. Chemical Engineering (1975a) reports that
in 1972, this index was 137.2 but had risen to 180.6 by April 1975. There-
fore, the estimated installed capital cost (rounded) of each sedimentation
process system is:
t ^ f^ f\ f \
300
200 gpm process: ($20,000) fl80-6) = $26,
\137.2/
300 gpm process: ($25,000) f180-6j = $32,900
\137.2 /
Blecker and Nichols (1973) reported that the annual maintenance cost
for each process is about 15% of the installed cost or $3,900 and $4,900,
respectively. This report also states-that the process requires no opera-
tor attention. However, operating labor is estimated at 3 hr/day for rou-
tine checks on the process to see that it functions properly.
Periodically, the sludge must be removed and landfilled or incinerated,
The cost of sludge removal is included in the maintenance cost. The cost
of land for landfill or the cost of incineration process is excluded in
this estimate.
Blecker and Nichols (1973) report that the expected life of these
systems is between 25 and 60 years, and the life is taken to be 40 years
for the purpose of depreciation of the installed costs. (See Appendix B.)
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Filtration Process Costs - The wastewater is pumped from the sedimentation
process (at the same rate as the inflow) into a sand filter to further
remove suspended solids. The flow rate through a sand filter can'vary
depending upon the design, but a typical flow rate according to Envirogenics
Systems Company (1973) is about 3.2 gal/sq ft/min. Thus, the required fil-
ter area for the 200 and 300 gpm flows is about 70 and 100 sq ft, respec-
tively. A back-up filter is required for each process since the plant
operates 24 hr/day.
The installed cost for the filtration process is obtained from the
report by Blecker and Nichols (1973). The graph on page 66 of this report
shows that the installed cost of a 70 sq ft filter is $50,000 and a 100
sq ft filter is $60,000. Since these costs are in 1972 dollars, the April
1975 costs (rounded) are:
200 gpm filtration process: (2)($50,000) [!§0.6\ = $131,600
\ i J / • ^ I
300 gpm filtration process: (2)($60,000) /!§0.j6\ = $158,000
\ JL J / • £~ ]
Blecker and Nichols (1973) reported that the annual maintenance cost
for each process is about 5% of the installed cost or $6,600 and $7,900,
respectively. This report states that the filtration process requires no
operator attention. Hox^ever, operating labor is estimated at 3 hr/day for
routine checks on the process to see that it functions properly.
Periodically, the filters are backwashed into a sump to remove the
filtered solids. Removal of the sludge from the pit is included in the
maintenance costs given above. The cost of land for landfill or the cost
of incineration of the sludge is excluded in this estimate.
74
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Blacker and Nichols (1973) reported that the expected life of the
filtration process is between 10 and 20 years and is taken to be 15 years
for the purpose of depreciation of the installed costs (see Appendix B).
Resin Adsorption System Costs - Velsicol Chemical Corporation designed a
system and estimated the costs for an Amberlite XAD-4 resin process to
treat 100 gpm of wastewater. A system is described and the costs are esti-
mated in their R&D grant application submitted to EPA to conduct a project
entitled, "Chlorinated Hydrocarbon Pesticide Removal from Wastewater," In
another document written by Marks (September 1974), the installed capital
equipment costs (1973 dollars) were estimated by Velsicol to be $60,000
(excluding the filtration process) for purchased parts and $27,000 for in-
stallation of the process, or a total of $87,600. These costs were item-
ized by Velsicol as follows:
Purchased Farts
2 Resin columns with headers
2 Solvent tanks
3 Transfer pumps
Instrumentation
Valves and piping
Contingency on purchased parts
$16,000
22,000
6,000
4,000
4,800
7,200
$60,000
$60,000
75
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Subcontracts
Mechanical and electrical construction $22,000
Slab and related civil works 5,600
$27,600 27,600
Total cost $87,600
Chemical Engineering (1975a) shows that the 1973 CE plant cost index
was 144.1 so that the April 1975 estimated cost of the XAD-4 resin process
is:
($87,600) f.I§2ii) . $no,000
\144.1/
This cost is for a 100 gpm flow rate and must be scaled up to 200 and
300 gpm, respectively. Since this process involves tanks, pumps, piping,
and resin columns, the best available method to scale. up this plant is the
logarithmic relationship known as the "six-tenths factor" (see Appendix B) .
Using this method, the installed cost for the XAD-4 resin process is:
(200\°*6
— 1 = $167,000
300 gpm process: ($110,000) | 300] " = $212,700
These costs do not include the cost of neutralizing the treated waste-
water. Since the current practice at Hercules is to neutralize the toxaphene
wastewater with limestone prior to treatment, the only cost added by the
XAD-4 resin system would be the cost of the limestone since the neutraliza-
tion process facility already exists.
76
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The cost of the limestone is negligible in this treatment system
compared to the cost of the resin and isopropyl alcohol (discussed sub-
sequently) since the amount of limestone required to neutralize the waste-
water is less than the amount of sodium carbonate required in the reductive
degradation system (Cywin, 1973), which amounts to 44,100 Ib/year for a
100 gpm plant. The cost of limestone is only about one-tenth the cost of
sodium carbonate, or about $10/ton (Cywin, 1973). On an annual basis, this
amounts to a cost of $220 to neutralize the wastewater of a 100 gpm plant.
For the 200 gpm and 300 gpm plants the annual costs would be $440 and $660,
respectively, which are negligible in this case.
The material costs are essentially the Amberlite XAD-4 resin and the
isopropyl alcohol used to regenerate the contaminated resin columns.
Velsicol (Vitalis, 1975) estimates that the cost of the resin to charge
the resin columns for the 100 gpm system is $63,000 (current prices) and
that the resin has an operating lifetime of 5 years. Rohm and Haas Company
(Kennedy, 1973) estimates that the cost of the regeneration isopropyl al-
cohol makeup is $30,000 per year (1972 prices) for a 100 gpm process. The
average 1972 price of isopropyl alcohol was about $0.45/gal (Oil, Paint and
Drug, 1972) and the current price is $0.70/dal (Chemical Marketing Reporter,
1975), so that the isopropyl alcohol cost in April 1975 prices is (0.70/0.45)
($30,000) or $46,700/year for a 100 gpm plant.
Using a linear relationship to scale up the resin and isopropyl alcohol
required for the two process flow rates gives:
77
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Resin;
200 gpm process: $63,000 ( 20° ) = $126,000
V100/
300 gpm process: $63,000 ( 30° ] = $189,000
V100/
Isopropyl alcohol:
200 gpm process: ($46,700/year) f £00 ) = $93j4QO/year
100
300 gpm process: ($46,700/year -. = $140,100/year
V100/
Blecker and Nichols (1973) reported that the annual maintenance cost
for each process is about 5% of the installed equipment cost, or $8,400
and $10,600, respectively.
The operating labor time is estimated at 9 man -hours /day on a 24 hr/
day operating basis for the 100 gpm system based upon the estimates given
for ion exchangers (Blecker and Nichols, 1973). This gives a requirement
of 3,150 man-hours annually (based on 350 operating days /year). To scale
this labor time up to the 200 and 300 gpm process flow rates, the "one-
fourth factor" is used (Popper, 1970). This method (see Appendix B) gives
the estimated operating labor time for each process as follows:
200 gpm process operating labor: (3,150 hr) flP-P-1 ' = 3,750 hr
300 gpm process operating labor: (3,150 hr) f3-0^! ' = 4,150 hr
Rohm and Haas (Kennedy, 1973) estimates that the expected life of the
XAD-4 resin process equipment is 10 years and that the life of XAD-4 resin
78
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charge is 5 years for the purpose of depreciation of the installed costs
of the capital equipment and resin.
Reductive Degradation System Costs - Envirogenics Systems Company (Sweeny
et al., December 1973) designed a pilot plant demonstration system and es-
timated the cost of a reductive degradation process to remove the endrin
from wastewater flowing at 100 gpm. The system is fully described in the
Envirogenics Report (Sweeny, December 1973) and the associated costs (1973
dollars) are given in detail.
In this document the installed capital equipment costs were estimated
by Environgenics Systems Company (Sweeny, December 1973) to be $58,900.
These costs were itemized as follows:
Purchased Parts
2 Reagent mix tanks, 200 gal. with mixers,
low-level alarm and proportional feed pump $3,000
1 Transfer pump with low-level alarm 1,000
1 pH adjustment tank, approximately 2,000 gal. 2,000
1 Mixer and impeller, 2 h.p. 3,000
1 Low and high level alarm for above 500
1 5 h.p. feed pump 700
1 pH sensing and control unit 2,000
5 Rotameters 900
Valves and piping 1,810
5 Reactor columns with distributors 10,000
79
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Reagents 190
Total 25,100
Contingency on purchased parts 5,000
30,100
Subcontracts
Mechanical and electrical construction 20,000
Slab and related civil works 4,000
Total 24,000
Contingency on subcontracts 4,800
28.800
Total $58,900
The 1973 Chemical Engineering Plant Cost Index was 144.1 (Chemical
Engineering , 1975a) so that the April 1975 cost of the reductive degrada-
tion process is:
($58,900) ( i = $73,800
\144.1/
This cost is for a 100 gpm process and must be scaled up to 200 and
300 gpm, respectively. Since the process involves tanks, pumps, reactor
columns, and miscellaneous equipment, the best available method for scale-
up is the logarithmic relationship known as the "six-tenths factor," previ-
ously described (see Appendix B) . Using this method, the installed cost for
the reductive degradation process is:
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200 gpm process: $73,800 ^T'" . $111,900
300 gpm process: $73,800 ( 300 \°'6 = $142,700
\100/
The material costs for the system are the replacement of the iron
reductant, the copper catalyst, and the sodium carbonate consumed in the
process operation. Envirogenics Systems Company (Sweeny, December 1973)
determined that the losses of iron reductant for processing existing endrin
wastewater were 5.0 mg/liter of effluent, and losses of copper catalyst
were 0.1 mg/liter of effluent. The amount of sodium carbonate required to
adjust the pH of the wastewater to 7.0 was determined to be 126 Ib/day for
the 100 gpm plant. Sodium carbonate was used by Envirogenics and is used
in this estimate, though its cost is higher than, say, lime. Since it is
not known whether or not lime can be used as a neutralizing agent in this
process, the savings realized from using the cheaper lime cannot be deter-
mined. The difference in price of the. two neutralizing agents would not
greatly affect the overall process cost.
The annual material usage for the 100 gpm process, then, is as follows:
Iron /5.0 mg Fe\ flOO galA /3.85 liter\ /1. 440 min\ /2.2 x IP"6 lb\ /350
reductant: liter ) min ) gal. ) day ]\ mg )\ y
year
= 2,130 Ib/year
Copper /O.I mg Cu\ flOO gal.\ /3.85 liter\ f 1,440 min\ /2.2 x IP"6 lb\ /350
catalyst:^ liter / \ min ]\ gal. / V day / \ mg J\ year
= 45 Ib/year
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Sodium
carbonate
/126 lb\/350 days\ ,, ... ...
Z—\ = 44,100 Ib/year
: \ day /\ year /
The costs of replacing the iron reductant and copper catalyst are
negligible since iron powder costs $0.20/lb and copper sulfate costs $0.70/
Ib (Chemical Marketing Reporter, 1975), and the quantities are quite small.
The sodium carbonate cost, however, is substantial since its current price
is about $100/ton (Chemical Marketing Reporter, 1975) and a large quantity
is required. The sodium carbonate needed for the 200 gpm and 300 gpm pro-
cesses is proportional to the flow rate so that the annual cost of sodium
carbonate for the two plants is:
200 gpm plant: (^lOOJbW^/^05\ . $4,400/year
' \ year \IOOJ\ Ib /
300 gpm plant: [44,100 IbW300W^O.05] = $6,600/year
^ year /\l°0/\ lb /
Blecker and Nichols (1973) reported that the annual maintenance costs
are 5% of the installed capital equipment costs, or $5,600 and $7,100 for
the 200 gpm and 300 gpm processes, respectively.
The operating labor time is estimated at 9 man-hours/day on a 24 hr/
day operating basis. This gives a requirement of 3,150 man-hours annually
(based on 350 operating days/year). Scaling this labor time up to the 200
and 300 gpm processes is accomplished with the "one-fourth"factor," previ-
ously mentioned, and the annual operating labor time for each process
becomes:
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200 gpm process operating labor: (3,150 hr) (IP-P.] ' = 3.750 hr
\100/
300 gpm process operating labor: (3,150 hr) [IP-0-] * = 4,150 hr
\100/
The expected life of the reductive degradation process equipment is
taken to be 10 years for the purpose of depreciation of the installed equip-
ment costs (see Appendix B).
Costs for the Resin Adsorption System and Reductive Degradation System in
Series - The cost of a system which puts the XAD-4 resin system and reduc-
tive degradation system in series is the same as the sum of the costs for
each separate system with only one exception: Only one sedimentation and
one filtration process is necessary for the two systems in series, that is,
each system does not have a separate sedimentation and filtration process.
Therefore, the cost of the two systems in series is the sum of the cost of
the two separate systems less the cost of one sedimentation process and one
filtration process.
The fact that the toxaphene content of the wastewater treated by the
reductive degradation system is lower, since the wastewater has already been
treated by the XAD-4 resin system, does not reduce the cost of the reductive
degradation system in series to any extent for two reasons: (a) The amount
of wastewater treated is the same for the reductive degradation system
whether alone or in series with the XAD-4 resin system, and the reductive
degradation system must be of approximately the same size in both cases;
and (b) the loss of iron reductant and copper catalyst will be lower for
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the reductive degradation system in series but the cost of operating the
system in series is unaffected since the cost of replacing these materials
is negligible.
Total Capital Investment Costs for the Resin Adsorption System and the
Reductive Degradation System - The cost of purchasing and installing the
capital equipment for each system has been presented in the previous dis-
cussions. In addition to the previous cost estimates a contingency of 30%
is added to these costs to allow for unanticipated expenses. Table 7 sum-
marizes and totals the capital investment for the three systems.
Annual Operating Costs for the Resin Adsorption System and the Reductive
Degradation System
The total annual costs to operate each system at both the 200 and 300
gpm flow rates are estimated below. Most of these costs are a percentage
of either the installed capital equipment cost or the labor costs previously
described. The following list shows all of the cost items considered in
this estimate.
Direct costs Indirect costs
Depreciation
Materials Property taxes
Labor Insurance
Supervision Capital cost
Payroll charges Plant overhead
Maintenance
Operating supplies
Utilities
Laboratory services
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Table 7. INSTALLED CAPITAL EQUIPMENT COST FOR THE XAD-4 RESIN SYSTEM, THE REDUCTIVE DEGRADATION
SYSTEM, AND THE XAD-4 RESIN SYSTEM AND REDUCTIVE DEGRADATION SYSTEM IN SERIES
Sedimentation
Filtration
XAD-4 resin process
Equipment
Resin
Reductive degradation
system
Subtotal
Contingency, 30%
XAD-4 resin system
200 gpm 300 gpm
26,300 32,900
131,600 158,000
167,000 212,700
126,000 189,000
450,900
135.300
592,600
177.800
Reductive degradation
system
200 gpm 300 gpm
26,300 32,900
131,600 158,000
Two systems
in series
Total (1975 $) 586,200 770,400
111.900 142,700
269,800 333,600
80.900 100.100
350,700 433,700
200 gpm 300 gpm
26,300 32,900
131,600 158,000
167,000 212,700
126,000 189,000
111.900
562,800
168,800
731,600
142,700
735,300
220,600
955,900
-------
Materials - The only material cost of any consequence is the sodium car-
bonate used to neutralize the wastewater and the isopropyl alcohol used
to regenerate the resin (the Amberlite XAD-4 has a 5 year useful life and
is depreciated with the capital equipment). These costs have been pre-
viously given.
Labor - Labor costs are wages paid to operating labor. The total annual
labor required for the three systems (based on 350 operating days/year) is:
Annual man-hours
Reductive degra- Two systems
XAD-4 resin system dation system in series
Process 200 gpm 300 gpm 200 gpm 300 gpm 200 gpm 300 gpm
Sedimentation 1,050 1,050 1,050 1,050 1,050 1,050
Filtration 1,050 1,050 1,050 1,050 1,050 1,050
XAD-4 resin
process 3,750 4,150 - - 3,750 4,150
Reduct ive
degradation
process - - 3,750 4,150 3.750 4,150
Total 5,850 6,250 5,850 6,250 9,600 10,400
The hourly earnings of production or nonsupervisory workers in the
chemical and allied products industry was $5.18/hr in March 1975 (Monthly
Labor Review, 1975). For April 1975, the estimated wage rate is $5.20/hr.
This gives an annual operating labor cost for each of the systems as follows:
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200
300
200
300
200
300
5,850
6,250
5,850
6,250
9,600
10,400
$5.20
5.20
5.20
5.20
5.20
5.20
$30,400
32,500
30,400
32,500
49,900
54,100
Flow rate Annual Hourly Annual operating
System (gpm) man-hours wage labor cost
XAD-4 resin
Reductive degradation 200
Two systems in series
Supervision - Supervision of labor is normally estimated as a percentage
of operating labor, a typical value being 20% (Jelen, 1970). Using this
typical value of 20% of operating labor costs for labor supervision costs
gives the following estimates:
Reductive degradation Two systems
XAD-4 resin system system in series
200 gpm 300 gpm 200 gpm 300 gpm 200 gpm 300 gpm
Annual labor $6,100 $6,500 $6,100 $6,500 $10,000 $10,800
supervision
cost
Payroll charges - These costs are the result of the many fringe benefits
employees receive in addition to their salaries. Recent emphasis on these
benefits in labor contracts make this cost substantial and it is steadily
increasing with time. According to Perry and Chilton (1973), the sum of
fringe benefits may add between 15 and 40% to the wage rate of employees,
and this varies widely from company to company. In this estimate, payroll
charges (fringe benefits) are taken to be 30% of the wages paid to both
labor and supervision. These payroll charges are thus estimated to be:
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Total operating
Flow rate
(gpm)
200
300
200
300
200
300
labor and
supervision cost
$36,500
39,000
36,500
39,000
59,900
64,900
Payroll
Charge
$11,000
11,700
11,000
11,700
18,000
19,500
System
XAD-4 resin
Reductive degradation
Two systems in series
Maintenance - Maintenance costs have been determined previously for each
process. They are summarized here to give the total annual maintenance
costs for each system.
Annual maintenance cost ($)
Reductive degra-
XAD-4 resin system dation system
Process
Two systems
in series
200 gpm 300 gpm 200 gpm 300 gpm 200 gpm 300 gpm
Sedimentation $3,900
Filtration 6,600
XAD-4 resin 8,400
process
Reductive
degradation
process
$4,900 $3,900 $4,900 $3,900 $4,900
7,900 6,600 7,900 6,600 7,900
10,600 - - 8,400 10,600
5,600
7,100
5,600
7,100
Total $18,900 $23,400 $16,100 $19,900 $24,500 $30,500
Operating supplies - Operating supplies are items such as lubricating oil,
instrument charts, etc., that are neither raw nor repair materials. The
cost of these items is typically 6% of labor costs (Jelen, 1970). This
amounts to an annual cost for operating supplies of:
88
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Reductive degradation Two systems
XAD-4 resin system system in series
200 gpm 300 gpm 200 gpm 300 gpm 200 gpm 300 gpm
Annual operating $1,800 $2,000 $1,800 $2,000 $3,000 $3,200
supplies cost
Utilities - The utilities required for the processes are primarily electrical
power. Little water is required if we assume that processed wastewater is
recycled to the filter backwash and sodium carbonate mixing tanks. The es-
timated annual electrical cost for the 100 gpm reductive degradation system
is $1,350; for the XAD-4 resin system is $650 (Marks, September 1974); and
for pumping 100 gpm of wastewater in the sedimentation and filtration process
is $100.
These costs are scaled up by direct proportion to give an annual elec-
trical cost to each system as follows:
Annual electrical costs ($)
Reductive degradation Two systems
XAD-4 resin system • system in series
Process 200 gpm 300 gpm 200 gpm 300 gpm 200 gpm 300 gpm
Sedimentation and
filtration 200 300 200 300 200 300
XAD-4 resin
process 1,300 2,000 - - 1,300 2,000
Reductive degra-
tion process - - 2,700 4,100 2,700 4,100
Total 1,500 2,300 2,900 4,400 4,200 6,400
Laboratory services - Laboratory services furnished to support the treatment
processes and monitoring operations are estimated at 20% of labor cost (Jelen,
1970). The annual laboratory services cost for the systems, therefore, are:
89
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Reductive degradation Two systems
XAD-4 resin system system in series
200 gpm 300 gpm 200 gpm 300 gpm 200 gpra 300 gpm
Annual laboratory $6,100 $6,500 $6,100 $6,500 $10,000 $10,800
service cost
Depreciation - Depreciation is a periodic charge that distributes the installed
capital investment cost over its expected service life. The cost estimate uses
straight line depreciation and assumes all capital assets have a zero salvage
value (see AppendixB) . The capital investment costs and expected lives of all
depreciable assets have been previously given and are used below to determine
the annual depreciation cost for the three systems (rounded to nearest $100).
Annual depreciation cost ($)
XAD-4 resin Reductive degra- Two systems
Life system dation system in series
Capital asset (years) 200 gpm 300 gpm 200 gpm 300 gpm 200 gpm 300 gpa
Sedimentation process 40 900 1,100 900 1,100 900 1,100
Filtration process 15 11,400 13,700 11,400 13,700 11,400 13,700
XAD-4 resin process 10 21,700 27,700 - - 21,700 27,700
XAD-4 resin charge 5 32,800 49,100 - - 32,800 49,100
Reductive degradation 10 - 14,600 18,600 14,600 18,600
process
Total 66,800 91,600 26,900 33,400 81,400 110,200
Property taxes, insurance, and capital costs - Property taxes, insurance and
capital costs are estimated as a percentage of the installed capital equip-
ment cost. These costs are calculated and reported in this report separately
to show the cost breakdown of these three items.
Jelen (1970) reports that property taxes are taken to be 2% of investment
cost, and that insurance is generally about 1% of investment cost. Capital
cost (or interest) is a charge to finance the investment expenditures. This
90
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interest may be a real cost when funds are borrowed to finance the invest-
ment, or an assumed cost when internal funds are used (since internal funds
would earn interest if loaned out rather than purchase capital assets).
The annual rate of interest (see Appendix B) has varied widely in the recent
past and is taken to be 10% for 10 years due to current market interest
rates and current cost literature (Chemical Engineering, 1975b). As shown
in Appendix B, this is equivalent to an annual interest rate of 6.3% of
capital investment.
Using the above percentage gives the following indirect costs for
the three systems:
Annual cost ($)
XAD-4 resin Reductive degra- Two systems
process dation system in series
Cost item 200 gpm 300 gpm 200 gpm 300 gpm 200 gptn 300 gpm
Property 11,700 15,400 7,000 8,700 14,600 19,100
taxes (2%)
Insurance (1%) 5,900 7,700 3,500 4,300 7,300 9,600
Capital 36,900 48,500 22,100 27,300 46,100 60,200
cost (6.3%)
Plant overhead - Plant overhead is a charge to the costs of the manufac-
turing facility which are not chargeable to any particular operation and
are normally charged on an allotted basis. Overhead includes such cost
items as plant supervision, plant guards, janitors, cafeterias, adminis-
trative offices, accounting, purchasing, etc. Overhead costs will vary
from company to company and are usually calculated as a percentage of direct
labor cost or a percentage of installed capital investment for the entire
91
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facility, and allocated to each operation based on its labor or investment
cost.
Jelen (1970) reports that plant overhead can range-from 40 to 60% of
direct labor costs or 15 to 30% of direct costs. In this report, the plant
overhead is estimated to be 20% of the direct costs.
Total Cost Estimates for the Resin Adsorption System and the Reductive
Degradation System
The total costs of the resin adsorption system, the reductive degrada-
tion system and the two systems in series are given in Table 8. The table
shows that the total installed capital equipment costs for the three sys-
tems are: (a) XAD-4 resin system, $586,200 (200 gpm) and $770,400 (300 gpm);
(b) reductive degradation system, $350,700 (200 gpm) and $433,700 (300 gpm);
and (c) the two systems in series, $731,600 (200 gpm) and $955,900 (300 gpm).
The estimated total annual operating costs are: (a) $324,300 and $433,200;
(b) $154,100 and $181,800; and (c) $410,300 and $537,500, respectively.
The estimated cost (per 1,000 gal. of effluent) of treating the toxaphene
wastewater effluent is (a) $3.21 and $2.87; (b) $1.53 and $1.20; and (c)
$4.07 and $3.55, respectively. The estimated unit operating cost to treat
toxaphene wastewater per pound of toxaphene product (based on 50 million
pounds of annual production) are: (a) $0.0065 and $0.0087; (b) $0.0031
and $0.0036; and (c) $0.0082 and $0.0108, respectively. (The current sale
price of toxaphene is reported to be 38 to 400/lb (Heiners and Mumma, 1975b)).
92
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Table 8 (Concluded)
VO
Reductive degradation
XAD-4 resin system
Cost item
Indirect costs
Depreciation
Property taxes
Insurance
Capital cost
Plant overhead
Subtotal
Total annual operating costs
(1975 $)
Unit operating costs
Cost ($)/!, 000 gal. effluent
Cost, $/lb of toxaphene
200 gpm
66,800
11,700
5,900
36,900
33,800
155 , 100
324,300
3.21
0.0065
300 gpm
91,600
15,400
7,700
48,500
45,000
208,200
433,200
2.87
0.0087
system
200 gpm
26,900
7,000
3,500
22,100
15,800
75,300
154,100
1.53
0.0031
300 gpm
33,400
8,700
4,300
27,300
18,000
91,700
181,800
1.20
0.0036
Two systems
in series
200 gpm
81,400
14,600
7,300
46 , 100
43,500
192,900
410,300
4.07
0.0082
300 gpm
110,200
19,100
9,600
60,200
56,400
255,500
537,500
3.55
0.0108
(50 million pounds produced
in 1975)
-------
Carbon Adsorption Process Costs
As indicated in Figure 12, the toxaphene process wastewater will re-
quire (a) sedimentation, (b) filtration, and (c) neutralization prior to
adsorption on carbon. The costs of sedimentation and filtration have been
discussed earlier in this report, and the costs of the neutralization were
discussed in the portion of this report dealing with the costs of the re-
ductive degradation process.
The capital equipment costs of the carbon adsorption unit in the sys-
tem are estimated below at two contact times. Following this are the cost
summaries for the entire system which includes sedimentation, filtration,
neutralization and carbon adsorption.
A conceptual flow diagram for a carbon adsorption process is shown
in Figure 12. The portions of this process which deal with removal of
suspended solids and pH adjustment in the wastewater are taken to be iden-
tical to the process steps of sedimentation, filtration and neutralization,
which are used in the reductive degradation system. Hager (1974) indicates
that suspended solids in amounts exceeding about 50 mg/liter should be re-
moved prior to treatment of effluent in carbon adsorption beds and that pH
adjustment can be employed to enhance adsorption efficiency.
Following removal of suspended solids, the wastewater is conducted
through a two-stage carbon adsorption system which consists essentially
of (a) two on-stream carbon adsorption units operating in series and one
standby unit packed with granular activated carbon, and (b) the required
auxiliary equipment (pumps, piping, process instrumentation, etc.).
95
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When the concentration of toxaphene in the effluent from the first
unit is equivalent to the feed concentration the carbon in the unit is ex-
hausted and the unit is taken off stream (Hutchins, 1975a). The second
unit then becomes the lead unit and the standby column is put on stream
as the second column in the series. The exhausted unit is discharged, re-
filled with fresh carbon, and used as standby. Because of the small re-
quirement for activated carbon, regeneration of the carbon is not econom-
ically justified (Hutchins, 1975b). The exhausted carbon is disposed of
by incineration; the costs for incineration are not included in this study.
The cost of a carbon adsorption process to treat 300 gpm of toxaphene
contaminated wastewater is estimated from cost information obtained from
two sources. The first source is Mr. Roy H. Hutchins, Development Associate,
Product Development Department, ICI United States, Inc., Wilmington, Delaware
(Hutchins, 1975a). The second source is a process design manual for carbon
adsorption (Cornell, 1973).
The treatability of a particular wastewater by activated carbon and
the relative capacity of carbon for treatment can be estimated from adsorp-
tion isotherm data, obtained by batch testing. However, carbon performance
and design criteria are best determined by pilot tests under dynamic flow
conditions. The required contact time for a given carbon adsorber column
(i.e., the residence time required for the wastewater in a carbon column)
is an important design consideration for carbon adsorption systems. The
contact time data can only be accurately determined by pilot tests which
96
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simulate full-scale operating conditions. Unfortunately, contact time data
of this type are not available. Therefore, two different assumed values of
contact time were used in this study as a means for estimating a range of
investment and operating costs. The two contact times considered were:
1. Thirty minute (30 min) contact time (15 min retention in each of
two carbon columns in series). This retention time was shown to be effec-
tive for endrin by data reported by Robeck (1965) (Table 13, p. 198).
2. Sixty minute (60 min) contact time (30 min retention in each of
two carbon columns in series).
Capital Investment Costs for Carbon Adsorption System with 30 Min Contact
Time
As recommended by Hutchins (1975a) the adsorption isotherm in Figure 8
by Hager (April 1974) was extrapolated to determine the toxaphene removal
per unit of carbon corresponding to a toxaphene concentration of 500 ppb
(i.e., the estimated concentration in the wastewater to be treated by car-
bon adsorption). The value obtained by extrapolation is 7% weight pickup.
This isotherm applies for carbon contact with toxaphene in distilled water.
Robeck (1965, Figure 6, p. 192) shows a relationship between the adsorption
capacities; the adsorption capacity is greater in distilled water than in
river water. River water most closely approximates the operating conditions
which would be encountered. Making an adjustment for river water results
in a loading value of about 3.9% (0.039 lb pesticide adsorbed per pound of
carbon used).
97
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The total quantity of toxaphene to be removed per day (reduction from
500 to < 5 ppb) by the conceptual adsorption system is estimated by con-
sidering that final effluent may contain 2 ppm toxaphene.
300 gpm x 3.785 liter/gal x 500 ug/liter = 567,750 ug/min, toxaphene
entering
300 gpm x 3.785 liter/gal x 2 ug/liter = 2,270 ug/min, toxaphene
leaving
Difference (rounded) = ~ 565,500 ug/min, toxaphene
retained on carbon
The estimated carbon requirement at 3.9% pickup is;
0.565 g/min x 60 x 24 ., .. , . , .
a = 46 Ib carbon required per day
453.6 x 0.039
Hutchins (1975a) has stated that the efficient use of carbon in the ad-
sorption system can be maximized by a counter-current type of operation as
depicted in Figure 12. In this conceptual process, two adsorber columns
are operated in series continuously, while a third adsorber unit is always
held on standby. All three columns would have the same physical size and
initial fresh carbon charge. When break-through occurs in the first ab-
sorber (i.e., the total charge becomes fully spent) the unit is taken out
of service. The second column then becomes the lead column (No. 1), and
the standby adsorber is then placed in service as the second adsorber. The
original No. 1 adsorber column is then discharged, the spent carbon dis-
posed of as solid waste to be incinerated and the drained wastewater is re-
processed through the system; the column is then recharged with fresh car-
bon and held on standby for a subsequent repetition of the operation
98
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described above. In this arrangement there is no regeneration of spent
carbon. Hutchins (1975a) has estimated that one carbon unit (~ 12,000 Ib C)
would become spent about every 5 months.
On the basis of data provided by Robeck (1965) and Cornell (1973) and
at the recommendation of Hutchins (1975a), it was considered that the two
on-stream adsorbers would have a total wastewater to carbon contact time
of 30 min (i.e., 15 min contact in each of two adsorbers) and that the flow
f\
rate through the carbon bed would be 4 gpm/ft'' of adsorber bed cross-
sectional area.
At 300 gpm, a 15 min contact time corresponds to a holding volume
per vessel of 300 x 15 or 4,500 gal. or 602 ft3. Cornell (1973) recommends
50% additional adsorber volume to provide for backwash operations. Thus,
the total volume of each vessel would be 1.5 x 4,500 or 6,750 gal. or
903 ft3. On this basis, the size of each contactor would be approximately
10 ft I.D. (30P = 75 sq ft cross-sectional area) by about 11 ft high.
Hutchins (1975a) has recommended an initial charge of 12,000 Ib carbon*
per vessel. Considering downflow operation of the contactors, the effective
volume (carbon volume) in each adsorber (contactor) would be
12,000 Ib = 522 fj.3 (approxiniateiy a 7-ft bed depth of carbon)
Cost for Carbon Contactor Units - Cost data reported by Cornell (1973)
(Figure 5-1, p. 5-4) were used to estimate the installed cost for three
* Hydrodarco 4000 sold by ICI, United States, Inc.
99
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equal-sized carbon adsorber columns (contactors). Cornell's Figure 5 relates
the construction cost to effective contactor volume. Since the volume (522
o
ft0) of the contactors considered in this study is off-scale on the low side
in this figure, the 0.6 power factor relationship was used to estimate the
contactor cost. A contactor with an effective volume of 1,000 ft^ has a
construction cost of $80,000 (Figure 5-1, Cornell, 1973). By the 0.6 factor
relationship (see Appendix B):
$80,000 = 1>000 °'6 C C - $54,200/contactor
522
Then, the cost for three contactors would be 3 x $54,200 or $162,600. Up-
dating this cost for inflationary changes using Marshall and Swift cost
indices for 1975 and 1973 gives:
443-8 x $162,600 = $209,700
344.1
Cost for Influent Pump Station - As shown in the Cornell (1973) cost data
(Figure 5-5, p. 5-11), the cost for an influent pump station for a 300 gpm
or 0.43 x 103 gpd is about $10,000. Updating by Marshall and Swift cost
indices for 1973 and 1975 gives:
443-8 x $10,000 - $12,900
344.1
Initial Carbon Charge and Carbon Replacement Costs - As recommended by
Hutchins (1975a) each of three contactors would have an initial charge of
12,000 Ib of granular activated carbon (Hydrodarco 4000, ICI, United States,
Inc.) at a cost of $0.38/lb. Then,
100
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3 x 12,000 x $0.38 = $13,700
Estimated make-up carbon costs (at 2 refills per year) is 2 x 12,000
x $0.38 = $9,100/year.
Plant investment costs for the carbon adsorption equipment (30 min
contact system) are:
Estimated
Installed costs (1975 $)
Influent pump station $ 12,900
Carbon contactors (3) 209,700
Initial carbon charge 13,700
Subtotal $236,300
Adjustment to account for 47,000
engineering, legal, adminis-
trative land and interst
expenses, 20% of subtotal
(Cornell, 1973)
Total $283,300
Capital Investment Costs for Carbon Adsorption Unit with 60 Min Contact Time
At 300 gpm, a 30 min contact time in each carbon adsorber corresponds
to a holding volume per vessel of 300 x 30 = 9,000 gal. or 1,204 ft3.
Cornell (1973) recommends 50% additional adsorber volume to provide for back-
wash operation. Thus, the total volume of each vessel would be 1.5 x 9,000
or 13,500 gal. For a flow rate of 4 gpm/ft2, the cross-sectional area of
each contactor would be *£ . 75 ft2 and the effective volume would be
2 x 522 or 1,044 ft .
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Cost data by Cornell (1973) (Figure 5-1, p. 5-4) show that the cost
for a contactor with 1,044 ft3 of effective volume is about $80,000. For
three contactors, the cost is 3 x $80,000 or $240,000. Updating by Marshall
and Swift cost indices for 1975 and 1973 gives:
443.8
344.1
= $240,000 - $309,500
The initial carbon charge would be twice as large as for the 30 min
total contact system or 2 x $13,700 = $27,400.
It is considered that the influent pump station cost would be the same
as for the 30 min contact system or $12,900.
Summary of Capital Investment - Estimated plant investment costs for the
carbon adsorption equipment (60 min contact time) are:
Item
Influent pump station
Carbon contactors (3)
Initial carbon charge
Subtotal
Adjustment to account for
engineering, legal, ad-
ministrative, land and
interest expenses; 20% of
subtotal (Cornell, 1973)
Total
Estimated
Installed Costs (1975 $)
$ 12,900
309,500
27,400
$349,800
70,000
$419,800
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Summary of Installed Capital Equipment Costs - Table 9 summarizes the
capital investments for the two carbon contact times considered in this
study.
Table 9. INSTALLED CAPITAL EQUIPMENT COST FOR THE 300 GPM
CARBON ADSORPTION SYSTEM
Capital investment cost (1975 $)
Contact time. 30 min Contact time. 60 min
Sedimentation $ 33,000 $33,000
Filtration 158,000 158,000
Carbon adsorption 283,300 419.800
Subtotal 474,300 610,800
Contingency, 30% 142,300 183.200
(see Appendix B)
Total $616,600 $794,000
Annual Operating Costs for Carbon Adsorption System (Including Sedimentation
Filtration, and Neutralization)
The total annual costs to operate the system at the 300 gpm flow rate
are estimated below. Most of these costs are a percentage of either the
installed capital equipment cost or the labor costs previously described.
The following list shows all of the cost items considered in this estimate.
103
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Direct costs
Materials
Labor
Supervision
Payroll charges
Maintenance
Operating supplies
Utilities
Laboratory services
Indirect costs
Depreciation
Property taxes
Insurance
Capital cost
Plant overhead
Operating Labor and Maintenance for Carbon Adsorption Plant - Operating
labor time is estimated from cost data reported by Cornell (1973) (Figure 5-7,
p. 5-18). The flow (432,000 gpd) for the conceptual carbon adsorption sys-
tem is off-scale on Figure 5-7. The one-fourth factor (see Appendix B) is
used to scale down labor requirements from one plant size to a smaller plant
size. From Figure 5-7 (Cornell, 1973), the operating labor requirement for
a flow of 2 MGD is 750 annual man-hours. Scaling down this value by the
one-fourth factor (see Appendix B) gives:
750 -( 2 Y*'25 c c = 51° man-hours for a flow of 0.432
\0.432/ M gpd (300 gpm)
Operating labor time for the 60 min contact system is taken to be the
same as for the 30 min contact system or 510 man-hours per year.
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The annual maintenance cost for the carbon adsorption operation is
estimated as 5% of capital investment (see Appendix).
For 30 min contact system, 0.05 x $283,300 = $14,200.
For 60 min contact system, 0.05 x $419,800 = $21,000.
Materials - The material costs are the limestone ($660/year) used to neu-
tralize the wastewater and the activated carbon makeup each year ($9,100/
year).
Labor - Labor costs are wages paid to operating labor. These costs are
taken to be the same for the 30 and 60 min contact systems. The total
annual operating labor required for the plant is:
Process Annual man-hours
Sedimentation 1,050
Filtration 1,050
Neutralization 1,050
Carbon adsorption 510
Total 3,660
The hourly earnings of production or nonsupervisory workers in the chemical
and allied products industry was $5.18/hr in March 1975 (Monthly Labor Review,
May 1975). For April 1975, the estimated wage rate is $5.20/hr. This gives
an annual operating labor cost of $19,000.
Supervision - Supervision of labor is normally estimated as a percentage of
operating labor, a typical value being 20% (Jelen, 1970). Using this typical
value of 207, of operating labor costs for labor supervision costs gives a
cost of $3,800/year. (Applies for both 30 min and 60 min contact systems).
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Payroll Charges - This cost is the result of the many fringe benefits em-
ployees receive in addition to their salaries. Recent emphasis on these
benefits in labor contracts make this cost substantial and it is steadily
increasing with time. The sum of fringe benefits may add between 15 and
40% to the wage rate of employees (Perry and Chilton, 1973), and this varies
widely from company to company. In this estimate, payroll charges (fringe
benefits) are taken to be 30% of the wages paid to both labor and super-
vision. This cost amounts to $6,800. (Applies for both the 30 min and the
60 min contact systems.)
Maintenance - Maintenance costs have been determined previously for each
part of the process. They are summarized here to give the total annual
plant maintenance costs.
Annual maintenance
Process 30 min system 60 min system
Sedimentation $ 5,000 $ 5,000
Filtration 7,900 7,900
Neutralization 2,900 2,900
Carbon adsorption 14.200 .21.000
Total $30,000 $36,800
Operating Supplies - Operating supplies are items such as lubricating oil,
instrument charts, etc., that are neither raw or repair materials. The
cost of these items is typically 6% of labor costs (Jelen, 1970) and amounts
to an annual cost of $1,100. (Applies for both 30 min and 60 min contact
systems.)
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Utilities - The utilities required for the process are primarily electrical
power. The estimated annual electrical cost for this system estimated from
cost data reported by Cornell (1973) (Figure 5-9, p. 5-20). Figure 5-9 shows
an annual power cost (at $0.02/KWH) of 4,600/year. Adjusting from 1973 to
1975 by Marshall and Swift cost indices for electrical power industries gives
ft-37'-- x 4,600 = $6,200. (Applies for both the 30 min and 60 min contact
322.2
systems.)
Laboratory - Laboratory services furnished to support the treatment process
operation are estimated at 20% of labor cost (Jelen, 1970) or $3,800/year.
(Applies for both the 30 min and 60 min contact systems.)
Depreciation - Depreciation is a periodic charge that distributes the in-
stalled capital investment cost over its expected service life. This cost
estimate uses straight line depreciation and assumes all capital assets have
a zero salvage value. The capital investment costs and expected lives of
all depreciable assets have been previously given and are summarized and
totaled below (rounded to nearest $100):
Life Annual depreciation cost ($)
Process (years) 30 min system 60 min system
Sedimentation 40 800 800
Filtration 15 W.500 10.500
Carbon adsorption 10 28,300 4
Total 39>600 5
Pro
perty Taxes. Insurance, and Capital Costs - Property taxes, insurance
and capital costs are estimated as a percentage of the installed capital
107
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equipment cost. These costs are calculated and reported in this report
separately to show the cost breakdown of these three items.
Property taxes are taken to be 2% of investment cost, and insurance is
generally about 17. of investment cost (Jelen, 1970). Capital cost (or in-
terest) is a charge to finance the investment expenditures. This interest
may be a real cost when funds are borrowed to finance the investment, or
an assumed cost when internal funds are used (since internal funds would
earn interest if loaned out rather than used to purchase capital assets).
The annual rate of interest has varied widely in the recent past and is
taken to be 6.37. per annum (see Appendix B).
Using the above percentages gives the following indirect costs for
this system:
Annual cost ($)
Cost item 30 min contact system 60 min contact system
Property taxes (27.) 12,300 15,900
Insurance (170) 6,200 7,900
Capital cost (6.37.) 38,800 50,000
Plant Overhead - Plant overhead is a charge to the costs of the manufac-
turing facility which are not chargeable to any particular operation and
are normally charged on an allotted basis. Overhead includes such cost
items as plant supervision, plant guards, janitors, cafeterias, administra-
t
tive offices, accounting, purchasing, etc. Overhead costs will vary from
company to company and are usually calculated as a percentage of direct
labor or a percentage of installed capital investment for the entire
108
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facility, and allocated to each operation based on its labor or investment
cost.
Plant overhead can range from 40 to 60% of direct labor costs or 15 to
307o of direct costs (Jelen, 1970). We estimate that plant overhead is 207.
of direct costs in this report.
Total Cost for Carbon Adsorption System (Including Costs of Sedimentation,
Filtration, and Neutralization)
The total cost of the carbon adsorption system is the sum of the total
capital investment costs plus the annual operating cost. These costs have
been estimated in the preceding three sections of this report.
The total estimated capital investment costs for the carbon adsorption
system are presented in Table 10.
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Table 10. ESTIMATED TOTAL INVESTMENT AND ANNUAL OPERATING COSTS
FOR GRANULAR ACTIVATED CARBON ADSORPTION SYSTEMS
(300 gpm Toxaphene Wastewater Flow Rate)
Carbon adsorption system total contact time, min
Cost item
Total installed capital equipment cost
(including costs for sedimentation and
filtration equipment)
Annual operating costs:
Direct costs
Materials
Operating labor
Supervision
Payroll charges
Maintenance
Operating supplies
Utilities
Laboratory charges
Subtotal
Indirect costs
Depreciation
Property taxes and insurance
Capital cost (interest)
Plant overhead
Subtotal
Total (rounded)
Unit operating costs
Cost ($)/!,000 gal. effluent
Cost, $/lb of toxaphene product
(50 million pounds product in 1975)
Costs $ (1975)
30 60
616,600 794,000
9,800
19,000
3,800
6,800
30,000
1,100
6,200
3.800
80,500
39,600
18,500
38,800
16.100
113,000
194,000
$1.28
0.0039
9,800
19,000
3,800
6,800
36,800
1,100
6,200
3.800
87,300
53,300
23,800
50,000
17.500
144,600
232,000
$1.53
0.0046
110
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REFERENCES
Black, Crow, Eidsners, Inc., Engineers, Houston, Texas (a subsidiary of
Hercules, Inc.), "The Effect of Toxaphene on Sewage Treatment," a report
to Hercules, Inc., September 1971.
Blecker, H. G., and T. M. Nichols, "Capital and Operations Costs of Pollu-
tion Control Equipment Modules--Vol. II—Data Manual, EPA-R5-73-023b,
July 1973.
Borenstein, N.~, Pollution Control Research Department, Rohm and Haas
Pollution Control Research Department, telephone communication with
Mr. Gary Kelso, October 3, 1975.
Chaddock, R. E., Affidavit before the Environmental Protection Agency
concerning proposed toxic pollutant effluent standards for aldrin/
dieldrin, etc., FWPCA (307) Docket No. 1, Washington, D.C., March 15,
1974.
Chemical Engineering, "Economic Indicators, July 7 (1975a).
Chemical Engineering, p. 89, July 21 (1975b).
Chemical Marketing Reporter, April 29, 1975.
Cohen, J. M., L. J. Kamphake, A. E. Lempke, C. Henderson, and R. L.
Woodward, "Effect of Fish Poisons on Water Supplies, Part I, Removal
of Toxic Materials," J. Amer. Water Works Assoc.. 52., 121551 (1960).
Cornell, Rowland, Hayes, and Merryfield, Clair A. Hill and Associates,
"Process Design Manual for Carbon Adsorption," U.S. Environmental
Protection Agency, October 1973.
Cywin, A., and E. E. Martin, "Development Document for Proposed Effluent
Limitations Guidelines and New Source Performance Standards for the
Major Inorganic Product Segment of the Inorganic Chemicals Manufactur-
ing Point Source Category," September 1973.
Dunn, C. L. Manager, Ecological Research, Synthetic Department, Hercules,
Inc., Wilmington, Delaware, letter to Mr. C. E. Mumma, October 7, 1975.
Enviro-Labs, Inc., of Starkville, Mississippi, "Completion Report, Waste
Water Treatability Studies, Vicksburg Chemical Company, Vicksburg,
Mississippi," engineering report to Vicksburg Chemical Company,
August 31, 1975 (report required for NPDES permits).
Ill
-------
Ferguson, T. L., and Lawless, E. W., Visit to Hercules, Inc., offices,
Wilmington, Delaware, on November 17, 1971, to discuss the production
of toxaphene.
Ferguson, T. L., and A. F. Meiners, "Wastewater Management Review No. 3 -
Toxaphene," Final Report, EPA Contract No. 68-01-2379, to the Hazardous
and Toxic Substances Regulation Office, May 8, 1974.
Ferguson, T. L., and Mumma, C. E., Visit to Hercules, Inc., chemical plant
at Brunswick, Georgia, on August 20, 1975, to discuss the production of
toxaphene.
Gunther, F. A., "Reported Solubilities of 738 Pesticide Chemicals in Water,"
Residue Reviews, 2£: 1-145 (1968).
Hager, D. G., and J. L. Rizzo, "Removal of Toxic Organics from Wastewater
by Adsorption with Granular Carbon," paper presented at the Environmental
Protection Agency Technology Transfer Session on Treatment of Toxic
Chemicals, Atlanta, Georgia, April 19, 1974.
Hicks, H. E., Manager, Hercules Plant at Brunswick, Georgia, Letter Report
to Allen Cywin, Director, Effluent Guideline Division, EPA, June 24, 1975.
Hughes, R. A. et al., "Studies on the Persistence of Toxaphene in Treated
Lakes," a thesis submitted to the Graduate School of the University of
Wisconsin in 1970, published on demand by University Microfilms, Inc.,
Ann Arbor, Michigan (70-24, 751).
Hutchins, R. A., Development Associate, ICI United States, Inc., letter and
telephone communication to C. E. Mumma, October 1975a.
Hutchins, R. A., "Activated Carbon Regeneration - Thermal Regeneration Costs,1
Chemical Engineering Progress, 71.(5):80 (1975b).
Huritz, M., Rohm and Haas Company, telephone communication with Mr. Gary
Kelso, October 2, 1975.
Jelen, F. C., Cost and Optimization Engineering. McGraw-Hill Book Company,
New York (1970).
Jett, G., EGDB Assistant Project Officer (EPA), Visit to Hercules, Inc.,
plant at Brunswick, Georgia, on July 9, 1975.
112
-------
Kennedy, D. C., "Treatment of Effluent From Manufacture of Chlorinated
Pesticides With A Synthetic, Polymeric Adsorbent, Amberlite XAD-4,"
Environmental Science and Technology. J7(2):138 (1973).
Lair, M. D., and R. 3. Bruner, EPA Surveillance and Analysis Division,
Report on Investigation of Wastewater Discharges, Hercules, Inc.,
Brunswick, Georgia, for plant inspection conducted on March 3 to 6, 1975.
Marks, D. R., "Testimony of Daniel R. Marks Respecting Technology to
Remove Endrin From Water," FWPCA (307) Docket No. 1, State of Tennessee,
County of Shelby, March 14, 1974a.
Marks, D. R., "Status Report on Chlorinated Hydrocarbon Pesticide Removal
From Wastewater," EPA Grant No. S-803159-01-0, Velsicol Chemical Corpora-
tion, Memphis, Tennessee, September 30, 1974b.
Meiners, A. F., and C. E. Mumma, Plant Visit, Tenneco Chemicals, Inc.,
Fords, New Jersey, October 13, 1975a.
Meiners, A. F., and C. E. Mumma, Plant Visit, Riverside Chemical Company,
Groves, Texas, August 7, 1975b.
Meiners, A. F., and C. E. Mumma, Plant Visit, Vicksburg Chemical Company,
Vicksburg, Mississippi, October 14, 1975c.
Monthly Labor Rev., Vol. 98, No. 5, May 1975.
NPDES Permit No. 0000116, Tenneco Chemicals, Inc. (1972).
NPDES Permit No. 2S DOXW2 000021, Tenneco Chemicals, Inc. (1972).
NPDES Permit No. GA 0003735, RAPP Permit Application (5 pages of Section 2,
No. GA 0740YN 3 000 171) and NPDES permit of Hercules, Inc., Brunswick,
Georgia (1974).
NPDES Permit No. TX 0062448, Riverside Chemical Company (1975).
NPDES Application, Factsheet for, Application No. MS 0027 995, Vicksburg
Chemical Company (1975).
Oil. Paint and Drug, November 27, 1972.
Perry, R. H., and C. H. Chilton, Chemical Engineer's Handbook, 5th ed.,
McGraw-Hill Book Company, New York (1973).
113
-------
Popper, H., Modern Cost-Engineering Techniques, p. 252, McGraw-Hill Book
Company, New York (1970).
Robeck, G. G. et al., "Effectiveness of Water Treatment Process in Pesti-
cide Removal," J. Amer. Water Works Assoc.. 57., 181 (1965).
Rohm and Haas, "Preliminary Technical Notes, Amberlite® XAD-4" (1971).
Swank, R. R., Jr., Acting Chief, Industrial Pollution Branch, Southeast
Environmental Research Laboratory, Athens, Georgia, Conference with
A. F. Meiners and C. E. Mumma, September 29, 1975.
Sweeny, K. H., and J. R. Fischer, "investigation of Means for Controlled
Self-Destruction of Pesticides," Aerojet Final Report on FWQA Contract
No. 14-12-596, Water Pollution Control Research Series 16040 ELO 06/70,
June 1970.
Sweeny, K. H. , and J. R. Fischer, "Decomposition of Halogenated Organic
Compounds Using Metallic Couples," U.S. Patent No. 3,737,384, for U.S.
Department of the Interior, June 1973.
Sweeny, K. H., A. F. Graefe, R. L. Schendel, and R. D. Cardwell, "Devel-
opment of Treatment Process for Chlorinated Hydrocarbon Pesticide
Manufacturing and Processing Wastes," Envirogenics Systems Company,
EPA Contract 68-01-0083, July 1973.
Sweeny, K. H., A. F. Graefe, R. L. Schendel and R. D. Cardwell, "Develop-
ment and Demonstration of Process for the Treatment of Chlorinated
Cyclodiene Pesticide Manufacturing and Process Wastes," Envirogenics
Systems Company, December 1973.
Sweeny, K. H., "Development of Treatment Process for Chlorinated Hydro-
carbon Pesticide Manufacturing and Process Wastes," Report No. L-0305-25,
Envirogenics Systems Company, EPA Contract No. 68-01-0083, May 1974.
Sweeny, K. H., "Status of Developments of Reductive Degradation Treatment
of Endrin-Heptachlor and Chlordane Manufacturing Wastes," Envirogenics
Systems Company, EPA Contract No. 68-01-0083, September 1974.
Sweeny, K. H., Program Manager, EPA Contract No. 68-01-0083, Envirogenics
Systems Company, Personal communication to Mr. C. E. Murama, Midwest
Research Institute, October 6, 1975.
114
-------
Vitalis, J. S., "Velsicol Plant Notes Summary," Record of Communication to
Walter J. Hunt, Chief, Effluent Guidelines Development Branch, June 2,
1975.
Weston, Roy F., Inc., Draft, "Development Document for Effluent Limitations
Guidelines and Standards of Performance - Miscellaneous Chemicals Industry,"
EPA Contract No. 68-01-2932, February 1975.
Worley, J. W., Works Manager, Tenneco Chemicals, Inc., Fords, New Jersey,
Letter Report on Strobane®-T to Mr. W. J. Hunt, U.S. Environmental Pro-
tection Agency, Effluent Guidelines Division, Washington, D.C., August 13,
1975.
115
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APPENDIX A
ENGINEERING INFORMATION PERTINENT TO TOXAPHENE WASTE TREATMENT
AT THE HERCULES, INC.. PLANT AT BRUNSWICK, GEORGIA
The information contained in this Appendix was obtained from an
engineering report supplied by Mr. C. L. Dunn, Manager, Ecological Re-
search, Hercules, Inc., to Mr. Richard K. Ballentine, Toxic Substances
Branch^ EPA, on December 16, 1975. This information was not received in
time to be incorporated into the toxaphene manufacture report.
A-l
-------
A. Background
Systematic sampling and determination of toxaphene content of
Brunswick Plant waste effluent was undertaken in 1970. Monitoring prior
to that time was done on an irregular schedule, but had identified toxa-
phene as an undesirable pollutant. Various methods for toxaphene pollution
abatement were studied, including adsorption, thermal and chemical decom-
position. Deep well injection was studied intensively and Earth Science,
Inc., was contracted to develop a preliminary proposal which was completed
January 20, 1969. Additional proposals were obtained from International
Pollution Control, Inc., and Dow Chemical Company. Although the reports
were generally favorable, both the Georgia Water Quality Commission and
Hercules, Inc., had reservations about the desirability of this concept.
By mutual agreement, this concept was dropped from consideration in the
spring of 1970. Reconsideration of alternative treatment methods resulted
in the design and installation of the present system. The Georgia Water
Quality Commission issued a construction permit in early 1971, and the
system was completed in stages during 1972. A schematic drawing of the
toxaphene process and the related pollution abatement system can be found
in Figure A-l.
B. Description of System
1. Containment
It was recognized from the beginning that the process area,
packaging area, storage areas and all areas that might be contaminated
with toxaphene would have to be enclosed by dikes, curbs or other suitable
barriers. All process water and rainfall runoff is presently collected
and treated. The area contained is indicated in Figure A-2, an aerial
photo of the Toxaphene Area.
2. Sumps and Settling Tanks
All process water, spillage, floor drainings, etc., from the
process area is treated in a settling tank to separate, recover and recycle
any free toxaphene or toxaphene solution. A system of sumps is used for
the same purpose in the solution makeup, packaging and shipping areas.
Rainwater runoff is also passed through a number of sumps and toxaphene
or toxaphene solution is also collected in these sumps and recycled.
3. Neutralization
All wastewater from the process area is neutralized. Since the
bulk of this stream consists of dilute, waste by-product hydrochloric acid,
A-2
-------
Camphene
Chlorine
01
o
Floor
Washings'
Etc.
Limcrock
Lime
Caustic
Rain Water
CO
C-1
> Toxaphc-nc
Vent
JL
Water
^^
^
. ... Ny-
V-
/
PH
Control
N
f
Lagoons
~s
-N
^
v^
*•
Solution
Makeup
Xylena
Solids
V,'aste Water
Toxapher,
Solution
Figure A-l. Hercules toxaphene process schematic
A-3
-------
"TV
2*
Figure A-2 - Aerial Photo of Hercules
Toxaphene Plant, Brunswick, Georgia
'
-------
these facilities are extensive. After the process wastewater is passed
through the settling tank for recovery of free toxaphene, the wastewater
stream is passed through several parallel limerock basins. Contact with
crushed limerock neutralizes the bulk of the acidity. The effluent from
the limerock basins is then combined with spent scrubbing liquors from
the vent scrubbers and the pH of the combined streams is adjusted with
caustic in a two-stage stirred tank. The heart of this pollution abate-
ment design centers on the fact that toxaphene is strongly adsorbed on
inorganic particulate matter originating in the limestone, lime and caustic
neutralization steps. A great deal of work was carried out on both a
laboratory, and pilot scale to develop and prove in the effectiveness of
this abatement process.
4. Solids Separation
All wastewater, after pH adjustment, is passed through a series
of lagoons to settle out suspended solids. Rainwater from the rainwater
lagoon is mixed with the influent to the solids separation lagoons. Solids
separation is of course an essential feature of any pollution abatement
system. In this case, however, solids separation serves a dual purpose.
As noted above, because of the hydrophobic nature of toxaphene, the toxa-
phene present in the wastewater is strongly adsorbed on the separated
solids. The source of the solids in the wastewater is the inert sand and
clay present in the limerock used for neutralization. An aerial photo
of the lagoon system can be found in Figure A-3.
5. Solid Waste Disposal
The solids collected in the lagoons are disposed of by landfill.
The landfill operation is operated under permit from the Gerogia Department
of Natural Resources.
6. Miscellaneous
a. A special housekeeping crew is used to clean up spills,
clean sumps and to maintain the high level of cleanliness necessary to
meet the difficult effluent standard.
b. Essentially all maintenance is done within the contained
area. If it is absolutely necessary to remove a piece of equipment from
the contained area, it is thoroughly decontaminated.
c. Analyses are run in a separate laboratory. Unused samples
are returned to the process. Sample containers are recycled without
cleaning when possible. If not possible, disposable containers are used.
A-5
-------
C. Design Criteria
The pH control system was essentially in operation before issuance
of the permanent NPDES permit. Capacity and design are largely based on
operating experience. The design criteria for the lagoon system is as
follows:
Influent Effluent
Flow 300 gpm 300 gpm
Toxaphene 2,000 ppb toxaphene 200 ppb toxaphene
Solids 4-10 tons/day Negligible
pH Approximately neutral Approximately
neutral
The controlling design criteria was a maximum of 1 Ib/day of
toxaphene in the total plant effluent. Because of uncontrolled sources
of toxaphene, the effluent from the lagoon must contain significantly less
than 1 Ib/day of toxaphene.
The influent to the lagoons is extremely variable and the lime-
rock used for neutralization contains variable amounts of inert solids.
Because of this variability and the difficulty of accurately sampling
this mixture, the influent is not routinely sampled. The effluent is,
however, sampled daily. In addition, the total plant effluent composed
of the toxaphene waste plus all other process wastewater, is also sampled
daily. This sampling is at the outfall designated 001. Reports are sub-
mitted to state and federal authorities at monthly intervals.
D. Method of Operating
Sumps and settling tanks are cleaned as needed and the recovered
toxaphene returned to the appropriate process step. Limerock is fed to
the system as needed by conventional conveying equipment. Caustic or acid
is added to the influent to the pH adjustment facilities automatically as
needed to achieve the desired pH. The desired pH is normally slightly
acidic since a higher pH results in unnecessary difficult-to-settle hy-
droxides. Because of the relatively small quantity of toxaphene waste-
water, compared to the total plant effluent, the slight acidity of the
toxaphene effluent stream is insignificant.
Rainwater runoff surges are impounded in the rainwater lagoon and
the rainwater is then mixed with the process wastewater at a uniform rate.
The rainwater runoff is essentially neutral and requires no other treatment,
A-6
-------
The present method of operating the lagoons is to pass the waste-
water through two lagoons in series. The lagoons presently being used are
baffled so as to divide them in half. Essentially, they are now the equiv-
alent of four lagoons in series. The lagoons not now in service contain
solids collected in prior service and are dewatering. These solids will
be transferred to the drying bed in the near future prior to transporting
to the landfill site. Figure A-3 clearly shows the drying bed (partially
empty), the two lagoons in active service, the two lagoons dewatering and
the rainwater lagoon.
E. Chemical Additive Rates
The only additives used are the alkalies used for pH control.
In theory, about 0.67 Ib of hydrochloric acid or equivalent must be neu-
tralized for each pound of toxaphene produced. Some acid is sold and
need not be neutralized. Some of the waste acid is neutralized in the
vent scrubbers by caustic or lime and the balance is neutralized by lime,
limerock or caustic. In 1974, consumptions of the various alkalies per
pound of toxaphene were:
Lime 0.05 Ib/lb
Caustic 0.016 Ib/lb
Limerock 0.51 Ib/lb
F. Pollution Abatement Efficiency
The design toxaphene abatement efficiency for the lagoon system
was about 90%. The actual efficiency is probably greater than 95%. Con-
tainment and meticulous control of leaks and spills in process and materials
handling has resulted in an appreciable lowering of the toxaphene load pre-
sented to the lagoon system.
A-7
-------
Figure A-3 - Aerial Photo of Lagoons
and Drying Bed at Hercules Toxaphene
Plant, Brunswick.Georgia
A-8
-------
APPENDIX B
DEFINITION OF TERMS AND DISCUSSION OF CONVENTIONAL
ENGINEERING PRACTICES USED IN ESTIMATING COSTS
OF PESTICIDE WASTEWATER TREATMENT PROCESSES
B-l
-------
Several terms used in the cost estimates require further defini-
tion and have been placed in this appendix to avoid a lengthy discus-
sion in the text of the report. The terms which are defined and dis-
cussed in this appendix are (a) limits of error for cost estimates, (b)
cost indexes, (c) six-tenths factor, (d) one-fourth factor, (e) payroll
charges, (f) .operating supplies, (g) control laboratory costs, (h) main-
tenance and repairs, (i) depreciation, (j) capital cost, (k) plant over-
head, and (1) contingency for capital investment.
LIMITS OF ERROR FOR COST ESTIMATES
The probable limits of error for the study cost estimates in this
report range from 307» above to 30% below the actual costs. Study cost
estimates are commonly used to estimate the economic feasibility of a
project before expending significant funds for piloting, market studies,
land surveys, and requisitions. They may be off by 3070 but they can be
prepared at relatively low costs using minimum data as follows (see Fig-
ure A-l).
Location of site;
Rough sketches of process flow;
Preliminary sizing and material specifications of equipment;
Approximate sizes of buildings and structures;
Rough quantities of utilities;
Preliminary piping;
Preliminary motor list; and
Engineering and drafting man-hours.
B-2
-------
5
o
X ~
Moit probable eo«t
-
1
4
4
1
4
4
i *
i
4
9 ~
i
<
1
s *
i
• *
i
i
Required luformotion
Well-developed sit* pfor plan & topographical mop
West a s.jts
Substations, nu^oer a siies, soec^icot-ons
Pretimmory hqr-.r.ng jsectfrcatsons
Engineered s">3t«-lin« diogron-s t?o*tr d iiqntj
Product cowct'T. loeorion ft (,tt r«qgi»ts. flow mortriQit a fii.sntd product
hortdhng a storoqe requirements.
w
*
?i?S
* * »•
?
*1
3
S *
15
5i
*
— ~
«
•o
3
c
o
m
0
C^
f
!if
Figure B-l. Estimating Information Guide
B-3
-------
COST INDEXES (Peters and Timmerhaus, 1968)
Host cost data which are available for immediate use in a prelimi-
nary or predesign estimate are based on conditions at some time in the
past. Because prices may change considerably with time" due to changes
in economic conditions, some method must be used for converting costs
applicable at a past date to equivalent costs that are essentially cor-
rect at the present time. This can be done by the use of cost indexes.
A cost index is merely a number for a given year showing the cost
at that time relative to a certain base year. If the cost at some time
in the past is known, the equivalent cost at the present time can be
determined by multiplying the original cost by the ratio of the present
index value to the index value applicable when the original cost was
obtained.
Present cost =
original cost index value at present time
index value at time original cost was obtained
Cost indexes can be used to give a general estimate, but no index
can take into account all factors, such as special technological advance-
ments or local conditions. The common indexes permit fairly accurate
estimates if the time period involved is less than 10 years.
Many different types of cost indexes are published regularly.
B-4
-------
Engineering News-Record Construction Cost Index
Relative construction costs at various dates can be estimated by
use of the Engineering News-Record construction index. This index
shows the variation in labor rates and materials costs for industrial
construction. It employs a composite cost for 2,500 Ib of structural
steel, 1,088 -fbm of lumber, 6 bbl of cement, and 200 hr of common labor.
The index is usually reported on one of three bases: an index value of
100 in 1913, 100 in 1926, or 100 in 1949.
Marshall and Swift (Formerly Marshall and Stevens) Equipment-Cost Indexes
The Marshall and Stevens equipment indexes are divided into two cate-
gories. The all-industry equipment index is simply the arithmetic average
of the individual indexes for 47 different types of industrial, commercial,
and housing equipment. The process-industry equipment index is a weighted
average of eight of these, with the weighting based on the total product
value of the various process industries. The percentages used for the
weighting in a typical year are as follows: cement, 2; chemicals, 48;
clay products, 2; glass, 3; paint, 5; paper, 10; petroleum, 22; and rub-
ber, 8.
The Marshall and Stevens indexes are based on an index value of 100
for the year 1926. These indexes take into consideration the cost of
machinery and major equipment plus costs for installation, fixtures, tools,
office furniture and other minor equipment.
B-5
-------
Chemical Engineering Plant Construction Cost Index
Construction costs for chemical plants form the basis of the Chemi-
cal Engineering plant construction cost index. The four major components
of this index are weighted in the following manner: equipment, machinery,
and supports, 61; erection and installation labor, 22; buildings, mate-
rials, and labor 7; and engineering and supervision manpower, 10. The
major component, equipment, is further subdivided and weighted as follows:
fabricated equipment, 37; process machinery, 14; pipe, valves, and fit-
tings, 20; process instruments and controls, 7; pumps and compressors, 7;
eletrical equipment and materials, 5; and structural supports, insulation,
and paint, 10. All index components are based on 1957 to 1959 = 100.
SIX-TENTHS FACTOR (Perry and Chilton, 1973)
Cost estimates in this report are given for processes that require
scaling up from a given capacity to a larger capacity (e.g., 100 gpm to
300 gpm and 600 gpm). Equipment size and costs were shown to correlate
fairly well by the logarithmic relationship known as the "six-tenths
factor." The simple form of this method is:
Cn - r°-6 C
where Cn is the new plant cost, C is the previous plant cost, and
r is the ratio of the new capacity to the old capacity.
This method is the best available for estimating the cost of the sys-
tems in this report since each system involves multiple pieces of equip-
ment, piping, instrumentation, etc. The exponent actually ranges from
B-6
-------
0.45 to 1.15 for different pieces of equipment, but in complex systems,
such as the ones described in this report, estimating the new capacity
cost for each piece of equipment is beyond the scope of this study.
Therefore, when scaling the costs up, for example, from a 100 gpm
plant size to other plant sizes, the exponent 0.6 is used as an approxi-
mation of the scale-up factor for the entire system. In each case, some
error may be involved using this method, but no other method is available
for this study.
ONE-FOURTH FACTOR (Peters and Timmerhaus, 1968)
The "one-fourth factor" uses the same principle as the "six-tenths
factor" with the exception that the exponent 0.25 is used instead of 0.6.
This factor is used to scale up labor requirements from one plant size
to a larger plant size, and takes into account the fact that larger plant
sizes require less than proportional labor forces due to economies of
scale.
PAYROLL CHARGES
These costs are the result of the many fringe benefits employees
receive in addition to their salaries. Recent emphasis on these bene-
fits in labor contracts make this cost substantial and it is steadily
increasing with time. The sum of fringe benefits may add between 15 and
40% to the wage rate of employees (Perry and Chilton, 1973), and the per-
centage varies widely from company to company. In this report, payroll
charges (fringe benefits) are estimated to be 307. of the wages paid to
both labor and supervision.
B-7
-------
OPERATING SUPPLIES
Operating supplies are items such as lubricating oil, instrument
charts, etc., that are neither raw nor repair materials. The cost of
these items is typically about 67, of operating labor (Jelen, 1970).
CONTROL LABORATORY COSTS
Depending on company practice and the type of project, operating
costs may include several charges by other units of the company, e.g.,
charges by a control laboratory.
Laboratory costs may be estimated as a percentage of operating
labor cost, in the range of 3 to 10%, but the complex situations as
high as 20% (Jelen, 1970). Since treatment systems require more labora-
tory support than typical production processes, in this report the cost
of these services is estimated to be 20% of operating labor costs.
MAINTENANCE AND REPAIRS (Peters and Timmerhaus, 1968)
A considerable amount of expense is necessary for maintenance and
repairs if a plant is to be kept in efficient operating condition. These
expenses include the cost for labor, materials, and supervision.
Annual costs for equipment maintenance and repairs may range from
as low as 2% of the equipment cost if service demands are light to 20%
for cases in which there are severe operating demands. The annual main-
tenance costs are given separately for each process in this report, and
range from 5 to 15% of the capital equipment cost of the various processes.
B-8
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DEPRECIATION
Depreciation is a periodic charge that distributes the installed
capital investment cost over its expected service life. Instead of
charging the cost of the equipment as an expense in the year of pur-
chase, a portion of its cost is charged against revenues each year
throughout its estimated .useful life.
In this report the estimated useful life is determined by using the
arithmetic average of the high and low lifetimes of equipment when a
range is given, or 10 years if the useful life is unknown. In some
cases, the useful life may be too high by U.S. Treasury Department Stan-
dard Guidelines (such as the 40-year life for the sedimentation process)
which allows an 11 year depreciation for chemical plant equipment (Perry
and Chilton, 1973). However, using 11 years for all equipment would either
understate or overstate the real cost in most circumstances. When the use-
ful life is unknown, 10 years is used to conform to the guidelines of the
federal government.
A zero salvage value is assumed in all depreciation estimates and
straight-line depreciation is used.
CAPITAL COST
Regardless of whether the capital investment is to be obtained from
company funds or made available by bankers, it is logical that the in-
vested capital earn a fair interest. If the company funds are not used
B-9
-------
for the new unit, then they could be invested to bear a reasonable in-
terest. If the capital is raised by issuing bonds or by borrowing from
another corporation, interest would be paid the investor. It should be
pointed out that in order to offer a company the incentive to invest its
money in a new plant, it should be able to realize as large an interest
rate as it could earn by making other investments. Since the risk is
somewhat higher than certain conservative investments, the interest rate
should be higher than that offered by these securities. Excessive in-
terest rates are not realistic in view of today's regulatory laws. Nor-
>
mally, an interest rate of from 6 to 8% on the unpaid principal is con-
sidered satisfactory.
In computing interest, it is necessary to remember that the amount
of interest will decrease each year since the unpaid balance is reduced
by the depreciation allowed the previous year. An interest rate of 10%
would average approximately 6.3% of the total principal each year if the
principal is repaid in 10 annual installments. It is customary to ex-
press the interest as a uniform fixed cost item each year.
An interest rate of 10% is used in these estimates based on the
cost literature (Chemical Engineering, 1975).
In reality, the interest will decline each year and, therefore, the
payment on the principal will increase if uniform principal plus inter-
est payments are made. Uniform payments for n periods required to pay
the original sum P can be computed from the following equation (Petroleum
Refiner, 1957).
B-10
-------
• / t . • \ **
R = P *(1 + i)
(1 + i)n - 1
where P = original sum
R = uniform periodic payment
n - number of payments
i = interest rate as fraction per period
Thie expression (1 - i)n is the compound interest expression found in
table form in many handbooks (Lange, Handbook of Chemistry). Value of
i(l + i)n/(l + i)n - 1 for various values of n and i are listed
below (Petroleum Refiner, 1957).
(1 + i)n - 1
n
1
2%
1.020
4%
1.040
6%
1.060
8%
1.080
10%
1.100
5 0.212 0.225 0.237 0.250 0.264
10 0.111 0.123 0.136 0.149 0.163
If the original investment was $1,000,000 and the loan was at 10%
interest for 10 years, the uniform payment would be
R = (1,000,000)
0-1(1 + O;.1)0
(1 + 0.1)i0 - 1
R = 163,000
In 10 years the total payment would be $1,630,000. Thus, the total
interest is $630,000 and the average interest rate would be
630*000 - 6.3%/year
10(1,000,000)
B-ll
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PLANT OVERHEAD
Plant overhead is a charge to the costs of the manufacturing facil-
ity which are not chargeable to any particular operation and are normally
charged on an allotted basis. Overhead includes such cost items as plant
supervision, plant guards, janitors, cafeterias, administrative offices,
accounting, purchasing, etc. Overhead costs will vary from company to
company and are usually calculated as a percentage of direct labor cost
or a percentage of installed capital investment for the entire facility,
and allocated to each operation based on its labor or investment cost.
Plant overhead can range from 40 to 60% of direct labor costs or 15
to 30% of direct costs (Jelen, 1970). We estimate that plant overhead
is 20% of direct costs in this report.
CONTINGENCY FOR CAPITAL INVESTMENT (Fowler, 1975)
The selection of a contingency figure for an estimate is a matter
of the judgment of the estimator. This judgment must consider several
factors, such as:
(1) Data basis—laboratory, pilot or plant
(2) Allowance for inflationary trends
(3) Knowledge of construction costs at plant location
Under favorable conditions, the contingency factor may be as low as
10%. However, lacking actual plant cost and considering present infla-
tionary trends, a contingency figure of 30% would be justified.
B-12
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In the past, cost indexes have been a reliable method of esti-
mating cost based upon plant costs in earlier years. The plant indexes
are more reliable when used on plant cost rather than pilot plant costs.
It is much more difficult to use them successfully when equipment is
pilot plant size or when a small amount of equipment is used. The use
of the indexes in the last 2 years has not been as accurate as in the
past and can result in too low a plant estimate. Uncertainty increases
if cost indexes are used to update plant estimates rather than actual
costs.
Unless the estimator has made the original estimate or knows what
the plant costs include, a large amount of uncertainty exists when pro-
jecting plant costs to other plant capacities and times. It is necessary
to know whether a plant investment includes the cost of utilities, such
as a steam boiler or cooling tower, or whether steam and utilities are
available at the battery limits of the unit in any amount required. It
is also important to know whether the plant investment includes the cost
of the land and site preparation. Only if these factors are known can
the contingency factor be kept to a reasonable figure of 30% or lower.
B-13
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REFERENCES
1. Chemical Engineering, p. 89, July 21, 1975.
2. Fowler, F. C., Chemical Engineering Consultant to Midwest Research
Institute and President of Research Associates, Kansas City,
Missouri, Personal Communication to C. E. Mutnma, October 15, 1975.
3. Jelen, F. C., Cost and Optimization Engineering. McGraw-Hill Book
Company, New York (1970).
A. Perry, R. H., and C. H. Chilton, Chemical Engineers Handbook. 5th Ed.,
McGraw-Hill Book Company, New York (1973).
5. Peters, M. S., and K. D. Timmerhaus, Plant Design and Economics for
Chemical Engineers. McGraw-Hill Book Company, 2nd Ed. (1968).
6. Petroleum Refiner. Process Design Primer. September 1957.
B-14
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BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-440/9-76-013
3. Recipient's Accession No.
4. Title and Subtitle
Wastewater Treatment Technology Documentation, Manufacture
of Toxaphene
5. Report Date
Pub. June 1976
6.
7. Author(s)
A. F. Meiners. C. E. Mumma.. T. L. Ferguson, and G. L. Kelso
8. Performing Organization Rept.
No- 4127-C
9. Performing Organization Name and Address
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
10. Project/Task/Work Unit No.
11. Contract/Grant No.
68-01-3524
12. Sponsoring Organization Name and Address
Office of Water Planning and Standards
U.S. Environmental Protection Agency
401 M Street, S.W.
P. f. 20460
13. Type of Report & Period
Covered
14.
Interim Report, Edited
IS. Supplementary Notes
Some editing was performed by EPA.
16. Abstracts
This report was prepared to provide technologic supporting information for toxic
pollutant effluent standards proposed by EPA under S307(a) of the Federal Water
Pollution Control Act Amendments of 1972. The report identifies potential
technologies, assesses implementation feasibility, estimates final effluent
characteristics and estimates installation and operation costs for Toxaphene
manufacturers.
17. Key Words and Document Analysis. 17o. Descriptors
Wastewater
Waste Treatment
Cost Analysis
Cost Comparison
Pesticides
Manufacturers
I7b. Identifiers/Open-Ended Terms
Toxic Pollutant Effluent Standards
Federal Water Pollution Control Act
I7c. COSATI Field/Group
18. Availability Statement
Release unlimited
19.. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21. No. of Pages
147
22. Price
FORM NTis-35 (REV. 10-73) ENDORSED BY ANSI AND UNESCO.
THIS FORM MAY BE REPRODUCED
USCOMM-DC B26S-P74
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