MIDWEST RESEARCH INSTITUTE
EPA-440/9-76-009
WASTEWATER TREATMENT TECHNOLOGY DOCUMENTATION FOR DDT
MANUFACTURE
FINAL REPORT
February 6, 1976
Contract No. 68-01-3524
MR| Project No. 4127-C
EPA Project Officer
Mr. Ralph H. Holtje
REGION
PROTECTION AG1NCT
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 • 816561-0202
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WASTEWATER TREATMENT TECHNOLOGY DOCUMENTATION FOR DDT
MANUFACTURE
by
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
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 • 816 561-0202
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r
PREFACE
This is one of four reports on pesticide-containing wastewater pre-
pared by Midwest Research Institute for the Offi~e 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 DDTo
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. 4l27-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 INSTITUTE
s. !n2t=t Director
Physical Sciences Division
February 6, 1976
ii
l-'
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INTRODUCTION
Midwest Research Institute has performed a comprehensive examination
of the wastewater treatment technology-applicable to aldrin/dieldrin,
endrin, DDT, and toxaphene.
The work was perform~d for the Environmental
Protection Agency under Contract No. 68-01-3524.
The basic object~ves of the program were:
(a) to perform an examina-
tion of the wastewater management practices currently employed in the manu-
facture
of the specified pesticides; (b) to examine the
state of the art of potential wastewater treatment processes that might be
applicable to this industry; and (c) to select those processes that would
be applicable to EPA control technology requirements for toxic pollutants.
The cost of existing and proposed wastewater treatment methods was of
special interest.
This
- report concerns the wastewater treatment technology for
DDT manufacture.
iii
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(X) NTENTS
List of Tables.
. . . . . . . . . . . . . . . . . . . . . . . . .
---
List of Figures
. . . . . . . .
. . . .
. . . . . . . . . . . . ."
DDT MANUFACTURE
Sections
I
II
III
IV
Summary. . . .
. . 0 . . . . . .
. . . . . . . . . 0 .
. . .
Characterization of the Industry
. . . .
. . . .
......
Background and General Characteristics. . . . . . . . . .
,
DDT Manufacture. . . . . . . 0 . . . . . 0 . . . . . . . .
Wastewater Characteristics 0 . . . . . . . . . . . . . . .
Wastewater Treatment Methods. .
. . ...
. . . . . . . . . 0
" Present Wastewater Treatment Methods. . . . . . 0 . . . .
Alternate Wastewater Treatment Methods. . . . . . . . 0 .
Effluent quality 0 . . . . . . . . . . 0 0 . . . . . 0 . .
Comparison of Estimated Effluent Quality with Effluent
Limitation Guidelines. . . . . . . . . . . . . . . . . .
Estimated Time Required to Implement Wastewater
Treatment Methods. . . . . . . . . . . . . . . . . . . .
Effluent Disposal Methods.
. . . . . . . . .
. . . . . . . .
Current Disposal Method. . . . . . 0 . . . . . . .
Effluent Disposal for Potential. Wastewater Treating
. . .
Methods. . . . . . . . . . . . . . . . .
. . . . . . .
iv
PaRe
vi
vii
1
7
7
9
14
19
19
19
34
37
38
41
41
41
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CONTENTS (continued)
v
Wastewater Treatment Cost Estimates. . . . . . .
. . . ~ .
Cost Estimates for Present Wastewater Disposal
Method. . . . . . . . . . . . . . . . . . . . . . . .
Cost Estimates 'for Solvent Extraction/Friedel-Crafts
Process. . .
. . . . . . .
. . . .
..........
Cost Estimates for Two-Stage Solvent Extraction
- with MCB . . . . . . . . . . . . . . . . . . . . . . .
" Or4er-Of-Magnitude Cost Estimates for Carbon Adsorption
and Synthetic Resin Adsorption Treatment Processes. .
References. . . . . . . . . . . . . . . . . . . . . . .
Appendix:
- 'Definition of Terms and Discussion of Conventional
Engineering Practices Used in Estimated..Gosts of ~
Pesticide Wastewater Treatment p'rocesses':: ... .
v.
Pa~e
43
43
43
58
58
72
.. '
-.a.~-.i : ..~ ~ oW'
~ .. ". ~:
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I .- -
No.
1
2
3
4
5
6
7
8
~
TABLES
Title
DDT MANUFACTURE
Summary of Estimated Costs (1975) For DDT .Wastewater
Treatment and Disposal Systems. . . . ~ . . . . . . . .
Typical Composition of Untreated Alkaline Wastewater. . .
Summary of Cumulative Pesticide Removal at 10-ppb
wad. . . . . . . . . . . . . . . . . . . . . . .
. . .
Effluent Limitations Guidelines for Halogenated Organic
Pesticides. . . . . . . . . . . . . . . . . . . . . . .
Estimated Capital Costs - 10,000 Gal/Day Wastewater
Trea tment Plant. . . . . . . . . . . . . . . . . .
. . .
Estimated Daily Operating Costs - 10,000 Gal/Day Plant. .
Summary of Estimated Daily Operating Costs for Waste
Treatment by Solvent Extraction/Friedel-Crafts
Method. . . . . . . . . . . . . . . . . . . . . . . . .
Total Investment and Annual Operating Costs for Complete
Carbon Adsorption and Resin Adsorption Systems. . . . .
Page
4
17
27
.39
45
46
57
71
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!2:.
1
2
3
4
5
6
7
FIGURES
Title
DDT MANUFACTURE
Production and Waste Schematic for DDT . . . . . .
. . . .
Envirogenics Process for Destruction of Pesticides in DDT
Manufacturing Waste Streams. . . . . . . . . . . . . . .
Chemistry of Friedel-Crafts Reactions with DDT and
Metabolites. . . . . . . . . . . . . . . . . . . .
. . .
Conceptual Flow Diagram for Two-Stage Extraction of
Alkaline Wastewater with MOnochlorobenzene (MCB) . . . .
Simplified Adsorption Summary - DDT. . . .
.....
. . .
Removal of DDT From Solution as a Function of Carbon.
!>osage. . . . . . . . . . . . . . . . . . . . . . . . .
Conceptual Flow Diagram of the Amberlite XAD-4 Resin
System and the Activated Carbon Adsorption System For
Treatment of DDT Production Plant Wastewater. . . . . .
vii'
Page
12
21
23
25
28
29
32
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. ,
DDT MANUFACTURE
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I
SECTION I
SUMMARY
The Montrose Chemical Corporation is currently the sole manufacturer
of DDT in the United States and produces DDT only at its plant at Torrance,
California.
The estimated production of DDT at this plant for 1975 is
. about 60 million pounds.
The 1975 sales price for DDT (as technical grade)
was about 50~/lb.
The production capacity of this plant is about 85 mil-
lion pounds of DDT per year.
In the production process, monochlorobenzene and chloral are condensed
in the presence of concentrated sulfuric acid.
Sulfuric acid is recovered
and reused.
DDT is recovered by crystallization.
The manufacturing process
is essentially continuous and the plant operates on a three shift per day
basis for 360 days/year.
The current manufacture of DDT at the Montrose plant results in the
production of alkaline wastewater (30,000 gal/day, containing 119 lb/day,
or about 423 ppm of DDT + DDD + DDE) and acid wastewater (10,000 gal/day)~
At present, these wastewaters are hauled off-site by truck and are disposed
of in an approved Class 1 California dump.
Sufficient land is available
for at least another 25 years of this type of dumping operation.
Another
1
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.
waste stream from the production facility consists of wastewaters from the
engine room and from sanitary waste (a total of 5,000 gal/day containing
o to 5 ppb or 0 to 0.0002 lb/day of DDT + DDD + DDE); this waste is dis-
charged to a sewer leading to a municipal sewerage system.
Other. waste-
water flow is contained within the Montrose plant by a closed-loop pro-
,
cessing'system, and use of a sealed-bottom holding-recycling pond.
Within
recent years, Montrose has substantially reduced the volume of their waste-
water.
MOntrose is currently interested in alternatives to the presently
used dumping operation and is investigating potential methods for treat-
ment and disposal of the alkaline wastewater.
Montrose is also considering
incineration of its acid wastewater as a possible alternate to the current
disposal practice.
This report examines in detail four alkaline wastewater treatment sys-
tems that have promise of effectively reducing the concentration of DDT and
related compounds (DDD + DDE) and the daily load.
!hese systems are:
(a)
a solvent extraction/Friedel-Crafts method; (b) a two-stage solvent extrac-
tion system; (c) activated carbon adsorption; and (d) synthetic resin
adsorption.
A summary of' estimated costs for these selected alkaline wastewater
treatment systems is shown in Table 1 for the current flow rate of 30,000
gal/day (20.8 gpm).
Assumptions made in preparing these estimates are de-
tailed in the report.
The concentration of DDT in the treated effluent is
also estimated.
2
I\....J
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The 1974 cost for hauling and dumping all segregated alkaline waste-
water from the Montrose plant was about 0.48~/lb of product DDT or $26.40/
1,000 gal.
The cost for hauling and dumping the acid wastewater in 1974
was about 0.33~/lb of product DDT or $55.56/1,000 gal.
Solvent Extraction/Friedel-Crafts
This method has been developed and tested through the pilot plant
stage.
The estimated capital investment for this system is $381,000 and
-.--------"
the estimated operating cost is O.89~/lb of product DDT or $49.17/1,000
gal. of effluent.
This system has the potential of producing an effluent
containing about -590 ppb (1.4- 1b/day) of DDT and related compounds (DDD
+ DDE) including about 36 ppb of DDT, 116 ppb of DDD and 438 ppb of DDE.
For this system, costs are also given in Table 1 for a system which
treats 45,000 gal/day of wastewater, which is the estimated effluent rate
corresponding to operation of the DDT plant at full production capacity.
The estimated capital investment for this production rate is $485,000 and
the estimated operating cost is 0.86~/lb of product DDT or $45.09/1,000
gal. of effluent.
This system has not been fully developed and some potential scale-up
problems have been noted.
The estimated time to complete the engineering
design, construct the treatment plant and put this system on-stream is
3 to 4 years.
Two-Sta~e Solvent Extraction System
The wastewa~er treatment system which appears to have the most promise
from both a technical and economic' standpoint is a two-stage extraction
3
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System
..
Table 1. SUMMARY OF ESTIMATED COSTS (1975) FOR DDT WASTEWATER
TREATMENT AND DISPOSAL SYSTEMS
(Concerning Wastewater at Montrose Chemical Corporation Plant,
Torrance, California) "
Alkaline Estimated Cost cents Cost per
Status wastewater DDTY in Capital Annual per pound 1,000 gal.
of flow rate wastewater investment operating of DDT of effluent
system !2.!!! ~ ~ ~ cost ($) cost ($) produced ($)
Currently 20.sW 30,OO~1 -423,000 -119 Unknown 285,500 0.48 26.40
used
Developed in 20.~ 30,00021 - 590 - 1.4 38l,ooGil 531,00011 0: 8gil 49.171.1
pilot plant 31.2 45,000 - 590 - 1.4 485 , ooGiI 730,00011 O.8GiI 45.0911
30,OOoW "- 32M - 0.008 101,OOoh! 82,800 0.14 7.66
20 . s'9.I
Hauling and dumping in
Class I landfill!!
Solvent extractionl
Friedel-Crafts
Two-stage extraction
with monochlorobenzene
Conceptual for
grant applica-
tion, partially
developed
~
Activated carbon bed Conceptual 20.~1 30,OOoW < 2sY < 0.00~ 230,000&1 35,000&1 0.06&1 3.33&1
adsorption system
Synthetic resin Conceptual 20. p)J 30,OOoW < 2~1 < O.OO~I 209,000&' 72,000&1 0.12&1 6.8sal
(XAD-4) adsorption system
~/
~I
£1
1/
1.1
~I Data for operations in 1974--provided by Montrose Chemical Corporation, Torrance, California (Ferguson and Meiners, 1975).
~I These values apply for alkaline wastewater currently being handled at the Montrose Chemical Corporation plant in Torrance,
California. In addition, 10,000 gpd of acid wastewater, which is not amenable to treatment by solvent extraction or the
other potential treatment systems listed, is currently disposed of in an off-site Class I dump.
Includes DDT plus DDD and DDE, except where otherwise noted. .
Including 1 ppb of DDT or DDD and 30 ppb of p,p'-DDE.
Represents DDT only; does not account for DDD and DDE which are present.
Study estimates based on unpublished cost data developed from pilot plant tests (Sweeny, 1973).
Order-of-magnitude cost estimates based on meager data.
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system which uses monoch1orobenzene as a solvent.
This system would re-
turn all of the recovered pesticide to the DDT process and would result
in an effluent which would contain very low concentrations of DDT.and DDD
(1 'ppb of DDT or DDD plus 30 ppb of ~,~'-DDE).
So~e operating steps for this system have been partially deve.1oped in
laboratory and pilot stages; under an EPA-supported grant project (approved
in January 1976), Montrose and its subcontractors will conduct an intensive
investigation to develop and evaluate this potential process.
For the two-stage solvent extraction system, the estimated capital
investment is $101,000 and the estimated treatment cost is 0.14~/lb of
product DDT or $7.66/1,000 gal. of effluent.
This system has a potential
capability to produce an effluent containing about 32 ppb (0.008 1b/day)
of DDT and related compounds including 1 ppb of DDT, 1 ppb of DDD, and
30 ppb of ~,~'-DDE.
The estimated time required to complete the development of this sys-
tem and to design and construct a full-scale treatment plant is 3 to 4 years.
Activated Carbon Adsorption
Laboratory isotherm data have been determined for the adsorption of
DDT on activated carbon and at least one pilot-scale test has been conducted.
Also, laboratory studies have indicated the technical feasibility of this
potential treatment system.
The activated carbon adsorption system would have a capital investment
cost of about $230,000 and ~he estimated unit, operating costs would be
5
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0.06~/lb of product DDT or $3.33/1,000 ga1. of effluent.
This system
would have the potential for producing an effluent containing less than
25 ppb (0.006 lb/day) of DDT only; no evaluation could be made regarding
the DDD and DDE content of the treated wastewater.
The estimated time required to develop and implement this process
for plant operation is 3 to 3.5 years.
Synthetic Resin Adsorption
----
The resin adsorption system would use a patented synthetic polymeric
adsorbent which can be regenerated with recovery of the pesticide.
No
technical or cost data were found in the published literature concerning
the application of this process to DDT wastewater.
The synthetic resin adsorption system would require. a capital invest-
ment of about $209,000 and the estimated operating cost would be 0.l2~/lb
of product DDT or $6.85/1,000 gal. of effluent.
This system would be
potentially capable of reducing the DDT content in the treated wastewater
to less than 25 ppb; no evaluation could be made regarding the DDD and DDE
content of the treated wastewater.
The estimated time required for development of this system and the
design and construction of a full-scale treatment plant is 3 to 4 years.
6
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SECTION II
CHARACTERIZATION OF THE INDUSTRY
'The background and general characteristics of the DDT manufacturing
industry are discussed below.
The manufacturing process is described and
the in-plant controls and wastewater characteristics are discussed.
BACKGROUND "AND GENERAL CHARACTERISTICS
DDT (dich1oro-diphenyl-trich1oroethane), for many years one of the
most widely used pesticidal chemicals in the United States, was first
synthesized in 1874.
Its effectiveness as an insecticide, however, was
only discovered in 1939.
Shortly tnereafte~ during and after World War
II, the U.S. began producing large quantities of DDT for control of
vector-borne diseases such as typhus and malaria abroad, and for agri-
culture, home and garden, and public health purposes domestically.
By
the early 1950's, 13 companies were involved in the manufacturing of DDT
and exports had become substantial (EPA, 1975).
Domestic production reached a maximum of about 188 million pounds
in 1963.
By the late 1960's DDT output had declined by about one-third,
e.g. ,
123 million pounds in 1969.
Production then declined precipitously,
to an estimated 60 million pounds per year in the early 1970's (EPA, 1975).
7
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Among the last firms to cease producing DDT were:
Geigy Corporation
(1966), Allied Chemical (1969), Olin Corporation (1969), Diamond Shamrock
Corporation (1970), and Lebanon Chemicals (197l)(EPA, 1975).
Domestic use peaked at about 79 million pounds in 1959, but declined
to about 18 million pounds in 1971 and was 22 million pounds in 1972.
More recent estimates of use are not available (EPA, 1975), but are pre-
sumably very small because of cancellation actions (see below).
Export lagged behind domestic consumption up to 1958, and the maxi-
mum did not occur until 1963.
From 1958 onward, the quantity of DDT
exported continued to exceed domestic consumption (EPA, 1975).
In January 1971, under a court order (EPA, 1975) following a suit by
the Environmental Defense Fund (EDF), EPA issued notices of intent to cancel
a11 remaining federal registrations of products containing DDT.
The princi-
pal crops affected by this action were cotton, citrus, and certain vegeta-
bles (EPA, 1975).
In March 1971, EPA issued cancellation notices for all registrations
of products containing the DDT-like insecticide, DDD (also called TDE).
DDD (2.2-bis(c-ch1orophenyl)-1.1-dich1oroethane) was well known to be a DDT
._~C/.~'11 1-,,\f1, ~ -I- t1~ }~:..:.A1.;- .~;-r' 1\. tf' ;. ._~;-,. .J;-.-.,.: :._; ~'''.
metabolite.
In August 1971, upon the request of 31 DDT formulators, a
hearing began on the cancellation of all remaining federally registered
uses of products containing DDT.
On June 14, 1972, the EPA administrator
announced the final cancellation of all' remaining crop uses of DDT in the
u.S. effective D~cember 31, 1972.
The order did not affect public health
8
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and quarantine uses, or exports of DDT.
The administrator based his deci-
sion on findings of persistence, transport, biomagnification, toxicological
effects and on the absence of benefits of DDT in relation to the availability
of effective and less environmentally harmful substitutes.
The effective
date of the prohibition was delayed for 6 months in order to permit an
orderly transition to substitute pesticides (EPA. 1975).
.. ..F. Y' ~-'\- .I."-"':"*'\.:-~
. ,.
J1) /
.'
Immediately following the DDT prohibition by EPA, the pesticides in-
dustry and EDF filed appeals contesting the June order with several U.S.
courts.
Industry filed suit to nullify the EPA ruling while EDF sought
to extend the prohibition to those few uses not covered by the order.
The appeals were consolidated in the U.S. Court of Appeals for the District
of Columbia.
On December 13, 1973, the court ruled, that there was "sub-
stantial evidence" in the record to support the EPA administrator's ban
o~ DDT.~nd its metabolites (EPA,'1975).
..,. ...,.-,:::A'~ .-t~~:.-! _i;--'~-:-''''''''7''O.
.I" ,..
-1 ;..--,
......'" .
, DDT' MANUFACTURE
DDT is currently (1975) manufactured at only one plant in the United
States, the Montrose Chemical Corporation facility at Torrance, California.
The plant also prepares DDT formulations.
The current production capacity
is about 85 million, pounds of DDT per year' (Ferguson and Meiners, 1975).
The current (1975)' production rate for DDT at this plant is reported to be
about two-thirds of capacity (Sobelma~ 1975a), and the present sales price
for DDT (as technical grade) is about 50~/lb (Sobelman, 1975a).
The rate
of production for 1976 and 1977 is expected to be within ~ 10 to 15% of the
current rate (Ferguson and Meiners, 1975).
The rate of production is
9
REGION In IoIBRARY crY
ENVIRONMlNTAL PROT~CTION AG~M
-------
essentially constant during the year.
Montrose produces technical grade
DDT for sale to WHO, AID, and directly to foreign nations in the Northern
and Southern Hemispheres.
DDT (dichloro-diphenyl-trichloroethane) is a name that covers a few
isomers, the most active of which is 1,1,I-trich1oro-2,2-bis(~-chloro-
phenyl) ethane.
Its manufacture is relatively simple:
it is made by con-
densing monochlorobenzene and chloral in the presence of concentrated
--"
sulfuric acid (Lawless et a1., 1972).
Production Chemistry
C2H50H + C12 ~ CC13CHO~
,1. H2S04
2. NaOH > CC13CH(C6H4Cl) 2 + H20
) C6H5Cl~
C6H6 + C12
75-80%, p,p'-isomer
15-20%, o,p'-isomer
plus related compounds
including DDD and DDE*
"4_+)- "~~.:-I. ~.,.;,---:;...~ "'-;-..~.""- iI' ~'-...."\
The biggest problems in DDT manufacture are in the recove~y of un-
reacted ingredients and in steering the reaction toward production of the
desired isomer.
The reaction is kept below 30°C .and takes place at
atmospheric pressure in a stirred batch reactor system (Lawless et al.,
1972) .
DDT recovery, according to a Diamond Alkali Company patent (Miller,
1960) is by crystallization.
Impure DDT is washed with a caustic solu-
tion.
The washed DDT is then "dried and, crystallized into solid material
(Ferguson and Meiners, 1974).
*
DDD is 2,2-bis~-chlorophenyl)-~,1-dichloroethane; DDE is dichloro-
diphenyl-dichloroethylene.
10
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I.
A detailed description of DDT manufacturing has been given by Porter
(1962) of the Diamond Alkali Company.
for DDT is presented in Figure 1.
A production and waste schematic
The manufacturing process is continuous except for batch input to
the first stage of the reactor.
The plant operates on a three shift per
day, 7 days a week basis, except for routine maintenance and lost time
caused by breakdowns in operating equipment.
The on-stream time each
calendar .year is reported to be 360 days (Ferguson and Meiners, 1975).
The age of the plant equipment ranges from 28 years old to brand
new (Ferguson and Meiners, 1975).
Data for the Montrose DDT operations at Torrance, California, for
production equipment, raw-materials, by-products and other proce~s wastes
and losses are listed below (Ferguson and Meiners, 1974 and 1975).
Production Equipment
Process continuity:
semibatch
Equipment dedication:
DDT only
Equipment age:
Not available
Material
Received from
1. Chloral Henderson, Nevada
2. C6H5Cl
Henderson, Nevada
'3. Oleum
Compton or
Dominques,
California
Henderson, Nevada
4. Caustic
Est. annual production:
6Q MM lb/year (1975)
Plant capacity:
85 MM. lb/year
Formulation on site:
Yes
Raw Materials
Received by
StoraRe
Tank cars
Steel storage
plant site
Steel storage
plant site
Steel storage
plant site
tanks on
Tank cars
tanks on
Tank trucks
tanks on
Tank trucks
Steel storage tanks on
plant site
11
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I
.NaOH
H20
Floor and
Surface
Dr.ains
Vent
labs and
Wash-:-Up
Baghouse
Vent
Scrubber
li uid Waste
Holding and
Recycling
Water Pond
Vent and C6HSCI Recycle
C6HSCI Reac tor DOT DOT Crystallizer Formulation
CCI3CHO (2-Stage) Separator Washer Dryer Plant
H2S04 F 'aker
.... Spent Dilute
N
Acid Caustic Package
Recycle Acid Waste Neutra - Shipment
Acid Recovery Acid lizer
Plant'
liquid
Wastes
To Class 1
Dump
Figure 1 - Production and waste schematic for DDT (Montrose Chemical Company)
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Reaction By-Products
Material
Form
Amount produced
(lb/lb AI)
Disposition
1. None
Other Process Wastes and Losses
Material
Form
Amount prod uced
(lb/lb AI)
Disposition
1. Active in-
gredient
2. Solvents
3. Na2S04
Aqueous
Unknown
Class 1 dump
Aqueous.
0.87
10-15 cu yard/day
Holding
cycle
dump
pond, re-
Class 1
Disposition of Technical and Formulated Products
.
Shipments
Warehouse
on site
Technical product
Container Transportation
Formulated products
Formulation Container Transportation
x
50-1b bags
Boxcar
WP (75% AI) 100-200 1b
lined
fiber
drums an4
75 -lb
boxes
Truck for export
via Los Angeles;
boxcar for other
destinations
Hoods are located at points having emissions potential and exhaust
under vacuum to a baghouse.
No scrubbers are used.
Liquid formulations
are no longer being made (Ferguson and Meiners, 1974).
Quality control:
Montrose maintains its own quality control 1abora-
tory for routine analyses.
Setting point is the major quality control used.
To date they have had no off-specific~tion material that could not be re-
worked (Fergusoq and Meiners, 1974).
13
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Personnel safety:
No unusal safety or hazard problems are associated
with DDT production.
Standard personnel safety equipment is used (Ferguson
and Meiners, 1974)0
WASTEWATER CHARACTERISTICS
This portion of the report presents a general description of waste-
water produced in the manufacture of DDT plus a specific description
of the wastewater generated by the MOntrose Chemical. Corporation.
General Wastewater Characteristics
According to Atkins (1972) the wastes resulting from the DDT manu-
f~cturing process include spent acids (hydrochloric and sulfuric),
sodium monochlorobenzene sulfonate, chloral, NaOH caustic wastewaters,
monochlorobenzene, and sulphonic acid derivatives.
The waste streams may
contain DDT in the 1 to 5 mg/liter range with DDE and other related com-
pounds present in amounts up to four times the DDT level.
The pH of the
waste is low and the salt content is high.
The volume of spent acid ranges from 440 to 550 gal/ton of DDT made.
This liquid contains 55% acid and 5% other organic substances and water.
The first washwater, about 800 gal/ton of DDT made, contains from 2 to 6%
spent acid.
The second washwater, also about 800 gal/ton of DDT made,
contains a very small proportion of spent acid neutralized with sodium
carbonate.
In addition, about 90 gal/ton issue from centrifuges which
contain a smaller proportion of the neutralized acid (Grindley, 1950).
14
L-..;
-------
I
Wastewaters also result from the absorption of the mixed gases from
the manufacture of chloral alcoholate.
The gases are first water washed,
producing a 10% by weight solution of hydrochloric acid (2,700 to 2,900
gal/ton of DDT).
The gases are then washed with a caustic soda solution,
producting a solution (220 to. 440 gal/ton of DDT) containing sodium hypo-
chlorite equivalent to 2.0% chlorine, sodium chlorate equivalent to 0.2
to 0.5% chlorine, some sodium chloride and excess sodium hydroxide
(Grindley, 1950).
Wastewater Characteristics - Montrose Chemical Corporation
The process portion of the DDT plant has no liquid waste outfall
(Ferguson and Meiners, 1975).
Wastewater flow is contained within the
plant by a closed-loop processing system, and use of a sealed bottom
holding-recycling pond, except for about.30,000 gal/day of alkaline
wastewater and about 10,000 gal/day of acid waste, which are currently
removed by truck and placed in a California-approved Class 1 dump
(Sobelman, 1975b).
There is some decomposition of DDT in the process reactor, and HCI
and S02 are present in the vent gas.
The vent from the reactor is scrubbed
with caustic and water.
Liquid from off-gas vent scrubbers and surface
drainage from the DDT plant area is collected in a holding pond and re-
cycled to the process.
This pond serves as the surge capacity for the
P--",
...
~~
y. .,.,
- .....~~
cooling water system (Ferguson and Meiners, 1975).
Sobelman (1975a) has
reported that there is essentially no evaporation of water from this pond.
v LJ
,..
15
-------
The holding pond (approximately 75 ft x 50 ft x 15 ft deep) has
been used for about 20 years, but was lined with cqncrete about 5 years
ago to overcome the necessity of installing test wells to monitor pos-
sible leaching (Ferguson and Meiners, 1975).
Montrose indicates that
this recycle system has been satisfactory and that no significant changes
would be made if it had to be constructed "today (Ferguson and Meiners, 197?).
At present, the segregated alkaline wastewater from the MOntrose DDT
plant averages about 30,000 gal/day, but it is estimated that the dis-
charge rate could range up to about 45,000 gal/day if the plant were
operated at the maximum DDT capacity of about 85 million pounds per year
(Sobelman, 1975b).
Currently, there is one combined source of about 5,000 gpd of waste-
water which is being discharged into the sewer of the Torrance, California,
plant for DDT production.
The breakdown and analysis of this waste stream
for DDT and metabolites (DDD and DDE) is as follows:
Source
Gal/day
DDT + DDD
+ DDE (ppm)
Lb of
DDT/day
"".-:-"'"K
Engine room
Sanitary waste
2,500
2,500
5,000
0-0.005
0-0.005
0-0.005
0-0.0001
0-0.0001
0-0.0002
" ,
. ..v-
I ~.; v""
\ ---":
.,
,
/"
Sources of the principal waste, alkaline wastewater, are neutralized
caustic liquor from the DDT-washing operation, tar pot drainings, spills
and tank drainings.
In 1975, this effluent discharge rate was 30,000 gpd
and all of this wastewater was disposed of in a Type 1 landfill.
A typical
analysis for 1975 of the alkaline wastewater is shown in Table 2.
16
I"-.......J
-------
.
Table
2. TYPICAL COMPOSITION OF UNTREATED ALKALINE
WASTEWATER!I (Montrose DDT Plant,
Torrance, California)
" .-:"'\
Component
Sodium sulfate
Sodium salt of
monochlorobenzenesulfonic acid
Caustic
DDT (+ DDE, DDD)
Miscellaneous (tars, etc.)
Water
~I Average flow rate, 30,000 gpdo
~I Values were calculated from the
Source: Montrose Grant Application
,
V:..
Ij :.
Lb/dav
Concentration
(ppm)~1
.~
,
21,615
3,670
76,883
13,054
!
50
119
139
255.550
281,143
. ~;J
2 ~ ~j ~
~ -,-"'i .
. ./
! ..
177.8
423.3
494.4
J
,
"
,
,
~
~ .
lb/day data...
(1975).
i
".
..,»
The discharge rate and characteristics of this waste are fairly con-
stant and do not show seasonal fluctuations.
The DDT plant is' on stream
at this level of two shifts per week and 12 ~onths/year, excep.t for break-
down and routine maintenance.
In-Plant Control - Montrose Chemical Corporation
All drains and process sewers at the Montrose plant have been iso-
lated from the city sewer syst7m.
Only sanitary waste and boiler blowdown
water go to the city sewers.
The restroom lavatory basins, however, dis-
charge to the holding pond system.
Water consumption has been reduced
from about 20 million gallons to about 2 million gallons per month.
Water from the holding pond is also used for cooling water wit~out fil-'
tration.
This practice has caused 'no problem to date.
The "recycle"
water typically contains 10 to 15 ppm DDT (Lawless .et a1., 1972).
17
-------
.
Some 10 to 15 cu yards/day of solid waste, bags, empty containers,
etc., are also taken by a commercial disposal service to a Class 1 dump,
which is approved for wastes of this type in California.
Inciner~tion
is not appro~ed.
Equipment washdown is not a problem as this is normally done only
during shutdowns.
Washwater goes to the recycle pond.
Spills and 1eakers
have not been a major problem.
One spill occurred when a truck carrying
technical material had an accident and spilled DDT.
The material was
picked up along with the top 3 in. of soil and disposed of (Lawless et
al., 1972).
According to the company, DDT losses to the sewer were < 1 1b/day for at
least 2 years before modification of the waste trea~ment facilities and
never more than 10 to 15 lb/day since the 1940's.
The amounts of DDT
entering and leaving various Los Angeles city and county sewers from all
sources are uncertain (Dreyfuss, 1971 and Schmidt et al., 1971), but DDT
is apparently adsorbed strongly on sewage sediments:
the county sanita-
tion district removed 0.5 million pounds of sediments said to contain
4,500 lb of DDT (Air/Water Pollution Report, July 1971).
This sediment
apparently went also to a Class 1 dump.
18
l~
-------
SECTION III
WASTEWATER TREATMENT METHODS
A discussion of existing and potential treatment, methods for DDT-
contaminated wastewater is presented in the following subsections.
PRESENT WASTEWATER TREATMENT METHODS
In 1975, the MOntrose Chemical Corporation plant for DDT production
(Torrance, California) was disposing of wastewater by ponding, partial
reuse and by hauling and off-site disposal in an approved Class 1
California dump and was not treating the wastewater prior to disposal
(Ferguson and Meiners, 1975).
ALTERNATE WASTEWATER TREATMENT METHODS
The MOntrose Chemi~al Corporation currently utilizes an off-site
Class 1 dump for disposal of wastewater.
MOntrose is interested in a
potential alternative to the presently used landfill, and is investigating
other potential methods for treatment and disposal of its principal waste--
alkaline wastewater.
Montrose is also considering incineration of its
acid wastewater as a possible alternative to the current landfill practice
(Ferguson and Meiners, 1975).
A discussion of each potential alternate treatment method is presented
in the following subsections.
19
l
-------
The Solvent Extraction/Friedel-Crafts Wastewater Treatment Method
Under an EPA Grant (EPA Contract No. 68-01-0083, EPA Office of
Research and Monitoring), the Envirogenics Systems Company at E1 Monte,
California, conducted an investigation and evaluation of a potential pro-
cess for treatment of alkaline wastewater from the DDT process.
This method
is reported to be unsuitable for processing acid wastewater (Ferguson
and Meiners, 1975).
This process, which has been developed through the
pilot-plant scale, involves a two-stage treatment as shown in Figure 2
---
(Sweeny, 1973).
Pesticides are extracted continuously from the DDT manu-
facturing waste into a hydrocarbon solvent. (typically heptane) using a
loop-type extractor.
The extract is concentrated by distillation (re-
~covered solvent is recycled), and the pesticide components in the con-
centrate are then condensed to an insoluble form by treatment with a
catalyst which causes a modified Friedel-Crafts reaction (Sweeny, 1973).
The first treatment step (i.e., the liquid-liquid extra~tion of DDT
and its metabolites) utilizes a continuous extractor unit (loop-pump sys-
tem) designed for hig~-shear mixing (Sweeny, 1973).
In this unit the
two-phase mixture of wastewater and solvent is pumped through a loop
configuration at a rate considerably faster than the rate of bleed off.
After suspended solids are separated by settling, the mixture of waste
liquor and solvent is passed through a coalescing unit ~nd the solvent
extract is separated by decantation.
~he solvent extract is then con-
centrated in a reboi1er with the vaporized solvent being returned after
condensation to an extractor feed. tank (Sweeny, 1973).
20
-------
Make Up
Solvent
(Heptane)
Catalyst
J l
"-
Reactant
Solvent
Recyc 'e
D
~
I
G
Extract
Solids
Separation
Coalesce
and
Decant
Solvent
Recovery
Friedel-
Crofts
Destruction
Montrose DDT
Plant Waste
Holding Tanks
Solid Waste
To landfill
Liquid Waste
To Sewer
Solid Waste
To landfill
N
....
STREAM MATERIAL BALANCE - LBS OR (GAL) - BASIS - 1 HOUR OF OPERATION
COMPONENT A B C D E F*' G H I J K L M N
Heptane 34(6) 337(60) 337(60) 34(6) 303(54) 303(54)
Water . 822 822. 877 5 877
4 soluble
non-pesticides
Pesti cides 2.5 2.5 2.5 2.5 2.5
Other 16 16 16
Pesti ci de
free-solids
Chlorobenzene 2.8(0.3)
AICI3 1.3
HCI 0.26
Organic Waste 6.3
Total
900 34
(90) (6)
. * Nominal Solvent loss for system
Source: Sweeny (1973)
1237
1216
21 34
. (6)
305
(54)
877 303
(54)
2.5 2.8
(0.3)
1.3 0.26 6.3
. Figure 2.
Envirogenics process for destruction of pesticides in DDT manufacturing waste streams
«1.5 gpm) pilot plant f10wsheet and material balance).
-------
In pilot-plant demonstration tests, a modified Friedel-Crafts method
was found to be suitable for the degradation of pesticides extracted from
DDT manufacturing wastewater (Sweeny, 1973).
Batches of concentrated
pesticide residue were treated with ch1orobenzene solvent/reactant and
aluminum chloride (A1C13) catalyst.
The catalyst was added and slurried
~n the ch1orobenzene over a 1.5-hr period, and the mixture was allowed to
react for an additional hour at about 120°C.
This technique involves the
use of strong Lewis acids, such as anhydrous A1C13' to catalyze Friede1-
Crafts condensations of the pesticide with itse1f,or a solvent/reactant
to form a large, nonreactive, insoluble species.
Figure 3 shows the
chemistry of some possible Friedel-Crafts reactions of DDT and metabolites.
The condensation products of the reaction consist of a tarry residue.
This process has a potential disadvantage in that the capital investment
required for the pump-loop extractor is expected to be higher than that
for a conventional extractor (Swank, 1975).
One objective of 'this process
~-.'-
development is to produce a treated effluent suitable for discharging to
..., ~(-'
.. j"t)
- }.
. '.
the municipal sewerage system.
,~
Other Potential Wastewater Treatment Methods
A,number of other potential treatment methods for DDT manufacturing
wastewater are described in the technical literature (Ferguson and Meiners,
1974; and Sweeny, 1973).
These potential treatment methods are two-!:::t:a_~e~...n
s~!!~~~~~~ra~~ activated carbon adsorption, synthetic resin adsorption,
reductive degradation, photochemical irradiation, and ozonation.
,.' ~.'.'-~ :--,.:. . _.''-.L-'~' -,.-,.~.."'t ".-...-~~.
These
potential methods are discussed below.
22
-------
CI
~ ~I
H-C-C-el +
~ CI
CI
DDT
Alel3
.---
CI
~11
e=c
~CI
CI
DDE
+
RCI
CI
~11
C=C
~~I
CI
DDE
+ RCH=CH2
..
. Ct'
~11+
H-C - C
~~I
CI
~.
CI
~CICI
HQ-oC-~~O(c~CI
H "" \
CI-C-CI
CI CI
AICI,.
'--
..
CI
«
C=C
R-OCI
CI
Aiel HIGH
3 MOLECULAR
RCI WEIGHT
PRODUCTS
CI ~ H
«CH3
. R 6~'
'cJQJ
H" \ el
CH3
Source: Adapted from Sweeny (1973).
Figure 3. Chemistry of Friedel-Crafts reactions of DDT and metabolites.
23
-------
Two-Sta~e Solvent Extraction - A grant application (No. R8042930l) by
Montrose Chemical Corporation for research and demonstration of a potential
process for treating alkaline wastewater to remove DDT and its metabolites
was approved by EPA in January 1976.
This potential process, which is re-
ferred to as a two-stage solvent extraction process, consists essentially
of the operating steps shown in FJgure 4.
1.
The first-stage consists of extraction of the alkaline wastewater
with monochlorobenzene (MCB) in a high shear extra.ction system.
Fo llowi ng
separation of solids by settling, the mixture is allowed to coalesce and
the solvent phase is separated from the aqueous phase by decantation.
The
separated solvent phase may be returned to the DDT process or to the waste-
water treatment process.
The separated solid waste can be landfilled.
2.
The second-stage consists of extraction of the aqueous phase (from
. .
Step 1) with MCB in a packed-bed column, followed by decantation to separate
the solvent phase and treatment of the aqueous waste by adsorption on a
carbon bed filter to remove residual MCB.
The aqueous waste is discharged
to a sewer.
Periodically, MCB is removed from the carbon bed by application
of heat and vacuum and the recovered MCB is returned to the extraction
process.
Activated Carbon Adsorption System - Considerable laboratory data are avail-
able concerning the adsorption of DDT on activated carbon.
The effective-
ness of. powdered activated carbon on the removal of DDT from water has been
reported by Sigworth (1965) and Whitehouse (1967).
Sigworth's studies were
24
-------
Alkaline Wastewater 30,000 gpd
",423 ppm DDT+
to.)
V1
DDE + DDD
-
- High Shear Solids Coalesce Decant -
MCB Extraction Separation Solvent Pha
Return to D
or to Treat
Aqueous Phase
~ .
Solid Waste .MCB
to landfj II
-0
Q)
I:C '-
0
-0-
Q) U
..::I. a
U l:
a x
a.. w
Decant
and-
Filter
Aqueous Phase to
Solvent Phase I Sewer 30,000 gpd
se-
DT Process
ment Process
N 2 ppb of DDT+ DDT
""30ppb of P, p'-DDE
Figure 4.
I \ ~ I \.
Conceptual flow diagram for two-stage extraction of alkaline
.wastewater with monochlorobenzene (MCB)
., .
,7.. .. J
-------
conducted with initial concentrations of 5 mg/liter DDT, and he concluded
that 10 mg/liter carbon dosages in a treatment plant would accomplish 90%
removal of most of the pesticides that are extensively used today.
Whitehouse investigated the effect of carbon dosage and contact time on.
DDT removal from water, with initial DDT concentration of 0.0044 mg/liter
and showed that over 90% DDT removal could be obtained after 1 hr and
carbon dosages above 100 mg/liter.
The effectiveness of granular activated beds to remove DDT from water
has been investigated by Robeck (1965).
Following passage through two car-
bon columns, it was found that an initial concentration of 10 ~g/liter DDT
in water was reduced to below 0.1 ~g/liter.
These data are shown in Table
3.
.,y .,
Hager and Rizzo (1974) have prepared isotherm data for the adsorption
of DDT on carbon (Figure 5)0
The isotherm data of Hager and Rizzo (1974)
are not in agreement with the data reported by Whitehouse.
As shown in
,
"
Figure 6, a concentration of 0.2 ~g/liter (equivalent to a 95% DDT removal
from a solution containing 4.4 ~g/liter) would require over 200 mg/liter
of the type carbon that Whitehouse investigated.
In contrast, extrapolation
of the data of Hager and Rizzo (Figure 5) indicates that this same final
,/.
concentration (0.2 ~g/liter) would require only about 4 mg/liter of the
type of carbon that these investigators used (0.12% weight pickup).
This
large difference in reported carbon capability must obviously be resolved
before meaningfu~ statements can be made concerning the practicality of
DDT removal from water with carbon.
26
-------
jVE-w
Table 3. SUMMARY OF CUMULATIVE PESTICIDE REMOVAL AT 10-PPB LOAD
Pesticide removed (%)
Process DDT Lindane Parathion Dieldrin 2.4.5-T Ester Endrin
Chlorination (5 ppm) < 10 < 10 75 < 10 < 10 < 10
Coagulation and 98 < 10 80 55 65 35
Filtration
Carbon: Slurry
5 ppm 30 .> 99 75 80 80
10 ppm 55 > 99 85 90 90
20 ppm 80 > 99 92 95 94
N Carbon: Bed
.....
0.5 gpm/cu ft > 99 > 99 > 99 > 99 > 99 > 99
Source:
Robeck, 1965 (p. 198).
-------
%Weight Pickup
0.1
FILTERED
reo .
I
EPA
. LIMITS
FILTERED SAMPLE
FILTERED
ICO
I
N
co
0.01
0.1 1.0 10.0 100.0 .
Contaminant Concentration (Parts Per, Billion)
Source: Hager and Rizzo (1974)
Figure 5.
Simplified adsorption summary - DDT.
" ,
. .. ~.,
v ~ I;, ,
" 1.'. .-'
-------
100
90
7
-
E-4
Z
~ 60
U
0:::
~
n...
- 50
Q
N ~
\D 0 4
~.
~
0:::
E-4 30
o
Q
20
1
o
50
Source: Whitehouse
Figure 6.
\
\
\
o
DDT Concentration = 0.0044 ppm
Contact Time = 1 Hour
pH = 6
A Barneby-Cheney XH-2 (Wood Charcoal)
. 0 Fisher' Cocoanut'
100 .
150 200
CARBON DOSAGE (mg/l)
(1967)
250
300
\
Removal of DDT from solution as a function of carbon dosage.
. """
~' ,,:. ~
, '., ~ ". \! 4'"' 1
-------
Although the treatability of a particular wastewater by carbon and
the relative capacity of different types of carbon for treatment may be
estimated from adsorption isotherms, carbon performance and design criteria
are best determined by pilot tests.
Pilot carbon column tests are per-
formed for the purpose of obtaining design data for full-scale plant con-
struction.
Adsorption isotherms are determined using batch tests, but
the actual treatment of wastewater by activated carbon most often is ef-
----
fected in a continuous system involving packed beds similar to filtering
opera tions .
Pilot tests are required in order to provide the required
estimates of performance that. can be expected in a full-scale unit.
In-
formation which can be obtained from pilot tests includes:
* Type of carbon
* Contact time
* Bed depth
* Pretreatment requirements
*
Carbon dosage
*
Breakthrough characteristics
* Affect of biological activity
*
Headloss characteristics
Pilot carbon column tests for the removal of DDT from wastewater may
have been performed; but no pilot-scale data were available to the investi-
gators during this project study.
A conceptual flow diagram for a complete activated carbon system is
shown in Figure 7.
In this conceptual treatment system, the raw alkaline
wastewater from the DDT production plant is combined with a coagulant and
treated in a sedimentation process.
Settled solids (sludge) are sent to
a landfill operation.
Wastewater discharged from the sedimentation step
30
-------
is treated in a filtration process to remove suspended solids.
The filter
is backwashed periodically to maintain good filtration efficiency.
The
filtered wastewater is then pumped to an activated carbon bed adsorption
process.
The carbon adsorption process would consist essentially of two
on-stream adsorption units operating in series and the required auxiliary
equipment (pumps, piping, process instrumentation, etc.).
Synthetic Resin Adsorption System - The Rohm and Haas Company has developed
a synthetic, polymeric adsorbent which shows excellent promise of removal
of chlorinated pesticides from wastewater.
In this process, pesticides
are adsorbed on Amber1ite XAD-4, a synthetic, polymeric adsorbent possessing
high porosity (0.50 to 0.55 m1 of pore per milliliter of bead) high surface
2
area (850 m /g) and an inert, hydrophobic surface (Kennedy, 1973).
The
resin is regenerated with an organic solvent (such as isopropyl alcohol)
and the adsorbed pesticides are recovered in a concentrated form.
To the best of our knowledge, pilot-scale tests of the treatment of DDT
wastewater by this process have not been performed and no specific cost
data on such a potential process are available .in the published literature.
A conceptual process flow diagram for a resin adsorption system is
shown in Figure 7.
This system would be similar to the carbon adsorption
system described in this report.
The major process steps would involve
sedimentation and filtration to remove suspended solids and finally treat-
ment in the resin process to remove dissolved DDT and related compounds.
31
-------
1.1)
N
Untreated DDT
Alkaline Wastewater Coagulation Sand : Resin Process
30,000 gpd .. & Sedimentation ... Fi ftration . - or Activated
-
DDT Concentration: Process Process j Carbon Process
423,000 ppb '
t
1 ;p Monit
Fi Iter
Sludge - Backwash
~
,
oring Point
To Landfill
Effluent Discharge, 30,000 gpd
DDT Concentration: <.25 ppb
Fi~!!re.,,7. Conceptual flow diagram of the Amberlite XAD-4 resin system and the activated
. . .1-. ., carbon adsorption system for treatment of DDT production plant wastewater.
. . .~ ( ..j
-------
. Reductive Degradation - This method-consists essentially of ,contacting waste-
water with catalyzed iron, aluminum or zinc reductants which degrade the
pesticides.
Copper has been used as a catalyst.
Experimental laboratory tests have shown that the reductive degrada-
tion method, while suitable for degradation of DDT, is largely ineffective
for DDE-containing waste (Sweeny, 1973).
Early studies developed the in-
formation that DDE, a principal ingredient of the wastewater from produc-
tion of DDT was poorly degraded under ordinary conditions with catalyzed
iron, aluminum or zinc reductants.
Other experiments showed that DDE may
be reduced by Raney nickel; however, problems of the reaction stopping
because of hydrous oxide coating of the reductant were observed.
Later
work with more powerful reductants did not reveal a practical metho4 for
decomposing all of the pesticide components of DDT manufacturing waste.
. Photochemical Irradiation - This potential method for destruction of DDT
B
manufacturing waste consists essentially of exposing the waste to ultra-
violet radiation which results in photochemical oxidation.
Extensive laboratory investigations of this potential treatment tech-
nique have been made (Sweeny, 1973).
Treatment variations which were
I
;
.
studied included air or oxygen sparging of a pesticide solution, use of
selected hydrocarbon solvents, dehydrohalogenation before irradiation,
and other techniques (Sweeny, 1973).
-
33
I
-------
. -"
Photochemical irradiation of DDE leads to a reasonably rapid decomposi-
tion, but DDT is degraded more slowly and DDD still more slowly (Sweeny,
1973).
Ozonation - Experimental laboratory studies have been conducted to determine
the feasibility of destroying DDT waste materials by oxidation with ozone
(Sweeney, 1973).
The method consists essentially of passing ozone, prepared
from pure oxygen, through organic solvent solutions containing DDT, DDE,
or DDD.
Test results showed that ozonation degrades DDE, that DDD and DDT
are more slowly attached, and that ozonation of the solvent is
~
a substantial ~
J
problem (Sweeny, 1973).
EFFLUENT QUALITY
Solvent Extraction/Friedel-Crafts Treatment
Sweeny (1973) reports that the solvent extraction step can typically
reduce the pesticide concentration as follows:
DDT (both ~,~'- and ~,£'-) reduced 2,000- to 5,000-fold .
(3,500-fo1d average)
,p,,p'-DDD reduced 400- to 2,000-fold (1,200-fo1d average)
,p,,p'-DDE reduced 400- to 600-fo1d j
~,,p'-DDE reduced 120- to 400-fo1d
(for total DDE average is
,:..~
",.., B60-fo1d)
-...y
.... "){I
" ~-
"0
,
Data by Sweeny (1973) on wastewater composition indicate that DDT is
about 30% of the total pesticide present, that DDD is about 33% of the
total pesticide, and that DDE is about 37% of the total pesticide content.
34
-------
In addition, Sweeny (~973) has reported. that in experimental test-
ing, the Friedel-Crafts treatment of extracted pesticide-laden residue
(from the loop-extractor operation) led to apparently complete destruction
of p,p'- and o,p'-DDT, and p,p'-DDD and a 400- to 1,000-fold reduction
(average of 700-fold reduction) of the p,p'- and o,p'-DDE.
Thus, the
solid waste product from the Friedel-Crafts treatment would contain
essentially no DDT or p,p'-DDD and only small quantities of DDE.
On the basis of the above data, the pesticide content of the treated
wastewater discharged from the extraction step can be estimated as follows,
using the typical composition shown in Table 2 and the average extraction
data shown above:
I
DDT present in raw wastewater ~ 423,000 x 0.3 = 126,900 ppb
--
DDT
reduced from 126, 900 ~Pb. to ( 126,900 \
3,500 J
= - 36 ppb
DDD present ~ 423,000 x 0.33 ~ 139,600 ppb
'\
I!> 'j"
~'. .,,-'J
"~ "~
r
. ( 139 600)
DDD reduced from 62 mg/l~ter to ' = -116 ppb
1,200
DDE present ~ 423,000 x 0.37 ~ 156,500 ppb
"!
DDE reduced from 70 mg/liter to (156,500) = -435 ppb
360
Then the total estimated pesticide remaining in the treated wastewater
..&.'~
is 36 (DDT) + 116 (DDD) + 435 (DDE) = 587 ppb or 590 ppb (rounded).
35
-------
Process for Two-Sta~e Extraction with Monochlorobenzene
The Montrose Chemical Corporation grant application (1975) states that
the reduction of the current alkaline wastewater discharge of -423 ppm to
j
I
1 ppb of DDT or DDD and 30 ppb of ,p'E' -DDE is a tentative objective, which,:
is believed to be achievable. .
I
~.
Activated Carbon Adsorption System
Robeck (1965) has reported test data for coagulation, filtration and
..--
carbon adsorption of DDT wastewater; the influent contained 10 ppb DDTo
Coagulation and the filtration removed 98% of the DDT and carbon adsorption
removed more than 99% of the PDT.
Similar results were reported for waste-
waters 'containing other chlorinated hydrocarbon pesticides.
In this study,
it was considered that a similar overall removal efficiency would apply
for DDT wastewater discharged by the Montrose Chemical Corporation plant of
Torrance, California.
On this basis the estimated DDT content in the treated
effluent can be estimated as follows:
Estimated DDT content of untreated wastewater ~ 127,000 ppb
DDT retained in wastew~ter following coagulation and filtration is
0.02 x 127,000 or 2,540 ppb
DDT retained in wastewater following carbon adsorption treatment
< 0.01 x 2,540 or < 25 ppb.
Synthetic Polymer (XAD-4) Adsorption System
~
~.'"
No specific data were found concerning the effectiveness of removal
of DDT from prod~ction plant wastewater by a synthetic polymer system.
36
.-
,.
~....
~ c
\
, .
-
"
J
!
I
-------
It was considered in this case'that the removal of pesticide by syn-
thetic polymer adsorption would be the same as for carbon adsorption.
Thus, the DDT retained in wastewater following treatment in the resin ad-
sorption system is estimated to be less than 25 ppb.
COMPARISON OF ESTIMATED EFFLUENT QUALITY WITH EFFLUENT LIMITATION
GUIDELINES
The Envirorunental Protection Agency in its "general instructions"
to contractors (Part II) describes effluent limitations guidelines in
terms of Level I, II, and III technology.
These levels of technology are
briefly defined below and replace the terms "best practicable control
technol~gy currently available" (BPCTC~, "best available technology
economically achievable" (BATEA) and "best available demonstrated control
technology" (BADCT).
Level I - Control and Treatment Techno1ogv
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 cate-
gory or subcategory, but shall be leased 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
37
-------
industrial category, but is to be determined by identifying the very best
control and treatment technology employed by a specific point source within
the industrial category or subcategory, or where it is readily tr~nsferable
from one industry process to another, such technology may be identified as
Level II technology."
Level III - Control and Treatment Technolo~y
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 po1-
1ution control are available through the use of improved production pro-
cesses and/or treatment techniques."
Effluent limitations guid~lines have been tentatively recommended
(Weston, 1975) for the "Halogenated Organic Pesticides" subcategory of
the "Pesticides and Agricultural Chemicals Industry" category (Table 4).
ESTIMATED TIME REQUIRED TO IMPLEMENT WASTEWATER TREATMENT METHODS
The estimated minimum time period required to .implement each alternate
wastewater treatment system is discussed below.
These estimates are based
upon (a) an analysis of information concerning probable difficulties in
accomplishing the required process development and (b) the experience and
judgment of MRI project personnel.
The solvent extraction/Friedel-Crafts method has not been fully dec
ve10ped and some potential scale-up problems have been noted (Swank, 1975)..
The estimated time required .to complete the engineering design, construct
the plant and put this process on stream is 3 to 4 years.
38
-------
Table 4.
EFFLUENT LIMITATIONS GUIDELINES FOR HALOGENATED ORGANIC
PESTICIDES (Tentative Recommendations)
Effluent limitations
Average of daily values
for 30 consecutive days Maximum for
Level of Effluent shall not exceed anyone day
technology characteristic kg/kkg~/ mg/li ter kg/kkg mg/liter
Level I BOD5 1.01 1.80
(BPCTCA) Phenol 0.0015 0.002
TSS 84 156
Level II BOD5 1.01 1.80
(BATEA) Phenol 0.0015 0.0020
COD 1.53 2.12
TSS 42 78
Level III BOD5 1.01 1.80
(BADCT) Phenol 0.0015 0.0020
TSS 42 78
~/ kg/kkg Production is equivalent to pounds per 1,000 pounds production.
Source: Weston (1975).
The two-stage solvent extraction system using monochloro~enzene as
solvent is only partially developed; the system has not been tested thor-
ough1y on a laboratory scale and only limited pilot-plant testing has been
done.
The estimated time to complete the development and design and con-
struct a plant is 3 to 4 years.
The available data indicate that only a very limited amount of labora-
tory test work has been done on the potential carbon adsorption process.
The estimated time required to develop and implement this process is 3 to
3.5 years.
;-"
. '
39
-------
No research and development work have been reported on the application
of the resin adsorption process to DDT wastewater.
The necessary laboratory.
scale and pilot-scale process development on this potential proce~s would
probably require 1.5 to 2 years.
The engineering design and construction
of a full-scale treatment facility is estimated to require an additional
1.5 to 2 years.
Therefore, the total estimated time required for imp 1emen-
tat ion is 3 to 4 years.
q~'
40
-------
SECTION IV
EFFLUENT DISPOSAL METHODS
A brief discussion of the currently used disposal method and other
-----
potential disposal procedures is given in the following subsections.
CURRENT DISPOSAL METHOD
The current disposal method used for effluent from the Montrose
Corporation plant (Torrance, California) consists of hauling the DDT-
containing liquid waste (acid wastewater and alkaline wastewater) by
truck to a Class -1 dump, which is approved for wastes of this kind in
California.
Sobelman (1975a) has reported that sufficient land is avai1-
able to permit these landfill operations to continue for at least another -
25 years.
EFFLUENT DISPOSAL FOR POTENTIAL WASTEWATER TREATING METHODS
In the solvent extraction, modified Friedel-Crafts process, the ef-
fluent is treated with solvent to extract DDT and related compounds and
the treated wastewater is then discharged to a plant sewer leading to a
municipal sewage treatment plant.
41
) .
,~
/
1 -
. 4
"
./
c
-------
The extracted DDT and related compounds are treated by a modified
Friedel-Crafts reaction to condense the pesticide fractions and form in-
soluble and nonreactive products which can be safely disposed of by a
landfill operation or by incineration.
'~
For the two-stage solvent extraction system, the waste consists of :-
treated effluent and separated solids.
The effluent would be discharged
...
{>.~
'\ ~ '
to the municipal sewage system and the solid waste could be landfilled. - I
~.7
In the carbon adsorption system, the pretreatment operations would
include coagulation, sedimentation and/or filtration to remove suspended
solids and some of the pesticide.
Settled solids or filtration residue
could be disposed of by a landfill operation or an incineration step.
Clarified wastewater from the pretreatment would be processed in a carbon
adsorption system to .adsorb pesticide on granules of activated carbon.
The spent carbon could be regenerated using a regeneration furnace equipped
with a suitable off-gas treatment system or disposed of by incineration
and replaced with a fresh charge of carbon.
A 1;
The treated wastewater, which ~~ j
~ .
\ ~
,;J
-------
SECTION V
WASTEWATER TREATMENT COST ESTIMATES
COST ESTIMATES FOR PRESENT WASTEWATER DISPOSAL METHOD
MOntrose Chemical Corporation has estimated that in 1974 the total cost
of hauling and dumping the process wastewater amounted to about $485,500
($285,500 for alkaline waste and $200,000 for acid waste (Ferguson and Meiners,
1975» .
I
The operating manpower cost associated with wastewater disposal at
the Torrance plant has been estimated by Montrose representatives to be
about $39,400/year (Ferguson and Meiners, 1975).
The basis of this cost
is 4 man-hours per shift, three shifts per day (for 365 days), a labor
rate of $5/hr and an overhead factor of 1.8.
On the basis of estimated 1974 production (about 60 million pounds),
the unit disposal costs for hauling and dumping were:
for alkaline waste,
0.48~/lb of product DDT
for acid waste,
0.33~/lb of product DDT
COST ESTIMATES FOR SOLVENT EXTRACTION/FRIEDEL-CRAFTS PROCESS
Study cost estimates of the type described by Perry and Chilton (1973).
(probable error range i 30%, see Appendix B) were prepared for two average
43
-------
I
DDT manufacturing wastewater discharge rates:
30,000 gal/day, which is
the current (July 1975) rate for the Montrose plant at Torrance, California
(for a current DDT production rate of 60 million pounds per year) and
45,000 gal/day, which is estimated to be the discharge rate which would
apply if the production plant were operated at maximum capacity (85 million
pounds per year of DDT).
On the basis of data provided by Montrose
(Sobelman, 1975a and 1975b),
the 30,000 gal/day and 45,000 gal/day plants
..-.--'
were sized to have treatment capacities about 67% in excess of average
daily requirements to allow for reprocessing of some treated wastewater
which is off-specification and make-up capability after temporary forced
shutdowns for repairs of the wastewater process system.
The cost estimates are based on preliminary cost data reported in
unpublished literature by Sweeny (1973) for a 10,000 gal/day plant (see
Tables 5 and 6).
The capital cost data were adjusted to allow for some
additional construction costs (electrical installation, instrumentation,
thermal insulation, and engineering and supervision) and for cost increases
due to inflation and then used to estimate costs for other plant sizes.
The utility~costs were updated on the basis of cost data provided by the
Montrose plant (Sobelman, 1975a).
44
-------
.
Table 5.
ESTIMATED CAPITAL COSTS - 10,000 GAL!DAY
WASTEWATER TREATMENT PLANT
Item
Costs for
JulV 1973
Costs for
June 1975
Process equipment
Process equipment labor
Process materials
Process material labor
Electrical installation
(12% of purchased equipment)!!
Instrumentation and controls
(15% of purchased equipment)~!
Thermal insulation
(8% of purchased equipment)~!
Home office expense
Field expense
Engineering and supervision
(35% of purchased equipment)~!
$16,480
1,980
9,830
6,590
$20,930
2,200
12,480
7,300
2,512
3,140
9,830
6,590
1,674
11,177
7,315
7,325
Subtotal (rounded)
$51,300
$76,050
Start-up and modification
(10% of subtotal)
Contingencies
(20% of subtotal)
5,130
7,600
10,260
15,200
Total (rounded)
$66,690
$98,900
~! Using cost factors recommended by Peters and Timmerhaus (1968).
Source: Data used in cost estimates were obtained from pilot-plant
studies (Sweeny, 1973).
45
-------
Table 6.
ESTIMATED DAILY OPERATING COSTS--10,000 GAL/DAY PLANT
Costs for Costs for
July 1973 September 1975
Utilities
Steam $ 31.5o!/ $ 55. 13
Power 42.90!./ 75.08
Cooling water 2.4o!./ 4.20
Raw materials
.--.---- 13 . 30El
Solvent loss (makeup) 23.55
Solvent/reactant 5 .40£/ 11. 88
Catalyst 37 .8oEl 65.29
Labor
One operator (half-time) 97 . 20 119.33
To ta 1 $230.50 $354.46
!./ These costs were updated using a
cost data provided by MOntrose
and Meiners, .1975).
~/ These raw material costs were updated according to the ratio of
prevailing prices for the dates shown (Chemical Marketing Reporter).
£/ The solvent/reactant cost was updated by using a factor of 2.2 as
recommended by MOntrose Chemical Corporation (Ferguson and Meiners,
1975).
Source: Data used in cost estimates were obtained from pilot-plant studies
(Sweeny, 1973).
factor of 1.75 on the basis of
Chemical Corporation (Ferguson
46
-------
I
Cost Ad;ustments for Inflationary Effect and New Labor Rates
Marshall and Swift (M&S) Equipment Cost indices (1926 = 100), as
described in the literature are used for cost adjustments due to inf1a-
tion for process equipment and materials (these indices are discussed in
Appendix B).
For 1973, index = 344.1 (Chemical Engineering, 1975b).
For 1975, index = 437.0 (Chemical Engineering, 1975b).
Ratio of 1975 index to 1973 index is 437.0:344.1 = 1.27
A ratio of annual labor rates reported in the literature is used for
updating construction labor costs (Lowenstern, 1973 and 1975).
For 1973,
the contract ccnstruction labor rate is reported to be $6.38/hr and the
corresponding rate for March 1975 is $7.11/hr.
Thus, the labor rate
ratio is 7.11:6.38 or 1.11.
For home office expense, the inflation in
charges for finance and insurance from 1973 to 1975 is used,
i.e.,
$4.06/hr/3.57 = 1.137 as cost escalation factor (Lowenstern, 1975).
Capital Investment
Data on the capital investment for a 10,000 gal/day waste treat-
ment plant based on information obtained in pilot plant studies, are
given by Sweeny (1973).. These data were updated as shown in Table 5;
the estimated capital investment for the complete treatment system with
10,000 gal/day capacity is $98,900 for June 1975.
47
-------
The estimated capital investments for the two assumed treatment
plant sizes (a) average flow rate of 30,000 gal/day and capacity of
50,000 gal/day, and (b) average flow rate of 45,000 gal/day and capacity
of 75,000 gal/day) were calculated using the 0.6 power factor of the ratio
of plant sizes (Peters, 1968)' as described in Appendix B, and adding
estimated costs for additional
plant equipment specified by Montrose.
/'
,
The scaled-up costs apply for equipment capable of handling the capacity
flow rate.
Scaling up by the 0.6 factor gives
-
For 30,000 gal/day: (50.000)0.6 x $98,900 = $259,800
10,000
Information provided by Montrose personnel (Sobelman, 1975a),
-
1975) indicates that the Envirogenics capital costs (see Table 5, July
1973 data) do not include all equipment' which would be required iri an'
actual plant operation.
Montrose has pointed out that the 30,000 gal/
day wastewater treatment plant would probably require two 100,000 gal.
surge storage tanks at a cost' of $40,000 each plus flowmeters, pumps,
and other miscellaneous equipment (Sobelman, 1975a).
The surge
tanks would serve to hold raw wastewater during periods when the treat-
.~~
ment process is shut down for repair work or to hold treated effluent which
does not meet specifications and must be reprocessed.
One tank would pro~"
.j' !
. ~ u
J'.
vide about 3 days' holding capacity for raw wastewater and the other tank '
would be capable of holding 3 days supply of treated effluent.
Thus, the'
estimated investment for additional installed plant equipment is $80,OqO
for tanks and $25,000 for flowmeters, pumps, and other miscellaneous
48
-------
equipment plus 15% contingency for a total of $105,000 x 1.15 or $120,800.
Then, the total estimated fixed capital investment is $259,800 + $120,800
or $381,000* (rounded) for a 30,000 gal/day treatment plant.
. 0.6
For 45,000 gal/day: (75.000) x $98,900 = $331,300 (base
10,000
cos t)
The 0.6 power factor (see Appendix B) and cost data for the 30,000 gall
day plant were used to "estimate the costs for additional process equipment
which would be required in an actual plant operation at the 45,000 gal/"
day flow rate.
0.6
Cost for surge tanks: (45.000) x $80,000 = $102,000
30,000
Cost for flowmeters, pumps, and miscellaneous equipment:
(1.5)0.6 x $25,000 = $31,900
Cost for miscellaneous equipment:
15% x (102,000 + 31,900) .=
$20,100.
Total for additional equipment = $102,000 + $31,900 + $20,100 =
$154,000 (rounded).
. Then the total estimated capital investment for a 45,000 gal/day plant
is $331,300 + $154,000 = $485,000 (rounded).
Direct Costs
The estimated direct operating costs for the 30,000 gal/day and
45,000 gal/day plants are calculated as described in the following
paragraphs using the base cost data shown in Table 6, taken from a technical
* A Montrose representative has estimated that the capital investment for
a 30,000 gal/day treatment plant would be about $750,000 (for September
1975) including a contingency of 30% (Sobelman, 1975a).
Swank (1975) has stated that the Montrose estimate of $750,000 is
high.
49
-------
I
report by Sweeny (1973) on pilot plant studies of the loop-extractor,
modified Friedel-Crafts system.
These data were adjusted to allow for
inflationary effects from 1973 to 1975 as follows.
The utilities costs for 1975 were adjusted by a factor of
1.75 as recommended by the Montrose Chemical Corporation (Sobelman,
1975a).
Except as noted, the raw material costs (see Table 6) were adjusted
according to the ratio of chemical prices prevailing in the cost literature
(Chemical Marketing Reporter. 1973. 1975)" during September 1, 1975, and
July 2, 1973.
Solvent Loss (Makeup of Heptane)
For example, on July 2, 1973, the listed price for heptane in
the Chemical Marketing Reporter was $0.225 to $0.255/gal. average of
$0.24/ga1.
The corresponding price for September 1, 1975, was $0.425/
gal.
The cost adjustment on this basis (using base data from Table 6)
is:
$13.30 x 0.425 = $23.55/day
0.24
Solvent/reactant (monoch1orobenzene)
A factor of 2.2 was used as recommended by Montrose Chemical Corpora-
tion (Sobelman, 1975a),
$5.40 x 2.2 = $ll.88/day
Catalyst (aluminum chloride. anh~drous)
$37.80 x 0.285 = $65.29/day.
~1~
50
-------
Raw Materials Costs
These costs are taken to be directly proportional to scale of opera-
tion.
The base cost data (Sweeny, 1973) in Table 6 for 1975 are used.
ill9
30,000 gal/day plant
Solvent loss
Solvent/reactant
Cat~ly.st
Total
45.000 gal/day plant
Solvent loss
Solvent/reactant
Catalyst
Total
Utility Costs
= 3 x $23.55
= 3 x 11.88
= 3 x 65.29
= 4.5 x $23.55 =
= 4.5 x 11.88 =
= 4.5 x 65.29 =
=
70.65
35.64
195.87
302.16
=
=
105.98
53.46
293.81
453.25
These costs are taken to be directly proportional to scale of .opera-
tion.
The base cost data in Table 6 are used.
30,000 gal/day plant
Steam
Power
Cooling water
Total
45.000 gal/day plant
Steam.
Power
Cooling water
Tota 1
= 3 x $55.13
= 3 x 75.08
= 3 x 4.20
= 4.5 x $55.13 =
= 4.5 x 75.08 =
= 4.5 x 4.20 =
51
$/Day
=
165.39
225.24
12.60
403.23
=
=
248.09
337.86
18.90
604.85
-------
Operatin~ Labor and Supervision Costs
As suggested by Sweeny (1973), the labor requirement for the 10,000
gal/day plant is one operator half-time.
For the 30,000 and 45,000 gall
day plant, it is considered that the labor required increases by the 0.25
power of the scale of operation as described in the literature (Happel and
Jordan, 1975) and the labor cost shown in Table 6 is updated.
The operating labor cost is updated 'using data from the literature
(Lowenstern, 1975) and from a site visit (Ferguson and Meiners, 1975) for
labor rates in the chemical and allied products industry.
On this basis,
the hourly earnings are $4.48 for 1973 (Lowenstern, 1975) and $5.50 for
July 1975 (Fergu~on and Meiners, 1975) and the ratio is 5.50:4.48 = 1.228.
Thus, the estimated labor cost (i~cluding payroll, charges) for t~e 10,000
gal/day plant in 1975 would be $97.20/day x 1.228 = $119.33/day. . The
30,000 gal/day plant:
labor cost for the other plants would be:
operating labor =(300000) 0.25 x $11~.33 = $157.05/day
10,000
operating labor = (450000),0.25 x $119.33 = $173.74/day
10,000 '
45,000 gal/day plant:
Supervision of direct labor is required.
According to cost estimating
practice described in the literature (Jelen, 1970) the supervision (includ-
ing payroll charges) is considered to be 20% of operating labor cost.
For
30,000 gal/day, the supervision cost = 0.2 x 157.05 = $3l.41/day; and for
45,000 gal/day, supervision cost = 0.2 x 173.74 = $34.75/day.
52
-------
Laboratory Costs
Laboratory services furnished to support the ~reatment process opera-
tion are estimated at 20% of operating labor cost (Jelen, 1970).
30,000 gal/day:
$157.05 x 0.2 = $3l.4l/day
45,000 gal/day:
$173.74 x 0.2 = $34.75/day
Maintenance Costs
The literature (Happel and Jordan, 1975) suggests a factor of 10%
of the plant capital investment to cover these costs, where corrosive
materials are being processed.
The on-stream time per year is 360 days.
30,000 gal/day:
0.1 x $381,000
360
= $105.83/day
45,000 gal/day:
0.1 x $485.000
360
= $134.72/day
Pavroll Charges
These costs are the result of fringe benefits employees receive in
addition to their regular salary.
We assume that the base data (Sweeny,
1973) on labor rates used include all of these payroll charges.
For ex-
ample, these base data on labor rates show an hourly rate of $9.36/hr
for an operator, while the pay scale was about $5.50/hr in July 1975.
It was concluded that the difference accounts for all payroll charges.
Operating Supplies
These supplies are items ,such as lubricating oil, instrument charts,
etc., that are neither raw nor repair .materials.
The cost of these items
is assumed to be 6% of operating labor (Jelen, 1970).
53
-------
30,000.ga1/day:
157.05 x O.O~ = $9.42/day
45,000 gal/day:
173.74 x 0.06 = $10.42/day
Indirect costs
The estimated indirect operating costs are calculated as described
in the following paragraphs.
Depreciation - This cost estimate uses a straight line, 10-year deprecia-
tion charge and assumes all capital. assets have a zero salvage value
(Jelen, 1970).
30,000 gal/day:
$381,000 = $105.83/day
10 x 360
$485,000 = $134.72/day
10 x 360
45,000 gal/day:
Property taxes - Property taxes are taken to be 2% of investment cost
(Jelen, 1970).
30,000 gal/day:
$381,000 x 0.02 = $2l.l7/day
360
45,000 gal/day:
$485,000 x 0.02 = $26.94/day
360
Insurance - Insurance for each plant is assumed to be a typical value of
1% of investment cost (Jelen, 1970).
30,000 gal/day: $381,000 x 0.01 = $10.58/day
360
45,000 gal/day: $485,000 x 0.01 = $13.47/day
360
Capital cost - The annual rate of capital cost (or
interest) is taken to be
6.3% for a period of 10 years as suggested by in~erest rates reported in
the current cost literature (Chemical Engineering, 1975a) and explained
in the Appendix B.
54
-------
On this basis, the annual interest can be computed as follows:
30,000 gal/day:
$381.000 x 0.063 = $66.68/day
360
45,000 gal/day:
$485.000 x 0.063 = $84.88/day
360
Plant overhead - This is a charge to the costs of a processing facility
which is not chargeable to any particular operation and is normally
charged on an allotted basis.
Overhead includes cost items such as plant
supervision, plant guards, janitors, 'administrative offices, accounting,
purchasing, etc.
Plant overhead can range from 40 to 60% of direct labor
.
costs or 15 to 30% of direct costs (Jelen, 1970).
Assume that plant over-
head is 20% of direct costs in this' estimate (see Table 5).
30,000 gal/day: 0.2 x $1,041 = $208.20/day
45,000 gal/day: 0.2 x $1,446 = $289~20/day
Costs for landfill of solid wastes - The costs for on-site landfill of the
.solid wastes (see Figure 2) produced by the extraction operation and the
Friedel-Crafts reaction are estimated below.
Considering (a) that the total discharge of suspended solids, DDT
and metabolites is directly proportional to wastewater discharge rate, and
(b) treatment process efficiency remains unchanged, the discharge rates of
solid waste which would apply for the 30,000 gal/day and the 45,000 gal/day
wastewater flow rates are as follows.
For the 30,000 gal/day waste treatment plant, the estimated quantity
of dry solid waste (see Figure 2, which applies for 1.5 ga1/min or 2,160
gal/day), is:
30,000 x (16 + 6.3) x 24 = 7,433 lb/day or 3.7 tons/day of solid waste
2,160
For 45,000 gal/day:
45,000 x 3.7 = 5.6 tons/day
30,000
1:"1;'
-------
McMahan (1975) indicates that solids can be disposed of in simple
landfills at a cost in the range of $3 to $lO/ton of solids.
In this
study the average cost is taken to be $6/ton of solids.
On this basis
the daily costs are:
For 30,000 gal/day:
3.7 x $6 = $22.20/day
For 45,000 gal/day:
5.6 x $6 = $33.60/day
Summary of costs - A summary of the estimated waste treatment process
operating costs is shown in Table 7.
The estimated capital investments
are $381,000 and $485,000 for the 30,000 and the 45,000 gal/day plants.
The total operating costs for the 30,000 and the 45,000 gal/day plants are
estimated to be $l,475/day ($53l,000/year) and $2,029/day ($730,400/year),
respectively.
The estimated unit operating cost is 0.89~/lb of DDT for
the 30,000 gal/day plant and 0.86~/lb for the 45,000 gal/day plant.
The reported July 1974 cost for hauling and dumping of all segregated
alkaline wastewater from the Montrose plant is about 0.4~~/1~ of product
. .
DDT (Ferguson and Meiners, 1975).
A comparison with the cost data shown
above indicates that the operating cost for the 30,000 gal/day wastewater
treatment plant would be about 85% more than the total hauling and dump-
ing cost.
The estimated unit treatment cost for the 45,000 gal/day. unit
would be about 79% higher than the unit hauling and dumping cost.
56
-------
Table 7.
.
SUMMARY OF ESTIMATED DAILY OPERATING COSTS FOR WASTE TREATMENT
BY SOLVENT EXTRACTION/FRIEDEL-CRAFTS METHOD
($/Operating Day; 360 Operating Days/Year)
Plant size
30,000
(~a1/day)
45,000
(~a1/day)
Direct costs
Raw materials /
Operating labor!
Supervisio~ of 1abo~/
Maintenance
Operating supplies
Utilities
Laboratory charges
Subtotal (rounded)
$. 302.16
157.05
31.41
105.83
9.42
403.23
31.41
$1,041/day
$ 453.25
173.74
34.75
134.72
10.42
604.85
34.75
$1,446/day
Indirect costs
Depreciation
Property taxes
-Insurance
Capital cost (interest)
Plant overhead
Subtotal (rounded)
$
105.83
21.17
10.58
66.68
208.20
412/day
$ 134.72
26.94
13.47
84.88
289.20
$ 549/day
$
Cost for landfill of treatment
solid wastes
$22/day
$34/day
Total operating cost- (rounded)
$1,475/day
$2,029/day
Unit operatin~ cost
Cost, $/1,000 gal. effluent
Cost, cents/1b of DDT product~/
(rounded)
$49.17
0.8G£/
$45.09
o . 86~/
!!/
~/
These costs include payroll charges.
In July 1975 the sales price for DDT was 50~/lb (Ferguson and Meiners,
1975).
For DDT production rate of 60 million pounds per year (Ferguson and
Meiners, 1975).
For a possible DDT production rate of 85 million pounds per year (i.e.,
the reported plant production capacity at the Montrose, Torrance,
C~lifornia plant _(Sobelman, 1975b).
£/
E./
57
-------
COST ESTIMATES FOR TWO-STAGE SOLVENT EXTRACTION WITH MCB
Estimates of the capital investment and the treatment cost for this
process on the basis of treating 30,000 gpd of alkaline wastewater are
given in the Montrose grant application (1975).
These cost data for 1975
are summarized below.
, .~
) .;,)
i'
Total capital investment
$101,000
---
Treatment cost (including charges for
operators, laboratory technicians,
extractants, maintenance and supplies,
and amortized capital investment)
$229.89/day or $82,800/year
Unit treatment costs:
Cost, ~/lb of DDT product
Cost, $/1,000 gal. of treated
affluent
0.14 (rounded)
7.66
ORDER-OF-MAGNITUDE COST ESTIMATES FOR CARBON ADSORPTION AND SYNTHETIC RESIN
ADSORPTION TREATMENT PROCESSES t:-, '.J
>
./!,.'
Order-of-magnitude cost estimates were prepared for two treatment
methods (carbon adsorption and synthetic resin adsorption) which have some
promise for treatment of DDT wastewater.
As pointed out by Ferguson and
Meiners (1974) neither of these potential processes have been performed un-
der conditions which approximate actual use or on a scale sufficient to
permit accurate determination of operating conditions or costs.
These
estimates are presented below for conceptual plants processing a maximum
of 50,000 gpd (average of 30,000 gpd) of alkaline wastewater.
A conceptual
flow diagram for the resin system and the activated carbon system is shown
in Figure 7.
58
u
-------
I
Since each alternate system requires both a sedimentation and fi1tra-
tion process, and the costs' of these two processes are identical for each
system, these processes are examined first.
Following a discussion o~ the
treatment and filtration processes, each alternate system is discussed
separately.
The cost estimates for the system are then summarized and
~
totaled.
Estimated Capital Investment Costs
-----
Estimated costs for capital investment are discussed briefly in the
1 '
fo lowing subsections. ~
~~~
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 34.7 gpm
(50,000 gpd) is estimated from a report by Blecker .and Nichols (1973).
Extrapolation of the graph on page 126 of their report shows that the in-
stalled cost (1972 dollars) of a sedimentation system to handle a flow
rate of 50,000 gpd is about $6,000.
This installed system for the sedi-
mentation process includes 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
59
-------
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:
($6,000)(18006) = -$8,000
137.2
Blecker and Nichols (1973) reported that the annual maintenance cost
for the process is about 15% of the installed cost or $1,200.
This re-
port also states that the process requires no operator attention.
.
However,
operating labor is estimated at 3 hr/day for routine checks on the process
to see that it functions properly.
Periodically, the sludge must be removed and landfi11ed. or incinerated.
The cost of sludge removal is included in the maintenance cost and the
cost for 1andfilling of this sludge is estimated separately.
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).
Filtration Process Costs - The wastewater is pumped from the sedimentation
process (at the same rate as the inflow) into a sand filter to further re-
move suspended solids.
The flow rate through a sand filter can vary de-
pending upon the design, but a typical flow rate according to Envirogenics
Systems Company (1973) is about 3.2 ga1/ft2/min.
Thus, the required £i1-
ter area for the 50,000 gpd (34.7 gpm) flow is about 11 ft2.
A.back-up
filter is required for each process since the plant operates 24 hr/day~
60
-------
The installed cost for the filtration process is obtained from a re-
port by Blecker and Nichols (1973).
The graph on page 66. of their report
shows that the installed cost of a 11-ft2 filter is $22,000.
Since this
cost is in 1972 dollars, the April 1975 cost (rounded) is:
2 x $22 000 (180,6)= -$58 000
, ' 137.2 '
B1ecker.and Nichols (1973) reported that the annual maintenance cost
for each process is about 5% of the installed cost or $2,900.
This report
states that the filtration process requires no operator attention.
However,
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.
Blecker 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).
Carbon Adsorption Process - The installed investment cost for a carbon
adsorption process can be estimated from data in a report by Zimmerman
(1971) .
In Figure 2 (p. 12) of the Zimmerman report, extrapolation of
the graph shows that the cost for a 50,000 gpd system was about $80,000
in September 1973.
The Chemical Engineering Plant Cost Index was used to
escalate this cost to 1975 prices.
Therefore,.the estimated installed cost
for the carbon adsorption system i8:
61
-------
\
$80,000 x (180,6) = """$111,000
. 130.2
XAD-4 Resin Adsorption Process -. Kennedy (1973) has reported on the costs
for treatment of effluent from manufacture of chlorinated pesticides with
an Amberlite XAD-4 system.
These costs, which have been updated in an MRI
Interim Report on wastewater treatment technology documentation (July 1975)
and which apply for an influent of 200 ppm total chlorinated pesticides,
150,000 gpd, run to 1 ppm leakage are as follows for June 1975.
Capital investment (uninsta1led equipment)
$126,400
Installation costs at 46% of purchased equipment
cost as reported by Marks (September 1974)
58.100
Estimated total investment
$184,500 .
This cost is for a 150,000 gpd flow rate and must be scaled down to
50,000 gpd.
Using the "six-tenths factors" (see Appendix B) for scaling
down the estimated installed cost for the XAD-4 resin process gives:
Cost x/150.000) 0.6
\~ 50,000
= $184,500
C st =/184.500) = $95 300
o \ 1.935 '
The following tabulation of cost data summarizes and totals the capital
investment for the two wastewater treatment systems (50,000 gpd flow rate).
62
-------
.
Capital Investment, 1975 $
XAD-4 Carbon
Resin System Adsorption System
Coagulation and sedimentation
Filtration
XAD-4 resin system
Carbon adsorption system
8,000
58,000
95,000
8,000
58,000
111,000
Subtotal
161,000
177,000
Contingency, 30%
48,000
53,000
Total capital investment
$209,000
$230,000
Operating Costs
Sedimentation and Filtration - The operating cost for a coagulation and
sedimentation process can be estimated from cost data published by
Zimmerman (1971).
On page 13 of the Zimmerman report the cost data show
by extrapolation a treatment cost of 5.5~/1,000 gal. of wastewater.'
Other data by Zimmerman (1971) show by extrapolation that the treat-
ment cost for filtration through sand is about 3.3~/1,000 gal.
Combining these unit costs and updating according to escalated operat-
ing labor costs' from 1971 to 1975 (as an approximation of overall unit cost
ascalation) gives the following total unit cost.
Estimated base cost for sedimentation, coagulation and filtration
is 5.5 + 30 or 35.5~/1,000 gal. of wastewater.
Production worker pay rates for chemical industries have advanced
from $4.00/hr in October 1971 to $5.41 in July 1975 (Monthly Labor Reviews,
February 1972, Vol. 95, No.2, p. 111 and October 1975, Vol. 98, No. 10,
p. 96).
Thus, the labor rate escalation factor is 5.41/4.00 = 1.353.
Applying this factor to. update unit costs gives:
63
-------
.
35.5 x 1.353 = 48~/1,000 gal.
Then
0.48 x 30,000 gpd/1,000 = $14.40 per operating day (350
operating days/year)
Carbon Adsorption Process - The overall treatment cost for the carbon
adsorption system can be estimated from a report by Cywin (1973).
In
the Cywin report (p. 319), extrapolation of the graph shows that the
operating cost for a 30,000 gpd average flow rate system is about $1.50/
1,000 gal. in September 1973.
Updating this cost according to escalated
labor costs from 1973 to 1975 (as an approximation of overall unit cost
escalation) gives the following total unit cost.
Production worker pay rates for chemical industries have advanced
from $4.48/hr in 1973 to $5.43/hr i~ August 1975 (~urvey of Current
Business April 1975 and Monthly Labor Review October 1975).
Thus, the
labor rate escalation factor is 5.43/4.48 or 1.212; applying this factor
. to update unit costs gives:
$1.50/1,000 gal. x 1.212 = $1.82/1,000 gal. effluent
Then the estimated total operating costs for the comp1ete~!"bQ!:l.ad~2tJ)ti2.!L,
---:~ :.. .,....1::... --- - - - .
<1 :.J
D'J .
system is:
,
$/1.000 Gal. Effluent (1975)
Cost for coagulation and sedimentation
and filtration
0.48
Cost for carbon adsorption system
1.82
Total
2.30
Then, the estimated daily operating cost is:
$2.30 x 30.000
1,000
= $69/operating day.
64
-------
I
The annual cost is 69 x 350 = $24,200/year
For the wastewater flow rate of 30,000 gpd the corresponding produc-
tion rate for DDT product is 60,000,000 lb/year (Ferguson and Meiners,
1975).
The estimated treatment cost per pound of product is:
$24,200/year
60,000,000 lb/yea~
x 100 = -0.04C/lb DDT
The XAD-4 Resin Process - The estimated operating cost for this process is
based on cost data in the literature and upon data reported by companies
using this process for control of other pesticide wastewaters.
The material costs are essentially the costs for 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 a 100-gpm system is $63,000 (current prices)
and that the resin has an operating lifetime of 5 years.
In this estimate
the XAD-4 resin is depreciated with the capital equipment.
Rohm and Haas
Company (Kennedy, 1973) estimates that the cost of the regeneration iso-
propyl alcohol makeup is $30,000/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/ga1 (Chemical Marketing Re-
porter, 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.
65
-------
Using a linear relationship to "scale down the resin and isopropyl
alcohol required for the 30,000 gpd (20.8 gpm) process flow rate gives:
Resin:
63,000 (20.8) = $13,000
100
Isopropyl alcohol:
($46,700/year) ( 20.8) = $9, 700/year
100
Blecker and Nichols (1973) reported that the "annual maintenance cost
for each process is about 5% of the installed equipment cost, or $4~800.
The operating labor time is estimated at 9 man-hours per 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 re-
quirement of 3,150 man-hours annually (based on 350 operating days per
year) .
To scale this labor time down to the 20.8 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:
Operating labor x (100 )0.25
20.8
= 3,150 man-hours
Operating labor = 2,130 man-hours
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
charge is 5 years for the purpose of depreciation of the installed costs
of the capital equipment and resin.
66
-------
r
The hourly earnings of production or nonsupervisory workers in the
chemical and allied products industry was $5.l8/hr in March 1975 (Monthly
Labor Review, 1975).
For April 1975, the estimated wage rate Js $5.20/hr.
This gives an annual operating labor cost for the resin system as follows:
2,130 man-hour per year at $5.20/hr or -$11,000
Supervision is normally estimated as 20% of operating labor (Jelen,
1970).
On this basis, the cost is:
0.20 x $11,000 = - $2,200.
Payroll Charges - Payroll charges (fringe benefits) are taken to be 30%
of wages paid to both labor and supervision; on this basis, the cost is:
0.30 x (11,000 + 2,200) = -$4,000
Maintenance and Operating Supplies - Maintenance cost has been determined
previously for the resin process to' be $4,800/year.
Operating supplies are estimated as 6% of labor costs (Jelen, 1970).
Tpis amounts to an annual cost of:
0.06 x 11,000 = -$700
Utilities and Laboratory Services - The utilities r~quired for the resin
process is primarily electrical power.
The estimated annual electrical
power for a 100 gpm XAD-4 resin system is $650 (Marks, September 1974).
Scaling this cost by direct proportion to effluent flow rates gives:
20.8 x 650 = - $140/year
100
Laboratory services are estimated as 20% of labor cost (Jelen, 1970).
Thus, 0020 x $11,000 = $2,200.
67
-------
Depreciation - The cost estimate uses straight line depreciation and assumes
all capital assets have a zero salvage value (see Appendix B).
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 XAD-4 resin system (rounded to nearest $100).
Life Annual
(years) Depreciation Cost ($)
XAD-4 resin process equipment 10 9,500
XAD-4 resin charge 5 2,600
Total 12,100
Property Taxes, Insurance, and Capital Costs - Property taxes, insurance
and capital costs are estimated as a percentage of the installed capital
equipment 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 invest-
ment cost, and that insurance is generally about 1% of investment cost.
Capital cost (or interest) is a charge to finance the investment expenditures.
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.
68
-------
I - ,
Using the above percentage gives the following indirect costs:
Property taxes and insurance:
3% of $95,000 = -- $2,900
Capital cost:
6.3% of $95,000 = -$6,000
Plant Overhead - Jelen (1970) reports that overhead can range from 40 to
60% of direct labor costs.
The plant overhead is estimated at 50% of
direct labor or 0.5 x $11,000 = $4,500.
Costs for Landfill of Solid Wastes - The costs for on-site landfill of the
solid wastes produced by the extraction process are estimated below.
These
costs are the same for the resin adsorption system and the carbon adsorption
system because the processes are identical for sedimentation and filtration.
No specific process data are available concerning the quantity of solids
which would be removed during the coagulation, settling and fi1tratipn of
the raw DDT wastewater in the conceptual treatment systems for carbon ad-
sorption and synthetic resin adsorption.
For purposes of this estimate,
the solid waste quantity is taken to be the same as the susperided solids
separated by settling in the solvent extraction process (Sweeny, 1973).
For the 30,OqO gal/day waste treatment plant the estimated quantity
of dry solid waste (see Figure 2, solid waste item E which applies for
1.5 ga1/min or 2,160 gal/day) is:
30.000
2,160
x (16 x 24) = 5,340 1b/day or 2.7 tons/day of solid waste
69
-------
I~
McMahan (1975) indicates that solid wastes can be di~posed of in
simple landfills at a cost in the range of $3 to $lO/ton.
In this study,
the average cost is taken to be $6/ton of solids.
On this basis the daily
costs are:
2.7 x $6 = $16.20/day
and the annual cost is 360 x $16.20 =
$5,800.
Operating Costs for Resin Adsorption Process - The total estimated annual
operating cost for the resin adsorption process, exclusive of the cost for
the sedimentation and filtration processes is:
Direct Costs
Isopropyl alcohol
Labor
Supervision
Payroll charges
Maintenance and operating supplies
Utilities and laboratory services
$ 9,'700
11 , 000
2,200
4,000
5,500
2,300
Indirect Cost
Depreciation
Property taxes and
Capital cost
Plant overhead
insurance
12,100
2,900
6,000
5.500
Total
$61,200
Summary of Costs - The total estimated costs of the carbon adsorption sys-
tern and the resin .adsorption system are given in Table 8.
The table shows
the total installed capital equipment costs (in 1975 dollars) for the two
systems are:
(a) carbon adsorption system, $230,000; and (b) resin adsorp-.
tion system, $209,000.
The estimated total annual operating costs are:
I
.70
-------
.
(a) $34,900; and (b) $71,900, respectively.
The estimated unit cost
(per 1,000 gal. of effluent) of treating the DDT wastewater effluent is:
(a) $3.33; and (b) $6085.
The estimated unit operating costs to treat
DDT wastewater per pound of DDT product (based on 60,000,000 lb of annual
production) are:
(a) 0.06e; and (b) 0.12e, respectively.
Table 8.
TOTAL INVESTMENT AND ANNUAL OPERATING COSTS FOR COMPLETE
CARBON ADSORPTION AND RESIN ADSORPTION SYSTEMS
-
Cost item
Carbon
adsorption
system
Resin
adsorption
system
Total installed capital
equipment cost (1975 $)
$230,000
$209,000
Annual operating costs (1975 $)
Coagulation, sedimentation and
filtration processes
Adsorption processes
Landfill of solid wastes
Total ($/year)
5,000 5,000
24,200 61,200
5,800 S , 800
$35,000 $72,000
Unit operating costs.
Cost, $/1,000 gal. effluent
Cost, e/1b of DDT (rounded)
(60,000,000 1b/year of DDT)
3.33
0.06
6.85
0.12
71
-------
.~
REFERENCES
, .Air/Water Pollution Report, p. 285, July 12, 1971.
Atkins, P.
ment and
D.C., p.
R., "The Pesticide Manufacturing Industry: Current Waste Treat-
Disposal Practices," U.S. Government Printing Office, Washington,
32, January 1972.
Chem. 'Eng., p. 89, July 21, 1975a.
Chem. Eng., p. 168, September 1, 1975b.
Chemical Marketing Reporter, July 2, 1973.
Chemical Marketing Reporter, September 1, 1975.
Dreyfuss, J., Los Angeles Times, 'October 7, 1970 and March 18, 1971.
Environmental Protection Agency, "DDT--A Review of Scientific and Economic
Aspects of the Decision to Ban Its Use as a Pesticide," Report prepared
for Committee on Appropriations, U.S. House of Representatives, U.S.
Environmental Protection Agency, Washington, D.C., 300 pages, July 1975.
Ferguson, T. L., and A. F. Meiners, I~astewater Management Review No.4,
DDT," EPA Contract No. 68-01-2579, May 21, 1974.
Ferguson, T. L., and A. F. Meiners, Site Visit to MOntrose Chemical
Corporation Plant at Torrance, California, EPA Contract No. 68-01-3524,
MRI Project No. 4127-C, July 17, 1975.
Grindley, J., "Effluent Disposal in DDT Manufacture," The Industrial
. Chemist; Vol. 26, No. 310, pp. 467-469, November 1950.
Hager, D. G., and J. L. Rizzo, '~emova1 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.
Happel, J., and D. J. Jordan, Chemical Process Economics, 2nd Ed.,
Marcel Dekker, Inc., New York (1975).
'Jelen, F. C., Cost and Optimization Engineering, McGraw-Hill Book Company,
New York (1970).
Lawless, E. W., et a1., "The Pollution Potential in Pesticide Manufacture,"
prepared by Midwest Research Institute, EPA Technical Studies Report
TS-00-72-94, U.S. Government Printing Office, Washington, D.C., June ,1972.
Lowenstern, H., Executive Editor, MOnthly Labor Review, p. 96, May 1975.
Lowenstern, H., Executive Editor, Monthly Labor Review, p. 96, May 1973.
72
-------
1-
McMahan, J. R., Working Memorandum 2 to David G. Davis, EPA, Case 78493,
October 9, 1975.
Miller, et ale (to Diamond Alkali Company), U.S. Patent 2,932,672, April
12, .1960.
Montrose Chemical Corporation Application for Demonstration
EPA, "Demonstration of a DDT Manufacturing and Processing
Treatment System," loD. No. R804293-0l, August 8, 1975.
Grant From
Plant Waste
Perry, R. H., and C. H. Chilton, Chemical Engineers Handbook, 5th Ed.,
McGraw-Hill Book Company, New York, New York (1973)0
Peters, M. S., and K. D. Timmerhaus, Plant Design and Economics for Chemical
Engineers, 2nd Ed., McGraw-Hill Book Company (1968).
Porter, D. J., "Chlorine, Its Manufacture, Properties, and Uses," Chapter 20,
ACS Monograph No. 154, Reinhold Publishing Corporation, New York (1962).
Robeck, G. G., et al., "Effectiveness of Water Treatment Process in Pesticide
Removal," J. Amer. Water Works Assn., Vol. 57, pp. 181 (1965).
Schmidt, T. T., R. W. Risebrough, and F. Gress, Bull. Environ. Contam.
Toxicol., Vol. 6, pp. 235 (1971).
Sigworth, E. A., "Identification and Removal of Herbicides and Pesticides,"
oj. Amer. Water Works Assn., Vol. 57, No.8, pp. 1016-1022, August 1965.
Sobelman, M., Vice President of Operations, MOntrose Chemical Corporation,
Torrance, California, telephone communication to C. Eo Mumma and.A. F.
Meiners, September 12 and 22, 1975a.
. Sobelman, Mo, Vice President of Operations, Montrose Chemical Corporation,
Torrance, California, telephone communication to C. E. Mumma, October 17,
1975b.
Swank, R. R., Jr., Acting Chief, Industrial Pollution
Environmental Re~earch Laboratory, Athens, Georgia,
Meiners and C. E. Mumma, September 29, 1975.
Branch, Southeast
Site Visit by A. F.
Sweeny, K. H., et al., Envirogenics Systems Company, El Monte, California,
"Development of Treatment Process for Chlorinated Hydrocarbon Pesticide
Manufacturing and Processing Wastes," prepared for Office of Research
and MOnitoring, EPA Contract No. 68-01-0083, July 1973.
73
I
I
-------
Sweeny, K. H., Envirogenics Systems,. E1 Monte, California, telephone com-
munication with C. E. Mumma, October 6, 1975.
Whitehouse, J. D., ,~ Study of
University of Kentucky Water
8, December 1967.
the Removal of Pesticiqes from Water,"
Resources Institute, Research Report No.
Weston, R. F., Inc., Draft, "Development Document for Effluent Limitations
Guidelines and Standards of Performance - Miscellaneous Chemicals Industry,"
EPA Contract No. 68-01-2932, February 1975.
74
-------
APPENDIX B
DEFINITION OF TERMS AND DISCUSSION OF CONVENTIONAL
ENGINEERING PRACTICES USED IN ESTI}1ATING COSTS
OF PESTICIDE WASTEWATER TREATMENT PROCESSES
.B-1
-------
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) ~perating 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 30% 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 pilo.ting, market s'tudies,'
land surveys, and requisitions.
They mar be off by 30% but they can be
prepared at relatively low costs using minimum data as follows (see Fig-
ure A-I).
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
Erigineering and drafting man-hours.
B-2
-------
L-
3
'"
o
"~
i 0
; 0
..
co -
- 0
#N
o
~
.
o
.....
"':;-
,0
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O;.!. ~;;! )5i
~ 3 ~ it J 0.. ~.c
a!" t1~:.4 08
A-: ~.~ J;
. ~. a 8J
!. :J :
.-
O.
if
if
.
.
.
.
.
Figure A-l.
".. 30
::;:~
o3~=
!:~i
; ...
...
..
RIQuiud Ift10''''0110"
Location
Gen,rel C."";I'.Ol\
5011 blor,nQ
locatio" 6 d'''''''I.on, R R. roodt.imDouf\Gs. teftc.,
WllI-de.elooleS tit, olot 010" 6 t0009'Q~'''cot moo
W,II.otv,loC)'d I'" faClllft"
Rouqh ''''eteh,s
Prel.,,,,,,ory
E ...oint,red
Preltminary \izinQ 8 "'0"'101 'DICI'ltotiOtt,
Enqin."ed lO'CI'ICO'IO",
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GenItal a"onq.""nu 6 el,.O"O",
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.
COST INDEXES (Peters and Timmerhaus, 1968)
Most 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
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En~ineering News-Record Construction Cost Index
Relative construction costs at various dates c~n be estimated by
use of the En~ineerin~ 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 1b of structural
steel, 1,088.fbm of lumber, 6 bb1 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, 14j.pipe, va1ves,and fit-
"tings, 20; process instruments and controls, 7; pumps and compressors, 7;
eletrica1 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:
C = rO.6 C
n
whereC
n
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 descr~bed 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 1arger,p1ant size, and takes into account the fact that larger plant
sizes require less than proportional labor forces due to economies of
sc"a1e.
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 30% of the wages paid to
both labor an~ superv~sion.
B-7
-------
I
I.
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 6% 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 proc~ss in this report, and
range from 5 to 15% of the capital equipment cost of the various processes.
B-8
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I
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 y~ar 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-
fu1 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 ~o 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 custom~ry 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 Engineerin~, 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 ~ periods required to pay
the original sum P can be computed from the following equation (Petroleum
Refiner, 1957).
B-IO
-------
. n
R r:: p 1(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
The 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).
Values of 1(1 + i)n
(1 + On - 1
n 2%. 4% 6% 8% 10%
1 1.020 1.040 1.060 1.080 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 + 0.1)10
(1 + 0.1)10 - 1
R = 163,000
In 10 years the total payment would be $1,630,000.
Thus, the to ta 1
interest is $630,000 and the average interest rate would be
630,000 = 6.3%/year
10(1,000,000)
B-11
-------
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--1aboratory, 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
-------
r
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-l3
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-
. REFERENCES
. 3.
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 Comm~nication to C. E. Mumma, Octo~er 15, 1975.
Jelen, F. C., Cost and Optimization Engineering, McGraw-Hill Book
Company, New York (1970).
4.
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
-------
r
BIBLIOGRAPHIC DATA 11. Report No.
SHEET EPA-440/9-76-009
4. Title and Subtitle
Wastewater Treatment Teclmology Doaunentation,
Manufacture of DDr
r2.
3. Recipient's Accession No.
s. Report Date
Pub. Jtme
6.
1976
-
7. Amhor(s)
A. F. ~-Ieiners. C. E. Humma. 9 T.
9. Performing Organization Name and Address
~lidwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
L. Fer~on and G. L. Kelso
8. Performing Organization Rept.
No. 4l27-C
10. Project/Task/Work Unit No.
11. Conuac:c/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.
,.. .. Irrl-I"\n D.C 20460
1 S. Supplementary Note s
13. Type of Report &: Period
Covered
Interim Renort ~ Edited
14.
Some editing was perfonned by EPA.'
16. Abstracts
--
This report was prepared to provide technologic supporting infonnation for toxic
pollutant effluent standards proposed by EPA tmder S307 (a) of the Federal Water
Pollution Control Act Amendments of 1972. The report identifies potential
teclmologies, assesses implementation feasibility, estimates final effluent
characteristics and estimates installation and operation costs for DDr
manufacturers. ..
17. Key Words and Document Analysis.
Wastewater
Waste Treatment
Cos t Analysis
Cost Comparison
Pesticides
Manufacturers
170. Descriptors
.
17~ .Identifier~i!Open-Ended Terms
Toxic Pollutant Effluent Standards
Federal Water Pollution Control Act
17c. COSATI Field/Group
18. Availability Statement
Release unlimited
19.. Secmicy Class (This
Report)
'TTN(-T
2U. Securny Class (This
Page.
UNCLASSIFIED
THIS FORM MAY BE REPRODUCED
21. -No, of Pages
.-.- q q
~2. Price
1f. 5,00
FORM NTI50as IR~V. 10'731 ENOORSED BY ANSI AND UNESCO.
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------'----_._---_.~.._--_..__.._.- .--.--., -- -- -_-.___0.
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