SCREENING STUDY TO DEVELOP
BACKGROUND INFORMATION AND
DETERMINE THE SIGNIFICANCE OF AIR
CONTAMINANT EMISSIONS FROM PESTICIDE
PLANTS
-------
SCREENING STUDY TO DEVELOP BACKGROUND
INFORMATION AND DETERMINE THE SIGNIFICANCE OF
AIR CONTAMINANT EMISSIONS FROM PESTICIDE PLANTS
by
•C. N. Ifeadi
BATTELLE
Columbus Laboratories
Columbus, Ohio 43201
for the
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF PESTICIDE PROGRAMS
. STRATEGIC STUDIES UNIT
401 M St., S.W.
Washington, D.C. 20460
Jeff Kempter, Project Officer
March, 1975
EPA 540/9-75-034
-------
ABSTRACT
In this study, available background information is developed
and the significance of air contaminant emissions from the manufacture of
six pesticides determined. Pesticides studied are (1) insecticides:
methyl parathion and toxaphene; (2) herbicides: MSMA and trifluralin;
(3) Fungicide and wood preservation: pentachlorophenol; and (4) fumigant:
paradichlorobenzene. N
Background information is gathered from published data and
responses to the questionnaires sent to the pesticide manufacturing firms.
Based on the available data, production projections are made up to the
year 1980. A list of manufacturers of each pesticide is presented.
Manufacturing processes, raw and waste material handling, air contaminant
emission sources, quantity or quality, and pollutants, together with their
present practical control methods are discussed.
Significance of air contaminant emissions from the pesticide
industries is evaluated on the basis of available data on the emission
quantities and/or toxicity of the pollutant(s) emitted. Gaps in the
data required to make a complete evaluation of significance are identified
and recommendations to fill those gaps are made.
11
-------
SUMMARY
The essential findings of this study can be summarized as
follows:
Pesticide Production Inventory
(1) A severe lack of availability of past and present production
data, on individual pesticides exists. The U. S. Tariff Commission is the
main source of published data on production; however, its lists often are
incomplete. Some of the lists are not presented by individual pesticides,
but instead by groups of pesticides, such as aldrin-toxaphene or methanearsonic
acid salts.
(2) Available published data and expert opinion from the industry
and other knowledgeable people outside the industry were carefully evaluated
to develop a production table for each pesticide from 1970 to 1980. No
estimate on the number of new plants to be built and/or plants to be
significantly modified is made.
(3) A list of manufacturers of each pesticide in the United
States is included, including the plant (company) name and location. Estimates
of the design capacity of existing plants and their production are provided.
Manufacturing Processes
(1) One manufacturing process for each pesticide is identified..
(2) The manufacturing process is briefly described in terms of
the steps involved in the production process, aided by simple reaction
chemistry and simple production flow sheets.
Raw and Waste Material Handling
(1) Essential raw materials are enumerated. All hazardous
materials are identified.
(2) Precautionary safety measures taken by manufacturers
to safeguard the health of employees are described.
iii
-------
(3) Simple flowsheets for waste handling during the manufacture
of each pesticide are provided, identifying the waste disposal technique used.
Air Contaminant Emissions. Sources, and Rates
(1) A table of air contaminant emissions and their sources from
manufacturing processes and waste disposal systems is developed.
(2) Where possible, air contaminant emission rates are calculated
on the basis of simple reaction chemistry or where available are provided
by manufacturing plants.
Air Contaminant Control
(1) Air contaminants arising from production processes are
controllable by most of the methods used in the general chemical industries
to prevent dusts, fumes, and gases from leaving the production plant and/or
its waste treatment site.
(2) The present level of the air contaminant control for each
pesticide industry is evaluated, where enough information is available
from the manufacturers.
(3) Nationwide air contaminant emissions and the present emission
control situation are estimated.
Control Costs
(1) Cost estimates are presented only for those companies which
submitted such information in response to the survey. While a few companies
provided some data on the cost of control in their plants, the operating
conditions necessary for an adequate evaluation of the same are not provided.
This part of the research, together with the economic impact on the industry
due to the imposition of the best available control technique, is not
pursued because of resource limits for this study.
iv
-------
Significance of Emissions from Pesticide Plants
Determination of the significance of the air contaminant emission
in each pesticide industry is made by identifying the candidate pollutant(s),
their quality or emission (where possible), and toxicity.
-------
TABLE OF CONTENTS
Page
SECTION I
CONCLUSIONS 1
SECTION II
RECOMMENDATIONS 3
SECTION III
INTRODUCTION 4
Objectives of the Study 5
The Study Approach 5
Data Collection 5
Process Description 7
Analysis of Air Contaminant Emission and Control .... 7
Analysis of Air Contaminant Emission Control Costs ... 8
/
SECTION IV
BACKGROUND INFORMATION AND SIGNIFICANCE OF AIR CONTAMINANT
EMISSIONS 9
Insecticide - Methyl Parathion 13
Production Inventory 13
Future Production Trends 13
Manufacturing Process 15
Raw and Waste Material Handling 15
Air Contaminant Emissions, Sources, and Rates 18
Air Contaminant Emission Control 18
Control Costs
Significance of Air Contaminant Emission 21
Insecticide - Toxaphene • 22
Production Inventory 22
Future Production Trends' 24
Manufacturing Process 25
vi
-------
TABLE OF CONTENTS (Continued)
Raw and Waste Material Handling. 25
Air Contaminant Emissions, Sources, and Rates 27
Air Contaminant Emission Control 27
Control Costs 29
Significance of Air Contaminant Emissions 29
Herbicide - Monosodium Acid Methanearsonate (MSMA) 29
Production Inventory 30
Future Production Trends 30
Manufacturing Process 32
Raw and Waste Material Handling 33
Air Contaminant Emissions, Sources, and Rates 33
Air Contaminant Emission Control 36
Control Costs 36
Significance of Air Contaminant Emission . 37
Herbicide - Trifluralin 37
Production Inventory 37
Future Production Trends 37
Manufacturing Process 38
Raw and Waste Material Handling 40
Air Contaminant Emissions, Sources, and Rates. 40
Air Contaminant Emission Control 43
Control Costs 43
Significance of Air Contaminant Emission . 43
Fungicide and Wood Preservation - Pentachlorophenol 43
Production Inventory , 44
Future Production Trends 44
Manufacturing Process 46
Raw and Waste Material Handling 47
Air Contaminant Emissions, Sources, and Rates. ..... 48
Air Contaminant Emission Control . 48
Cost of Control 48
Significance of Air Contaminant Emissions 53
Fumigant - Paradichlorobenzene 53
Production Inventory 54
Future Production Trends 54
Manufacturing Process 56
Raw and Waste Material Handling . 57
Air Contaminant'Emissions, Sources, and Rates 57
Air Contaminant Emission Control 57
vii
-------
TABLE OF CONTENTS (Continued)
Control Cost 60
Significance of Air Contaminant Emission 60
SECTION V
REFERENCES 61
APPENDIX A
SUMMARY OF THE SELECTED PESTICIDES AND THEIR PRODUCERS A-l
APPENDIX B
SUMMARY OF NONPROPRIETARY INFORMATION OBTAINED FROM THE
SURVEY OF PESTICIDE PLANTS B-l
APPENDIX C
SAMPLE OF LETTER MAILED TO SELECTED PESTICIDE MANUFACTURING
COMPANIES C-l
viii
-------
LIST OF TABLES
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
Table 8.
Table 9.
Table 10.
Table 11.
Table 12.
Table 13.
Table 14.
Table 15.
Table A-l.
Table B-l.
Table B-2.
Table B-3.
Page
Research Plan 6
Production Estimates - 1970 to 1980 11
Producers of Methyl Parathion in the United States . . 14
Air Contaminant Emissions, Sources, and Rates
from Methyl Parathion Manufacture and Waste
Treatment 19
Producers of Toxaphene in the United States 23
Air Contaminant Emissions, Sources, and Rates
from Toxaphene Manufacture and Waste Treatment .... 28
Producers of MSMA in the United States 31
Air Contaminant Emissions, Sources, and Rates
from MSMA Manufacture and Waste Treatment 35
Air Contaminant Emissions, Sources, and Rates
from Trifluralin Manufacture and Waste Treatment ... 42
Producers of PCP in the United States,
45
Air Contaminant Emissions, Sources, and Rates
from PCP Manufacture and Waste Treatment 49
Air Contaminant Control Methods Used in PCP
Manufacture 52
Producers of Paradichlorobenzene in the
United States 55
Air Pollution Emissions, Sources, and Rates from
Paradichlorobenzene Manufacture and Waste Treatment. . 58
Air Pollution Control at Standard Chlorine 59
Uses, Classes, Producers, Production Volumes, and
Properties of Selected Pesticides A-l
Summary of Air Contaminant Emissions, Sources,
and Rates B-l
Summary of Air Emission Control Devices, Efficiency,
and Cost B-3
List of Contacts Having Expertise and Sources of
Significant Information about Selected Pesticide
industries ... .
B-4
ix
-------
LIST OF FIGURES
Figure 1.
Figure 2.
Figure 3.
Figure 4.
Figure 5.
Figure 6.
Figure 7.
Figure 8.
Figure 9.
Figure 10.
Figure 11.
Figure 12'.
Manufacturing Sites of the Selected Pesticides .... 10
Production Estimates (1970-1980) for Selected
Pesticides 12
Production and Waste Handling Schematic for Methyl
Parathion (Monsanto) 16
Parathion Residue and Off-Gas Incinerator.
20
Production and Waste Handling Schematic for
Toxaphene 26
Production and Waste Handling Schematic for MSMA ... 34
Simple Flowsheet for Trifluralin Manufacture ..... 39
Production and Waste Handling Schematic for
Trifluralin 41
Production and Waste Handling Schematic for
Pentachlorophenol. 46
Scrubbing Systems for the Control of HC1, Cl-
Emitted from PCP Reactor 50
Dust Collector Schematics for the Penta Emission
Control 51
Production and Waste Handling Schematic for
Paradichlorobenzene 56
-------
SCREENING STUDY TO DEVELOP BACKGROUND
INFORMATION AND DETERMINE THE SIGNIFICANCE OF
AIR CONTAMINANT EMISSIONS FROM PESTICIDE PLANTS
SECTION I
CONCLUSIONS
The prinicipal conclusions to be drawn from the information derived
in the study are as follows:
(1) Most companies are unwilling, for proprietary reasons, to
provide their production data to contractors. Published data are incomplete
and do not provide a basis upon which to develop a definite trend for fore-
casting future production. However, forecasts have been provided based on
projected raw material availability and demand in agricultural production
and other end uses.
(2) Essential health and safety precautionary measures adopted
by most firms are transport of materials in closed systems and requirement
for the use of protective clothing such as coveralls, rubber gloves, safety
glasses or goggles, hard hats, face shields, and respirators.
(3) Sources of air contaminant emissions vary from one pesticide
plant to another. The usual sources are reactor vents, vents along the
transport lines, raw material unloading area, product packaging area, and
waste and by-product recovery and disposal systems.
(4) Simple process chemistry is not sufficient in determining
the quality and quantity of the air contaminant emissions because of
variations in the production process.
-------
(5) The identified omissions consist of participates, gases, and
vapors. Each pesticide plant emits into the atmosphere at least one pollutant
which may require control. Some are known to create odor nuisance and
visibility problems. In some cases, odor nuisance may be experienced, but
the odorous compounds are not known. Very little information is available
on the emission rates because few companies conduct in-house sampling programs.
The popular and most pratically applicable technique used in controlling
emissions from the manufacture of the pesticides studied involves wet scrubbing
with water. A smaller percentage of plants employ alkali absorption and
adsorption processes and filter bags (baghouses). Wet scrubbing, absorption,
and adsorption processes are used mainly for controlling gases and vapors, with
particulates controlled to a lesser extent. Filter bags are used primarily
for controlling particulate emissions.
(6) A factual, realistic assessment of the significance of emissions
from pesticides plants is impractical at this time because of the limited
quantitative emission data available. This data limitation is compounded by
absence of state or Federal source emission standards on which to base such an
evaluation. However, in the manufacture of pesticides, there are significant
emissions of such compounds as S09, H9S, and NO , and these are substantially
^ ^ X
higher than emission standards in other related process industries.
-------
SECTION II
RECOMMENDATIONS
(1) A more effective means of obtaining data than the currently
employed method of requesting information by letter from manufacturer needs
to be developed. This new means of data collection must simultaneously
protect the legitimate proprietary claims of manufacturers, yet insure that
EPA and its contractor meet their obligations. Working through an intermediary
such as a trade organization may be one of the general strategies needed
to accomplish this end.
(2) The air pollution control aspects of the pesticide industry
have not been studied as closely as its water pollution control aspects. A
detailed study involving air monitoring and sampling at the manufacturing
plant and their waste disposal site should be pursued. The author of this
report has relied heavily on published data and scanty responses from the
pesticide manufacturers. It is recommended that this study be expanded to
include plant visits and sampling.
(3) The dearth of field measurements on pesticides emission
prevents development of a firm recommendation on source performance standards
for the pesticide industry. However, the intrinsic toxicity of intermediate
and final products is clear. It is, therefore, recommended that a field
emission study be undertaken at the earliest possible date to obtain the
data necessary to fully quantify pesticides emission standards.
-------
SECTION III
INTRODUCTION
Pesticides are important to the nation's economic life because
tliey arc used to help in the production of food and fibre and to control
organisms that destroy materials or threaten public health. However, the manu-
facture and use of the pesticides can create environmental and health concerns,
Consequently, EPA, through its Office of Pesticide Programs, has engaged in
studies of various aspects of pesticide production, use, and effects on the
environment.
Continuing in these important studies, the Strategic Studies Unit
of the Office of Pesticides Programs has noted a need to develop background
information and determine the significance of the air contaminant emissions
from the manufacture of some pesticides, in conformity with the 1970
Clean Air Act that requires the regulatory agencies to gather information and
develop standards for emissions from stationary sources. Because there are
large numbers of pesticides manufactured in this country, only one or two
pesticides from each class were selected for this background study. Six
pesticides were selected in total as listed below.
Insecticides - methyl parathion and toxaphene
Herbicide - monosodium methane arsonate (MSMA) and trifluralin
Fungicide and wood preservative - pentachlorophenol
Fumigant - paradichlorobenzene.
The choice of these specific pesticides by EPA was based on a
previous EPA study, which found that the selected pesticides are characterized
by high production and use, environmental concerns, regulatory interest, and
(1) *
increased use forecast.
* References are located on Page 61.
-------
Objectives of the Study
The first general objective of this study has been to develop
background information on the manufacture of six pesticides described earlier.
Specific objectives have been: (a) to prepare a list of manufacturers in the
United States specifying the plant name, location, capacity, and production;
(b) to describe the production processes for each pesticide; (c) to describe
the emission sources of air contaminants and their control, and estimate the
nationwide air contaminant emissions from the plants producing each pesticide;
and (d) to prepare a cost estimate of the best available emission control
systems and discuss the economic impact on typical firms in the industry if
such control were required.
The second general objective has been to determine the severity of
air contaminant emissions from the pesticide manufacturing plants and thus
identify the need to develop emission standards for such plants.
The Study Approach
The approach centered on the development of background information
on the manufacture of six selected pesticides. The study of each pesticide
was divided into four tasks as given in Table 1. The table contains the
specific information desired on each task.
Data Collection
Information gathering was focused on a literature survey of the
manufacture of the six pesticides in the United States. Principal information
sources were from BCL in-house data files and government, professional, and
trade association publications. Letters requesting data (see Appendices B and C)
were sent to 9 manufacturing plants to obtain factual information on various
aspects of the selected pesticide manufacture. Information sought included
plant capacities and production volumes; processes profiles such as flow
sheets, raw and waste materials handling descriptions; source, kind, and
-------
TABLE 1. RESEARCH PLAN
Tasks
Desired Information
1. Data Collection
2. Process Description
3. Air Contaminant Emissions and
Control
4. Control Cost
(a) List of Manufacturers
• Plant name
• Location
• Capacity
• Production
(b) Manufacturing Processes
• Nature of pesticide produced
• Raw materials
• Waste materials
(c) Air Contaminant Emissions
• Control technology
• Level of control
• Waste disposal involving air
pollution emission
(a) Description of the pesticide
produced
(b) Description of raw and waste
materials handling
(c) Manufacturing methods and processes
flowsheets
(a) Types and sources of air
contaminant emissions
(b) Types and levels of control
(c) Estimate of the present emission
control situation
(d) Estimate of future emissions
(a) Estimated cost for best available
control
(b) Economics impact on the industry
-------
quantities of air contaminant emissions, currently applied control methods;
and costs of such controls. Several telephone calls were made to the
manufacturing plants urging them to complete the forms; however, no plant
visits were made.
Process Description
Using the information gathered, flow sheets were developed, and
process profiles employed in the manufacture of each pesticide were described.
Each flow sheet identified, where possible, the following:
(1) Steps of manufacturing processes
(2) Raw materials
(3) Sources and types of air contaminant emissions
(4) Waste material disposal methods
(5) By-products
(6) Final end products.
/ '
Analysis of Air Contaminant Emission and Control
The air contaminant emissions from the manufacture of each pesticide
and the disposal of the wastes were identified and quantified where possible
together with the currently employed methods of emission control. The currently
employed emission controls were described in terms of gas and particulate
removal efficiency ranges, potential reduction of visibility, and odor.
Projections of future emissions were made. By relating these to
similar emissions from other sources, a quantitative estimate of the significance
of emissions from the manufacturing sector were made.
The qualitative and quantitative estimates of the present and
future nationwide air contaminant emissions from the plants manufacturing each
pesticide were based on the plants' capacities and the air contaminant emissions
rates.
-------
Analysis of Air Contaminant Emission Control Costs
Based on the information obtained from the foregoing tasks,
cost estimates were made on the currently employed control methods. The
costs consisted of the operating and capital cost estimates. Where possible,
and on the basis of available information, cost estimates of the best available
emission control systems for a typical firm were made. In addition, a
discussion of the economic impact on typical firms in the industry, if such
controls were required, was presented.
-------
SECTION IV
BACKGROUND INFORMATION AND SIGNIFICANCE
OF AIR CONTAMINANT EMISSIONS
For the convenient presentation of the desired information, the
research program outlined in Table 1 was subdivided as follows:
(1) Production inventory in the United States
(2) Future production trends
(3) Manufacturing process
'(4) Raw and waste material handling
(5) Air contaminant emissions, sources, and rates
(6) Air contaminant emission control
(7) Control costs
(8) Significance of air contaminant emission from the plants.
Available information on the individual pesticide is presented
sequentially under the above headings. However, before the discussion, a
general look at the manufacturing sites and production quantities is
necessary. The manufacturing sites of the selected pesticides are shown
in Figure 1. These sites do not include the formulation plant sites but
only the active ingredient manufacturing sites.
Quantitative information on the past, present, and future
production of the selected pesticides was difficult to obtain. Information
on past production was obtained from the U. S. Tariff Commission published
data; however, some of these production values are listed in pesticide groups
instead of individual pesticides utilized in the program. Present and
future production information was sought through the manufacturers, but
most failed to give the information for proprietary reasons. Since the
past production data did not present a definite trend, an extensive effort
was made to forecast production of each pesticide up to 1980. These
estimated production data are given in Table 2 and are graphically shown
in Figure 2. As will be discussed under each pesticide, a.number of factors
such as availability of raw materials, demand of the pesticide, and other
influences can significantly alter the forecast, so that its reliability
decreases as the time interval increases.
-------
WEST NORTH CENTRAL
+ X
EAST NORTH CENTRAL
WEST SOUTH-CENTRAL
Pesticides No.of Plonte
• Methyl parathion 4
V Toxaphene
• MSMA
-f* Trifluralin
X Pentachlorophenol
A P-dichlorobenzene
4
3
I
6
9
FIGURE 1. MANUFACTURING SITES OF THE SELECTED PESTICIDES
-------
TABLE 2. PRODUCTION ESTIMATES - 1970 TO 1980
Pesticides 1970
Methyl Parathion (MPT) , ,
Production, 106 Ib. 41.4la'
Percent Growth
Toxaphene , . .
Production, 10 Ibs. 50^ '
Percent Growth
Kor.osodium Methanersonate(MSMA} .
Production, 10° Ib. 30.5
Percent Growth
Trifluralin -
Production, 10 Ib. NA
Percent Growth
Pentachlorophenol (PCP) . .
Production, 10° Ib. 47. 2W
Percent Growth
Paradichlorobenze(PDCB) , .
Production, 106 Ib. 69. 6^ '
Percent Growth
1971
37.2
io(e)
65
30
24.5(a)
20
25(a)
16
50.9(a)
8
70.4
1
1972
5i.i«
37
85.1(C>
31
30.7(a)
25
2l(f)
10
49.7^
2(e)
77.3
10
1973
48i9(a)
4(e)
94.6
11
40.1
6(.)
85.0
10
1974
57
17
108 (d)
14
50.1
25
25.4
10
48.9
5
93.5
10
1975
65.6
15
124.2
15
62.6
25
27.9
8
51.4
5
95.4
2
1976
71.4
13
142.2
15
75.1
20
30.1
8
54.5
6
97.3
2
1977
81.5
10
162.8
14
90.1
20
32.5
8
57.8
6
99.3
2
1978
88.0
8
185.6
14
103.6
15
34.5
6
61.9
9
103.3
4
1979
93.3
6
207.9
12
119.1
15
36.6
6
68.1
10
107.4
4
1980
98.0
5
232.9
12
131.0
10
38.4
5
74.9
10
111.7
4
(a) United States Tariff Commission Report-Synthetic Organic Chemicals. (Reference 2)
(b) 55 percent of Toxaphene-Aldrin Group-quoted by U.S. Tariff Commission.
(c) 65 percent of Toxaphene-Aldrin Group-quoted by U.S. Tariff Commission.
(d) 70 percent of Toxaphene-Aldrin Group-quoted by U.S. Tariff Commission.
(e) Indicates percent of decrease in production.
(f) Riimker et al, Reference 1.
-------
12
1000
XJ
c
3
O
a.
c
O
O
u
3
T>
O
100
1970 1971 1972 1973 1974 1975 1976 1977 1978 1979 I960
FIGURE 2. PRODUCTION ESTIMATES (1970-1980) FOR SELECTED PESTICIDES
-------
13
Insecticide - Methyl Parathion
Methyl parathion is a broad-spectrum organophosphate Insecticide.
It is highly toxic to humans, a characteristic symptom being the impairment
of the nervous system. It is a nonpersistent contact pesticide being used
extensively in cotton production. Interest in its use in the production of
soybeans and alfalfa is increasing.
Production Inventory
Methyl parathion is manufactured in three southern states:
Mississippi, Alabama, and Tennessee. The manufacturing sites are under-
standably clustered in the major use region--the cotton production belt.
The names, location, plant design capacity, and the 1974 estimated production
volumes are given in Table 3. Over half of the present production volume is
manufactured by Monsanto Company.
The total U. S. capacity for the manufacture of methyl and ethyl
parathions [0,0-dimethyl 0-p-nitrophenyl) phosphdthioate] is 147 million Ib,
but three plants with total capacity of 53 million Ib were not producing
methyl parathion in 1974. The 1974 estimated production of methyl parathion
is 57 million Ib.
Future Production Trends
Future production will depend on the demand and available raw
materials. Major quantities of methyl parathion are exported; hence,
foreign demands will undoubtedly influence the volume of production in
this country. Increased application of methyl parathion to crops other
than cotton also will increase demand. Increased use is being further
accelerated by recent world food production demands. An absence of a
strong competing pesticide in the marketplace will force an upward trend
in production. For example, the recent cancellation of DDT registrations
has helped to push upward the production of methyl parathion. A factor
that certainly may lower the bulk usage for methyl parathion is the development
-------
14
TABLE 3. PRODUCERS OF METHYL PARATHION IN THE UNITED STATES
(3,4)
Company
American Cyanamid Company,
Agricultrual Division ^ '
Hercules Inc. ., v
Synthetics Department
Kerr-McGee Corporation
Kerr-McGee Chem. Corp.
Monsanto Company .., v
Agricultural Division^ '
tauffer Chemical Company,, ,.
Agricultrual Chem. Div. '
Vicksburg Chemical Company
Velsicol Chemical Corp.
Annual Capacity
Location millions of Ib
Lindern, N. J.
Plaquemine, La.
Hamilton, Miss.
Ann! a ton, Ala.
Mt. Pleasant, Tenn.
Vicksburg, Miss.
Bayport, Texas
Total
28
15
17
50
30
3
10
153
Estimated
1974 Production
millions of Ib
--
--
15
30
10
2
57
(a) Not operating by 1974.
(b) Volume includes ethyl parathion.
-------
15
of a more effective and efficient way of packaging and applying the insecticide,
such as encapsulation techniques.
The effect of the foregoing factors on future production of the
insecticide is difficult to predict. However, responding industries estimated
that the annual rate of increase in production will decline from the 1973-
1974 level of about 17 percent to about 5.0 percent by the year 1980. On this
basis, 1980 production will be about 98.0 million pounds.
Manufacturing Process
Methyl parathion is commonly manufactured from sodium p-nitrophenolate
by the reaction with 0,0-dimethyl phosphorothiochloridate. There are
three steps involved in the synthesis of methyl parathion. One common method
involves the reaction of an appropriate alcohol (methyl alcohol) with phosphorus
pentasulfide, followed by chlorination, and finally, the parathion formation in
acetone. The three steps are as follows:
S
P2S5 + 4ROH"
Diphosphoruspentasulfide Hydrogen sulfide
S S
it ii
(RO). PSH + C10 ^(RO)0PC1 + HC1 + S
£• i f.
ONa
S
/s~^\
NaCl
*• S^—^x* f- \^^/ i
0,0-dimethyl
Phosphorothiochloridate 0 *J°2 Parathion
Sodium p-nitrophenolate
Conditions of these reactions are not available as they are
proprietary.
Raw and Waste Material Handling
The raw materials are sodium p-nitrophenolate, methyl alcohol,
chlorine, and phosphorous pentasulfide. In the production of methyl
parathion, by-products such as NaCl and HCl are formed along with waste
products such as H_S, mercaptan, and sulfur. The production and waste*
-------
16
S02
t
Flare
S & RHS
i
S02
t
Incinerator
ROH-
Dialkyl
Ester
•S
-*-HCI-
Chlorinator
-^ Ch lor idothionate
NaOC6H4NO2-
Acetone
Parathion
Unit
T
NaCl-
Na2CO3-
Waste
Treatment
Plant
City
Sewer
Partial
Recovery
Parathion
Trace Quantities
of H2S, RHS, and
HCI emitted to air
FIGURE 3. PRODUCTION AND WASTE HANDLING SCHEMATIC FOR METHYL PARATHION
(Monsanto)(6)
-------
17
handling schematic is shown in Figure 3. The odorous compounds (H_S and
mercaptan) are flared and the sulfur i? incinerated, while liquid waste
effluents are neutralized with Na CO., and sent to a wastewater treatment
plant.
Since methyl parathion is very toxic, specific handling
precautions are taken. Kerr-McGee Corporation provides the following
precautionary steps in their plant:
(1) Raw materials except for SNP (sodium p-nitrophenolate)
are stored in tanks located in diked areas or in
submerged sumps. SNP is stored in powder form out of
doors. The SNP is stored in reconditioned, open head
type, bolted top ring drums. Drainage from the SNP
drum storage area is to the chemical complex drainage
ditches.
(2) Processing areas of the plant are curbed so that spills,
gland water from pumps, and contaminated runoff are
contained and treated as process wastewater.
(3) Liquid parathion is stored in a new roofed warehouse
that does not drain or discharge into any wastewater
effluent systems. The parathion is stored in 16 gauge,
tight head drums. In the event of a parathion spill
the following clean-up steps are taken in the order
listed:
e Put absorbent clay on the spill until the
spill is soaked up in the clay.
e Remove the clay and absorbed parathion.
• Put soda ash over the spill area. Vigorously
scrub soda ash into floor with a broom.
• Remove soda ash.
• Repeat Steps 3 and 4 several times .
• Wipe contaminated area with paper towel.
• Soak paper towel in carbon disulfide to
extract methyl parathion*
e Check carbon disulfide for methyl parathion
by infrared scan.
-------
18
• If the test is positive repeat Steps 3 through 8 until
the test is negative .
• Bury contaminated matter in closed drum.
Air Contaminant Emissions, Sources, and Rates
The manufacture of methyl parathion produces solid, liquid, and
gaseous waste materials.
The main sources of air contaminant emissions are: the reactor,
the chlorinator, and the Methyl Parathion unit (Figure 3). Odorous
pollutants arise from vents, liquid wastes, and residues. During the
disposal of by-products (for example, flaring of H_S and mercaptans and
incineration of sulfur), sulfur dioxide is given off. Also, during waste-
water treatment or lagooning, the odorous compounds such as H_S, mercaptans,
etc., are emitted.
The companies contacted were unable to furnish any data on the
rate of air pollutant emissions from their plants. Emission rates for
H_S, S, and NaCl were calculated as 460, 420, and 460 pounds per hour,
respectively, on the basis of 330 days per year and a 24-hour-per-day
operation.* Sulfur dioxide emission rates based on H»S and S oxidation
are estimated to be 1,550 pounds per hour from the following reactions:
ZHjS + 303~> 2S02 + 2H20
S + 02 > S02
The air emission sources, compounds, and rates are given in Table 4.
Air Contaminant Emission Control
Air contaminants arising from the production processes are
controlled by the methods used in general chemical industries to prevent
dusts, fumes, and gases from leaving the production plant into the outside
environment.
* These calculations are based on an annual production of 30 x 10 pounds
of methyl parathion and the estimates by Rawless, et al
-------
TABLE 4. AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES FROM
METHYL PARATHION MANUFACTURE AND WASTE TREATMENT
Sources of Emission
Manufacturing Processes
Reactor
Chlorination
MPT Unit
t
Waste Treatment Processes
Incinerator and
T* \ ~» _ J
Rates,
Particulates Ib/hr
None
Acid Mist,
e.g. HC1 460
S 420
Basic Mist,
e.g. NaCl 460
Methyl Mono-
chloride
P2°5
Rates, Rate,
Gases/Vapors Ib/hr Odor Odor Unit/hr
diphosphorus — mercaptan
pentoxide kylene
mercaptan H-S
H2S
PCI-
PSCI3
Methanol
Methyl chloride
HC1
—
SO 1,550 None
T* r\
Waste Treatment Plant None
Lagooning None
VO
mercaptan
mercaptan
mercaptan
mercaptan
-------
20
Practical sulfur dioxide emission control processes for H«S,
mercaptan, etc., available for methyl parathion plants are incineration
in series with scrubbing system and carbon adsorption. Control of visible
fumes created by the emission of diphosphorous pentoxide can be achieved
by a mist eliminator, while H_S and mercaptan emission control during the
wastewater treatment can be achieved by chemical oxidation and deodorization.
The air emission control system used by Monsanto is shown in
Figure 4. Incineration is used for the control of the off gases and residue,
while heavy chlorination is used for the control of the wastewater odorous
emissions. The scrubbing system used to control the incinerator emission
is quoted to achieve an efficiency of 95 percent for the removal of
diphosphorous pentoxide. The Brink Mist Eliminator provides about
99.9 percent visibility reduction. Incineration of sulfur may be considered
a better practical control method than recovery because the sulfur that can
be recovered in this process is inescapably contaminated with toxic methyl
parathion.
TO ATMOSPHERE J>_
WATER SUPPLY -. _^..
ff
SCRUBBING
TOWER
INCINER/.TOR v
OFF GASC
•>p
•l.Vj
•;r-;,-»
MIST ELIMINATOR
•\
\ STACK ,
Z
***• *' *
7]
I
s
LIMESTONE NEUTRALIZATION
TO SEWER
V
RECOVERED
PRODUCT
FIGURE 4. PARATHION RESIDUE AND OFF-GAS INCINERATOR
,(7)
Sulfur dioxide emissions presently are not controlled in methyl
parathion manufacturing plants. This means that for a plant producing
about 30 million Ib of methyl parathion per year, the S02 emission per year
will be about 12.3 million Ib or 1,550 Ib per hour; that is, by 1980 at the
present control status S0_ emission from MPT plants will be about 21.2
million Ib or 2,680 Ib per hour.
-------
21
On the basis of available information, Monsanto is the only
company manufacturing methyl parathion that is controlling air emissions;
the sulfur compounds by incineration, diphosphorous pentoxide by scrubbing,
and visibility by the Brink Mist Eliminator. However, S0_ produced during
the incineration of sulfur compounds is not controlled. It was estimated
that about 12.3 million Ib of SO were emitted in 1974. Both Kerr-McGee
Corporation and Stauffer Chemical Company vent their emission into the
atmosphere without any control. According to them, there are occasional
complaints of odor problems from H_S, mercaptan, etc., emissions. It was
estimated that H-S, S, and NaCl emissions from these plants were,
respectively, 3.2, 3.0, and 3.2 million Ib in 1974.
The future trend in air pollution from the manufacture of methyl
parathion will tend to increase due to increased future production unless
efforts are made to control the emissions. Large manufacturing companies,
such as Monsanto, tend to be able to install control equipment, but the
smaller companies indicated that control was economically unfeasible.
Control Costs
Monsanto declined to provide its air pollution control costs.
Estimation of the control costs by theoretical calculations are not possible
within the resources allotted for this study.
/
Significance of Air Contaminant Emission
The present emission control situation in the manufacture of
methyl parathion shows that only Monsanto Company controls the primary
emissions such as FLS, mercaptan, S, and phosphorous pentoxide, while
other companies do not control their emissions. However, in the process
of controlling the primary emissions, a secondary emission (S0?) is produced
and emitted without control.
Those companies that are not controlling lUS and mercaptan
emissions do have occasional odor problems; hence, control in the industry
is necessary. Kraft pulp mills may be compared with the methyl parathion
-------
22
plant in terms of odor problems. The emission requirement in Mississippi
and Alabama for the total reduced sulfur (TRS) is 1.2 and 2.0 Ib/ton of
/D \
pulp, respectively; whereas the calculated emission for HpS alone from the
methyl parathion plant was about 0.12 Ib/lb of active ingredient (AI). Also,
S0_ emission standard from sulfur recovery plants may be compared with that
emitted at the Monsanto plant. In Alabama, the standard is 0.08 Ib/lb of
sulfur processed, while the calculated emission from the Monsanto plant was
about 0.41 Ib/lb of AI. Consequently, these odorous compounds and S02 are
emitted in an amount higher than prevailing state standards for other related
process plants. Thus, the need for control of these emissions from the
methyl parathion plant is significant.
The economic impact of controlling these pollutants is not
assessed since the control costs were not available.
Insecticide - Toxaphene
Toxaphene, a nondefinite chemical compound, is a mixture of
polychloro-bicyclic terpenes with chlorinated camphene. Toxaphene contains
67 to 69 percent chlorine.
Toxaphene is less persistent in the environment compared with the
other compounds in this general group, e.g., aldrin, dieldrin, and endrin.
Toxaphene is severely toxic to aquatic ecosystems, especially to fishes.
It is also toxic to terrestrial ecosystems, but the effects are less
widespread than those caused by the more persistent chlorinated hydrocarbon
pesticides.
Toxaphene is an important agricultural insecticide, especially
in preventing cotton plant damage. It is normally applicable against the
boll weevil, boll worm, cotton aphid, and cotton flea hopper.
Production Inventory
Toxaphene is manufactured in three southern states; namely,
Georgia, Texas, and Missouri, and by three companies, namely, Hercules,
Sanford, and Vicksburg. Table 5 gives the inventory in the United States.
-------
23
TABLE 5. PRODUCERS OF TOXAPHENE IN THE UNITED STATES
(3)
Production
Design Estimate
Company
Hercules, Inc.
Synthetics Dept.
Sonford Chemical Co.
Tenneco Chemicals
Intermediates Div.
Vicksburg Chemical
r»^
LO.
Location Capacity
Brunswick, Ga. 50-75 ^b'
Houston, Tex. 40
Fords, N. J. 125 (b)
Vicksburg, Miss. 5
220-245
1974
65
20
20
3
108
(a) Produces strobane, a polychlorinated toxaphene-like
insecticide.
(b) Reference 1.
-------
24
The distribution conforms with the general location of raw material--
southern pine--and major use area--the southern cotton fields.
The plant capacities and production volume tor toxaphene are
difficult to estimate reliably. The firms contacted would not furnish
the information. Also, the U. S. Tariff Commission does not report
separately on toxaphene, but instead, as the aldrin-toxaphene group which
contains compounds: aldrin, chlordane, endrin, dieldrin, heptachlor, strobane,
and toxaphene. The production of this whole group showed a dramatic increase
from 1970 to 1972. The U. S. production of toxaphene was estimated to be
50 million Ib in 1970.^ An estimate discussed below for 1974 is 108
million Ib, showing that the production has substantially increased.
Future Production Trends
Estimates of toxaphene production are based on the trend in the
proportion of toxaphene in the aldrin-toxaphene group. In 1970, toxaphene
(2)
was about 55 percent of the group production. In 1973, it was about
65 percent, and with the recent registration withdrawal of some
insecticides of this group by EPA, such as aldrin, endrin, and dieldrin,
the proportion and, hence, the production of toxaphene is expected to
increase.
Increases in agricultural production will provide an upward trend
in production. However, like methyl parathion, new, more efficient, and
effective methods of packaging and application will tend to lower demands.
On the basis of these factors, the percentage of increase in
production of toxaphene will tend to decrease from the present estimated
rate of about 25 percent to about 12 percent by the year 1980, giving a
production volume of 233.0 million Ib per year at the end of the decade as
shown in Table 2. The above estimates have been made on the assumption
that no regulatory action will be taken to control the use of toxaphene or
that no substitute chemicals will be introduced.
-------
25
Manufacturing Process
The production of toxaphene involves two main steps: the
production of camphene in a reactor from ot-pinene, which is a compound
obtained from southern pine stumps; and the reaction of chlorine gas with
camphene in a solvent solution at the chlorinator.
The reaction chemistry is given below.*
Catalyst
CH,
Cl,
CH3 UV or cat^
o/-Pinene
Camphene
~ C10H10C18 + 6 HC1
Toxaphene (mixed isomers
and related compounds
67-69% Cl)
Details of the operating conditions in the manufacture are not
available since they are proprietary.
Raw and Waste Material Handling
The raw materials involved in the manufacture of toxaphene are
camphene, chlorine, and solvent, plus other compounds used in the effluent
treatments.
The production and waste material handling schematic used by
Hercules is presented in Figure 5. The gaseous emissions from the chlorinator,
chlorine gas, hydrochloric acid, and solvent vapors are passed through
condensers, caustic scrubbers, and a tower containing limestone, while the
liquid toxaphene is filtered, stripped, and formulated into marketable forms.
The wastewater is neutralized and subjected to primary treatment prior to
discharge to the creek.
Hercules claims to have rigorous safety standards. They maintain
a fire truck and crew on site. Production workers receive annual checkups
and have had an excellent health record, according to the company, with no
-------
Southern
Pine Stumps
-«»• 100 Other Products
<1 %
Pinene
Main Plant
Waste Stream
Reactor
Wastes
Chlorine
Solvent -
H20
Lime
NaOH
Lime-
•
Stone
Surface^
Waters "
T
i
Camphene
I
Mixed
Xylenes
Chlorinator
•HCI Gas
Absorber
T
Scrubbers
(2)
I
Neutralizer
Primary
Waste
Treatment
Plant
T
Discharge to
Tidal Creek
Toxaphene.
Solution
Recovered
Muriatic Acid
L
•Toxaphene —^-Solution
Jo Solid
"Waste
Dust
Formulation
Baghouse Dust
Collector
Atmosphere
90 % Toxaphene
k..,
^Shipments
ro
FIGURE 5. PRODUCTION AND WASTE HANDLING SCHEMATIC FOR TOXAPHENE
C6)
-------
27
correlations of death or illness with toxaphene handling. The company
stated that they are in compliance with all air pollution control regula-
tions promulgated by the State of Georgia under the Federal Clean Air Act
of 1970. Information on raw and waste material handling at other manu-
facturing plants is not available.
Air Contaminant Emissions, Sources, and Rates
Main sources of air contaminant emissions are the reactor, the
chlorinator, and toxaphene formulations. There is no information on
emissions from oi-pinene production.
The main emission from the reactor is chlorine gas; the emissions
from the chlorinator are chlorine gas, hydrochloric acid, and solvent vapor,
and toxaphene particulates are released during formulation. These compounds
and sources are given in Table 6. The emission rates of these compounds
are not available, except HC1 which is estimated to be 4,350 Ib/hr* from a
65-million-lb-capacity plant.
Air Contaminant Emission Control
Most systems available in chemical industries for controlling
acidic gases are applicable to the control of emissions from- the manu-
facture of toxaphene. There are three main control techniques: scrubbing
(alkali or water), stripping, and adsorption.
Hercules uses these control techniques to control HC1, chlorine
gas, and solvent vapor emissions. The emissions are initially passed
through condensers where the majority, of the solvent and hydrochloric acid
is removed. Following the condensers are caustic scrubbers which remove
additional traces of hydrochloric acid and chlorine. Finally, the effluent
is passed through large towers containing limestone, which Is said to remove
the "balance" of the hydrochloric acid. The final rate of emissions from
the limestone towers is not known, but Hercules claims up to 100 percent
efficiency.
* Estimated at 0.53 Ib/lb AI.
-------
TABLE 6. AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES FROM
TOXAPHENE MANUFACTURE AND WASTE TREATMENT
Sources of Emission
Participates
Rate, Gases/ Rate,. . Rate,
Ib/hr Vapors Ib/hr Od°r Odor Units/hr
Manufacturing Steps
^•-Pinene Production
NA
NA
NA
Camphene-Preduction
(Reactor)
NA
NA
NA
Chlorination-Toxaphene None
Production
Toxaphene Granular Toxaphene
Production Dust
Cl, gas
HC1
Solvent
Vapor
None
4350
(6)
NA
None
N>
00
Waste Treatment Processes
Wastewater Treatment Plant
None
Cl,
HC1
Possible
candidate
CU
-------
29
In chemical industries various control technologies are available
for controlling particulates, such as electrostatic precipitators, baghouses,
scrubbers, etc.
Hercules uses baghouses to control the toxaphene particulate
emissions. No information is available on the uncontrolled and controlled
emissions.
No definite statement can be made on the present air pollution
control status in the manufacture of toxaphene. Control information is
unavailable from other manufacturing plants.
Control Costs
Emissions from the manufacture of toxaphene are not controlled
separately; instead, they are passed together with emissions from the
manufacture of other pesticides in their class through the same control
system. Consequently, control cost information is unavailable.
Significance of Air Contaminant Emission
There is high emission of HC1 (about 0.53 Ib/lb AI) in the
manufacture of toxaphene. It is recognized that HC1 is a liquid at normal
temperature and pressure. However, fumes of HC1 are emitted, although the
rate of emission is not known.
A particularly important emission in the manufacture of toxaphene
is that of toxaphene particulates. Toxaphene is toxic to mammals; for
example, the toxic level for dogs is 20 ppm. However, data are
unavailable on the rate of emission from any plant. Consequently, an
assessment of the significance of emission from the plants is not possible
at this time.
Herbicide - Monosodium Acid Methanearsonate (MSMA)
MSMA is a selective herbicide of the organic arsenical group.
MSMA is not very toxic to animals and it degrades fairly readily in the
-------
30
soil. It is a postemergent herbicide used to control hard-to-kill grass
weeds.
Production Inventory
Monosodium acid methanearsonate is produced in three states--
Wisconsin, Texas, and New Jersey—and by three companies—The Ansul
Company, Diamond Shamrock Chemical Company, and Vineland Chemical Company.
The plant design capacities of the producers and their production are shown
in Table 7.
The U. S. capacities and production volumes are known for the
Ansul Company and Diamond Shamrock Chemical Company. Their combined
estimated production for 1973 and 1974 were 33.1 and 32.4 million Ib,
respectively. No information is available on the capacity and production
volume of Vineland Chemical Company. However, it is estimated that the
total production for the methanearsonic acid salts for 1973 and 1974 is about
40 to 50 million Ib, respectively.
Fviture Production Trends
The production of MSMA has been showing an upward trend since
1971. Ansul has been producing at design capacity while Diamond Shamrock
Chemical Company has maintained a production of about 50 percent above
design capacity. This means that either new plants will be built or
existing ones expanded, or both, to meet the demand. MSMA belongs to the
organic derivatives of the trivalent form of arsenic. Its selective,
postemergent efficacy against hard-to-kill grass weeds makes MSMA an important
herbicide in agricultural production. Therefore, its production in years ahead
will tend to increase with the recent increased demand in the production of
food and fibre. The appearance of competing herbicide in the marketplace
may lower the production of MSMA.
A conservative estimate for the production has been presented in
Table 1. Again, an increase in production is projected, but this rate of
increase will tend to decrease from the present 25 percent annually to about
10 percent annually by the year 1980.
-------
31
TABLE 7. PRODUCERS OF MSMA IN THE UNITED STATES
Company
Location
Design
Plant Capacity
million Ib
Production
Estimate
.million Ib
1973 1974
The Ansul Co., Chemical
Div.
Marinette, Wise.
Diamond Shamrock Chemical Greens Bayo, Tex.
Co., Agricultural Div.
10
17
16.1 15.7
17.0 16.7
Vine land Chemical Co.
Vine land, N. J.
NA NA
-------
32
Manufacturing Process
Three main steps are involved in the manufacture of MSMA:
production of sodium arsenite, methylarsonic acid, and MSMA.
The first step in the production of MSMA begins with the formation
of sodium arsenite by the reaction of arsenic trioxide and 50 percent caustic
soda solution. In the next step, 25 percent solution of the sodium arsenite
is treated under pressure with methyl chloride to give the disodium methane
arsenate (DSMA). Some companies sell a portion of the DSMA for herbicide
uses, but since DSMA is less soluble, it requires a higher application rate.
Most companies go a step further to prepare MSMA.
MSMA is prepared by adjusting the pH of DSMA with sulfuric acid
in a reactor. The material is centrifuged to remove salts such as sodium
sulfate and sodium chloride (which are waste by-products) and the resulting
solution is concentrated by evaporating the water. Hydrogen peroxide is
added to oxidize the unreacted trivalent arsenic to the pentavalent form.
The final product is formulated with a wetting agent and packaged into
1-gallon, 5-gallon, 30-gallon, or 55-gallon containers. The active
ingredient of MSMA is sold at a number of concentrations, but approximately
58 percent is the maximum concentration that can be prepared without undue
viscosity effects.
The simple process chemistry is given below.
As203 + 6NaOH > 2Na3As03 + 3H20
Arsenic Sodium
Trioxide Arsenite
Na3As03 + CH3C1
Methyl
Chloride
2CH3AsO(ONa)2 + H2SO^
DSMA
CH3AsO(ONa)2 + NaCl
-------
33
Raw and Waste Material Handling
Raw materials used to produce MSMA are arsenic trioxide, sodium
hydroxide, methyl chloride, and sulfuric acid. Arsenic trioxide is the
most toxic species, and it is imperative that this compound be handled
with care.
It is unloaded under a hood equipped with an exhaust blower that
pulls the dust through ducts to a dust collector, or scrubber. Employees
use respirators, and frequent employee health screening to check any
health danger is required by most firms.
The production and waste schematic is shown in Figure 6.
A major concern in the wastewater treatment is the disposal of
the mixture of sodium sulfate and sodium chlorate contaminated with arsenic.
Diamond Shamrock handles this by precipitation and centrifugation. After
washing, they are disposed of in a landfill which is registered with the
State of Texas. No information on air emissions from the disposal site is
available. Methanol, a side product of methyl chloride hydrolysis and
water, is recycled.
Air Contaminant Emissions. Sources, and Rates
The main source of air contaminant emissions during the
manufacture of MSMA is in the sodium arsenite production during the
unloading of arsenic trioxide. Minor emissions may occur during the
processing of the MSMA by evaporation from vents of the reactors.
The main emission during the production of sodium arsenite is
arsenic trioxide, which is very toxic. Diamond estimates the controlled
-8 8
emission of As 0~ to be 6 x 10 Ib/ton or 6.44 x 10 Ib/hr. During the
production of DMSA and MSMA, vapors of CH-jCl, Na^O^, and CH.O, are given off.
Arsenic-contaminated solid materials including NaCl, Na_SO,,
and MSMA are landfilled. No information is available on the emissions from
these disposal sites. The list of the pollutants from various sources is
given in Table 8.
-------
1
A O
KJ0f\LJ
H O
3
Dust
Collector
t
, k*. I |n;f
25%No3AsO3
Storage
1
Methylarsonic
> Acid Unit
\
Crude . .fei Purification fe. D^MA Salei
DSMA
i
... ^ ""SMA _.^ [•.,_»«.._»,.. »^ I^.^IT -_ fc TITy AA?I
j^ Reactor -•
1 1
Stripper « Aqueous By-Product
CH3OH Salts
i "2°r^ 1
CH-sOH \A/«eUar ^ No^SOx
3 Washer -^^2, 4
Recovered LLlqu5d T<> Approved
j Land Fill
u>
FIGURE 6. PRODUCTION AND WASTE HANDLING SCHEMATIC FOR MSMA
(1)
-------
TABLE 8. AIR CONTAMINANT EMISSIONS, SOURCES AND RATES
FROM MSMA MANUFACTURE AND WASTE TREATMENT
Sources of Emissions
Particulates
Rates,
Ib/hr
Gases/
Vapors
Rates,
ib/hr
. Rates,
Odor Odor Unit/hr
Manufacturing Steps
Sodium Arsenite Production
(Reactor Vents)
AS?°T 6.44x10
—8
DMSA Production
(Reactor Vents)
MSMA Production
(Reactor Vents)
None
None
CH3C1
CH3OH
NaCl
MSMA
Same
Same
MSMA Processing
(Evaporator and
Centrifuge)
MSMA
Waste Disposal Processes
Landfill
Ponds
NA
MA
Not Identified
Not Identified —
-------
36
Air Contaminant Emission Control
The only air pollutant controlled in this industry is As20,..
The compound is emitted as particulates and various control techniques
are available, such as baghouses, scrubbers, and electrostatic precipitators.
Diamond Shamrock operates the As20_ drum opening and dump bin
under a hood equipped with a blower that will pull the As20_ into a
bagfilter for collection. Ansul's plant controls the arsenic trioxide
emission by a scrubbing system. Efficiencies of these control systems
,are not known by the firms. The best control technique for this highly
toxic arsenic trioxide is to have both baghouses and scrubbers in series.
The bag filter is useful in recovering As20,, while the scrubber removes the
smaller size particles that normally will not be collected by the bag
filter. Unfortunately, the scrubbing system may create water pollution
problems.
Assuming an industry estimate of a controlled emission rate of
6.44 x 10"b Ib/hr As203, it is estimated that the amount emitted per year
by a plant of 17 million Ib capacity is 5.1 x 10* Ib.
Ansul Company observed occasional odor nuisance, but no
identification of the odor-producing compounds has been made.
A definite statement on the level of emission control is not
N
possible because of incomplete data. However, it can safely be stated that
all companies control arsenic trioxide emission but controlled emission
rates are not known. A definite need exists to monitor the emission of this
very toxic pollutant.
Future emissions will increase on the order of the production
projections if the present level of control is maintained. Assuming an
emission rate of As Q given by Diamond Company as 6.44 x 10"® Ib/hr AsoOs
emission for the industry by 1980 will be 0.0393 Ib/year.
Control Costs
Diamond Shamrock--with design capacity of 17 million Ib per year--
gives the cost for controlling As203 as $8,000 for capital cost, and $200
per year for the operating costs. An acidifier vent scrubber is said to
-------
37
cost $500 for the capital, and $100 per .year as the operating cost. Air
flow rates and hence sizes and efficiencies of the equipment were not
provided for verification purposes.
Significance of Air Contaminant Emission
Of importance in the industry is the control of As20_ emissions
because of their high toxicity and carcinogenic property. As of this date,
the responding firms do control As~0, emissions but the level of control
is not known.
Herbicide - Trifluralin
Trifluralin Is a selective soil-applied or preemergence
herbicide of the class Nltroaromatic. It is used to control annual grass
weeds and some annual broad-leaves. About 60 percent of the trifluralin
is used in the production of soybeans, 30 percent cotton, and 10 percent
others.^
Toxicity of trifluralln to mammals is low, but it is highly
toxic to fish. It is degradable by microbial activity, and moderately
persistent in the soil, with about 85 percent of the applied rate degrading
during the growing season.'^'
Production Inventory
Trifluralin is manufactured by only one firm, Eli Lilly and
Company, at their Tippecanoe Labs at Lafayette, Indiana. The plant capacity
is estimated to be 35 million pounds per year. Production volumes for
1971 and 1972 were estimated respectively as 25 and 21 million pounds.
Future Production Trends
The future production of trifluralin will depend on availability
of raw materials and sale of trifluralin. The impact of the availability
-------
38
of raw materials on trifluralin production is difficult to assess because
of many unpredictable influencing factors.
Since trifluralin is mainly used in agricultural production such
as cotton, soybeans, etc., the future growth rate of these crops will
influence the growth in production of trifluralin.
The production of these crops in the years ahead will increase
because of the current demand in agricultural production.
In the projections given in Table 1, increased agricultural
production was reflected in increased trifluralin production while the
appearance of potential competing herbicides was reflected in a decreased
percentage of growth. By 1980, it is projected that about 38 million pounds
will be produced.
Manufacturing Process
The manufacture of trifluralin involves two main steps: nitration
and amination. The simple process chemistry is given below while the flow
diagram is shown in Figure 7.
CF,
OH
HNO,
p-chlorobenzotrifluoride
CF,
Dipropylamine
Sodium Carbonate
Water
3,5-dinitro-4-chloro
benzotrifluoride
CF,
trifluralin
Nitration involves the reaction of the following compounds in
reactors: p-chlorobenzotrifluoride, sulfuric acid, and nitric acid. The
product of the reaction is 3,5-dinitro-4-chlorobenzotrifluoride, and the
by-product is spent sulfuric acid which is recycled. The main off-gases
are nitrogen oxides.
Amination is the second-stage reaction involving the reaction of
3,5-dinitro-4-chlorobenzotrifluoride, dipropyl amine, and sodium carbonate
in solution. The product of the reaction is trifluralin and the effluent is
brine solution which is treated for recovery.
-------
39
p-Chlorobenzotrlfluoride
Sulfuric Acid
Nitric Acid
Off Gases to Scrubber
NITRATION
3.5-Dinitro-4-chiorobenzotrifluoride
Dipropyl Amine
Sodium Carbonate
Spent Sulfuric Acid
Water
AMINATION
Trifluralin v
Brine Solution to
Treatment Facility
FIGURE 7* SIMPLE FLOWSHEET FOR TRIFLURALIN MANUFACTURE
-------
40
Raw and Waste Material Handling
The raw materials used in the manufacture of trifluralin are
nitric acid, sulfuric acid, sodium carbonate, dipropylamine, and
p-chlorobenzotrifluoride. The main toxic materials are the acids, and their
handling practices in chemical industries are well-known.
Eli Lilly provided information of the measures adopted to protect
the health of their employees. These included wearing protective
clothing.including self-contained breathing apparatus for certain unloading
operations, isolation piping and tanks for each raw material, containment
procedures and facilities for accidental spills, routine review procedures
between operators, and safety and material handling personnel.
Greater detail of the production and waste handling schematic
is shown in Figure 8.
Air Contaminant Emissions. Sources, and Rates
The main sources of air contaminant emissions are the nitration
reactor and condenser.
The main gaseous emissions from the nitration reactor are sulfur
dioxide, sulfur trioxide, hydrogen fluoride, hydrogen chloride, and nitrogen
oxides, while particulate emissions from the reactor consist of nitrate,
sulfate, and chloride. Emissions from the condensers are mainly aerosol
consisting of trichloromethane and trifluralin. The wastewater from the
plant is neutralized, and subjected to the conventional waste treatment
of primary clarification and secondary aerated biological treatment. There
are no odors or other air contaminant emissions during the wastewater
treatment. Table 9 is a list of the contaminants emitted and their
rates as measured by the company.
-------
PCBT
HNO3-
Monon it rotor
' Oleum.
±
Dinitrator
J
NO,
f
Scrubber
Waste
Water
Excess Acid
Sold
Acid
Recovery
Condenser
Vac
Exhaust
NH(C3H7)2
HoO
Na2CO3
I
Amination
Reactor
I
Filter
Salt
Water
Waste
Aromatic
Naptha
Trifluralin (e.c.)
FIGURE 8. PRODUCTION AND WASTE HANDLING SCHEMATIC FOR TRIFLURALIN(6)
-------
TABLE 9. AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES FROM
TRIFLURALIN MANUFACTURE AND WASTE TREATMENT
Sources
Manufacturing Process
Nitration
Condenser
Participates
nitrate
sulfate
chloride
cue 13
Trifluralin
Rate,
Ib/hr
1
1
1
NA
NA
Gases /Vapors
sulfur dioxide
sulfur tioxide
hydrogen fluoride
hydrogen chloride
nitrogen oxides
Rate,
Ib/hr
3
1 •
1
10
3
Rate,
Odor Odor Unit/hr
None
None
Was tewater Treatment
None
None
-------
43
Air Contaminant Emission Control
Air contaminant emissions from the manufacture of trifluralin
are primarily gases and particulates. Control of these compounds in the
chemical industry is achieved by many methods, but those directly applicable
to the trifluralin industry are wet scrubbers.
Eli Lilly uses wet scrubbers and their quoted efficiency is about
90 percent.
Control Costs
The Eli Lilly emission control system consists of 1- and 2-stage
venturi scrubbers and tri-mer wet scrubbers. The total flow through the
system is about 20,000 standard cubic feet per minute. Eli Lilly estimates
that capital cost so far is about one million dollars. They have no information
on the operating cost.
Significance of Air Contaminant Emission
There are a large number of air contaminant emissions in the
industry. The State of Indiana has no stationary source emission standard
for sulfur and nitrogen compounds from the process industry. However, the
emission rates of these compounds are small when compared with the State of
Massachusetts standards which are 10 Ib/hr for nitrogen oxides and 25 Ib/hr
for the process industry which are 10 Ib/hr for nitrogen oxides and 25 Ib/hr
(8)
for sulfur oxide. The toxic material emitted to the environment is
trifluralin which, according to present knowledge, is highly toxic only to
fish and not to mammals. Unfortunately, data are not available on emission rates,
Fungicide and Wood Preservation - Pentachlorophenol
Pentachlorophenol (PCP) is a wood preservative, but it is also
used as a contact herbicide. About 75 percent of the PCP is used as a
wood preservative for poles, crossarms, and pilings.
-------
44
It is hazardous Co man primarily because it is capable of
causing eye injuries such as conjunctival redness, iritis, and slight
corneal damage. In solution, it can be absorbed through the skin to toxic
amounts. Consequently, its handling requires due precautions.
PCP is biodegradable and thus gives no long-term pollution
problems.
Production Inventory
Pentachlorophenol is manufactured at five chemical companies in
five states. Unlike some agricultural pesticides, which are restricted
to the area of intense application, it is not restricted to one geographical
area. Because of its wide application in the field of industrial pres-
ervation, and logistics of distribution, it is produced in states widely
separated — Washington, Kansas, Texas, Michigan, and Illinois.
The present annual U.S. capacity for the manufacture of PCP is
about 97 million pounds. In 1973, the production was 46.6 million pounds(3)
and the estimate for 1974 is about 48.9 million pounds. The manufacturers
of PCP, their capacities, and estimated production for 1974 are shown in
Table 10.
Future Production Trends
With the increased cost of other wood preservatives such as
crude oil and coal tar crudes (creosote), the demand for PCP as a wood
preservative may increase.
However, since PCP is used almost exclusively as a wood pre-
servative for power and phone transmission poles, the increasing use of
underground transmission and nonwood-related materials for poles, such as
concrete and glass fibre, will tend to force PCP to peak about 1980 and
then diminish. Production projections to 1980 are given in Table 1. A
gradual increase in production is forecast from the present 5 percent to
10 percent by 1980. The greatest impetus to production appears to be
the lack of a> competing product like crude oil, which is supported by the
-------
45
TABLE 10. PRODUCERS OF PCP IN THE UNITED STATES
(3,9)
Company
Location
Annual Capacity,
million Ib
Eat. 1974
Production,
million Ib
Dow Chemical Co.
Monsanto Indiat. Chems,
Reichhold Chems.; Inc.
sonford Chemical Co,,
Vulcan Materials Co.
Chemicals Division
Midland, Michigan
Co. Sauget, Illinois
Tacoma, Washington
Houston, Texas
Wichita, Kansas
Total
18
26
16
18
19
?7
5
10
10
5.2
18.7
"4879
-------
46
estimates of some of the companies who think that their production will
double by 1980. The projected 1980 production is 74.9 million pounds.
Manufacturing Process
Almost all of the PCP produced in the United States is manufactured
by the chlorination of phenol. A simple reaction chemistry of the process
is shown below; and the simple schematic in Figure 9.
OH
Phenol
+ 5C1
Catalyst
- >
Elevated
temperature
+ 5HC1
Phenol
Chlorine
Aluminum
.Chloride
(Catalyst)
Pentachlorophenol
Chlorine
Scrubber
I
C6CIXOH
-1
Recovery
HCI
Recycle to
Chlorine
Plant
FIGURE 9. PRODUCTION AND WASTE HANDLING SCHEMATIC FOR PENTACHLOROPHENOL
(10)
-------
47
The general manufacturing process can be described as follows.
The chlorination is performed at substantially atmospheric
pressure in a reactor. The temperature of the phenol in the primary
reactor at the start is in the range of 65-130°C (preferably 105°C) and
is held in this range until the melting point of the product reaches 95°C.
About three or four atoms of chlorine are combined at this point, and the
temperature is progressively increased to maintain a temperature of about
10°C over the product melting point, until the reaction is completed in
5-15 hours. The mixture is a liquid, and a solvent is not required, but
the catalyst concentration is critical; about 0.0075 mole of anhydrous
aluminum chloride is usually'used per mole of phenol.
The PCP from the reactions may be further treated (formulated)
to effect more marketable products. At Reichhold, the PCP undergoes ingot
casting and shotting operation.
Raw and Waste Material Handling
The raw materials used in the manufacture of PCP are phenol, chlorine,
and a catalyst — aluminum chloride. Sources of raw materials vary from firm
to firm. Some manufacturers produce these materials on site, while others
purchase the same.
Dow Chemical makes phenol from benzene (via monochlorobenzene),
but this method of making phenol is being generally replaced by the
cutnene oxidation process. Monsanto also makes both the phenol and chlorine;
while Vulcan makes the chlorine, but purchases the phenol; and Reichhold
makes the phenol, but purchases the chlorine.
While some companies report that no particular precautions are
taken at PCP plants, others point out specific precautions such as handling
chlorine and phenol in closed systems, and the use of plant coveralls, rubber
gloves, safety glasses, goggles, and hard hats. There are occasional face
shields and respirators for employee protection when the situation calls
for their use.
-------
48
Air Contaminant Emissions. Sources, and Rates
In the manufacture of pentachlorophenol, there are three main
sources of air emissions: the PCP reactor, ingot and shotting operation,
and the acid system reactors. At the PCP reactor, the following compounds
are emitted: chlorine gas, hydrochloric acid vapor (HC1), and chlorinated
phenols. At the acid system reactors and process vents the chlorinated
phenol and chlorine are emitted. The particulate emission from the manu-
facturing process is limited to PCP dust from the ingot casting and shotting
operation.
There are no air contaminant emissions reported from the waste-
water treatment. The sources of emissions and pollutants are given in
Table 11.
Air Contaminant Emission Control
Major emissions from the manufacture of PCP are gases and parti-
culates, which are amenable to chemical industrial air pollution control
techniques. Practical controls used in the industry are scrubbers for the
gaseous emissions, and filter bags for the partlculates.
Reichhold by-product recovery systems and air pollution control
systems for gaseous and particulate emissions are shown in Figures 10 and
11, respectively. The control methods in terms of efficiencies are described
in Table 12.
Firms responding to our questionnaires reported that under
proper operation of these control devices, exhaust effluents are invisible
and free from odor.
Cost of Control
Reichhold gave the following control costs for their 12-million-
pound-capacity plant:
-------
TABLE 11. AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES
FROM PCP MANUFACTURE AND WASTE TREATMENT
Sources of Emission Particulates
Rates,
Ib/hr
Gases/Vapors
Rates, Rates,
Ib/hr Odor Odor Units/hr
Manufacturing Process
PCP Reactor
Acid System Reactors
Ingot Casting
Shotting Operation
Wastewater Treatment
None
None
PCP
PCP
(1) chlorinated phenol
(2) chlorine gas
(3) Hydrochloric acid
vapor
(1) chlorinated phenol
(2) chlorine gas
(3) Hydrochloric acid
vapor
None
None
-P-
vO
PCP
PCP
None
-------
Vent
Chlorinated phenol feed
I
1
1
1
1
I
1
1 ,
t
PCP
reactor
1
i
PCP
H
4
HCI + CI2 i.
gas
c
.
c
r* k
L.
ID
JQ
J3
•3
|UJ1
O
cn
O
c
a>
JZ
Q.
3
'
D
•"•
;
•y
_r
i
HCI gas
HCI |
gas /*3r^
v * ^ 1 ^ S\ A _: -i 1
* phenol ^VKJ Acid cooler
^*r*^
> 1 Phenol
1 1 i )
/ \
/ - . _ . \ ,
1 Phenol scrubber] ROW
V storage /pncnoi
^-rk
J
C
c
-J
^
Vent
V
X3
O
jQ
O
O
^L
1
JVater
3
L
JT
/
*
1
•A
JC
0
O
„ Water
spray
"~X To waste
L__^-
Acid tank
vent
HCI
storage
FIGURE 10. SCRUBBING SYSTEMS FOR THE CONTROL OF HCI, C12 EMITTED FROM PCP REACTOR
-------
Vent
Dust
collector
From PCP reactor
Dust I
Fume hood
Ingot
casting
Dust
collector
•Vent
Return to
shot pot
Forced draft
air
To product
packaging
FIGURE 11. DUST COLLECTOR SCHEMATICS FOR THE PENTA EMISSION CONTROL
-------
52
TABLE 12. AIR CONTAMINANT CONTROL METHODS
USED IN PCP MANUFACTURE
Control
Sys tern
Wet Packed and
Venturi Scrubber
(with water)
Efficiency,
percent
99-100
Compound Controlled
Controlled Emission, Ib/ton
C12 N.A.
HC1 N.A. ,
Phenol 2 -' ,
Sodium Penta- 4.32 -'
chloro phenate
Dust Collector
(bay filters) at
ingot casting
at shotting operation
99
95
PCP
Fume
PCP
0.1 -'
1 b/
(a) Controlled emission reported by Monsanto based on 1974 production.
(b) Controlled emission reported by Reichhold based on 1974 production.
-------
53
Operating
Name of Control Device Size Capital Cost($) Cost ($/yr)
Bag filter (2) (1) 2000 ft2* $ 70,000 $ 6,000
(2) 450 ft2
Mechanical Seals (for PCP reactor) 50,000 6,250
Phenol and Acid Scrubber 80,000 1,000
Area of bag filter.
According to Reichhold, the greatest problem arose from the dust
collectors because of the lack of reliability. They consider dust emissions
less than the present 1.0 Ib/ton to be too restrictive, since this will
require additional capital expenditures in excess of $100,000 and operating
costs of $10,000/year for their plant capacity of 16 million Ib/hr.
Significance of Air Contaminant Emissions
The quality of air contaminant emissions in the manufacture of
PCP is significant due to the fact that large numbers of compounds are emitted
at high emission rates. The control of the emissions is desirable as a
method of recovery of materials. Since PCP is toxic to human respiratory
tracts and eyes, its very efficient control is recommended. The present control
method which uses inadequate cloth area of bag filters needs augmentation.
Futnigant - Paradichlorobenzene
About 50 percent of the paradichlorobenzene (PDCB) is used as
lavatory space deodorant, about 40 percent in moth control, and the rest
as reactive intermediates in the production of chemicals such as agricul-
tural pesticides and as an industrial porosity control agent.
PDCB causes moderate irritation to the human eye, throat, nose,
and skin, with severe problems on long exposure. Continued exposure to
PDCB vapors for months or years causes headache, portal cirrhosis, or
atrophy of the liver.'^'
PDCB undergoes biological, nonbiological, and sunlight degrad-
ation at a moderate to rapid rate.
-------
Production Inventory
Paradichlorobenzene is manufactured by eight companies in nine
states. These companies, their plant design capacities, and estimated 1974
production are given in Table 13.
The annual U.S. capacity is about 150 million pounds. Capacities are
flexible and throughput depends on demand and available feedstocks. Benzene
has been in very short supply recently due to decreased petroleum supplies.
The production for p-dichlorobenzene in 1972 and 1973 was 77.3 and 85 million
pounds, respectively, and the 1974 production is estimated to show a moderate
increase of about 93.5 million pounds. Generally, production has varied
from 50 to 60 percent of plant capacity.
Future Production Trends
Based on demand and raw material availability, production of PDCB
is estimated to increase by about 2 percent per year through 1977.^ '
Various arguments have been presented for growth projection. Some feel
that the growth rate will be at least in line with gross national product and
an increase in disposable income, while others feel that continued rise
of polyester and newer synthetic fibre at the expense of wool and cotton
would tend to level off production.
Two smaller suppliers of PDCB have withdrawn from the market
since 1970, but expansions by others in the business have more than
compensated. Most producers see little or no growth for p-dichlorobenzene.
Still, there is strong feeling by some that the demand for the space
deodorant used in restaurants, public buildings, etc., will continue to
grow and the moth control market will hold its own.^11^ Projections up to
the year 1980 were provided in Table 1, and the production by the end of
the decade is estimated at 112 million pounds.
-------
55
TABLE 13. PRODUCERS OF PARADICHLOROBENZENE
IN THE UNITED STATES(3>4>
Company
Allied Chemical Corp.,
Industrial Chems . Div.
Chemical Products Corp.
Dow Chemical Co.
Monsanto Industrial
Chemical
PPG Industries, Inc.
Industrial Chem. Div.
Solvent Chemical Co., Inc.
Specialty Organics, Inc.
Standard Chlorine Chemical
Co., Inc.
Location
Syracuse (Solvay) , N.Y.
Cartersville, Ga.
Midland, Mich.
Sauget, 111.
Natrium, W. Va.
Maiden, Mass.
Niagara Falls, N.Y.
Irwindale, Calif.
Delaware City, Del.
TOTAL
Annual
Capacity,
Ib x 106
12
3
16
12
21
5 (a)
10
2(b)
60(b)
141
1974
Production
Ib x 106
9.0
NA
NA
NA
NA
12.0
2.0
24.0
(a) Production will be phased out in late 1974.
(b) These are processors — they buy crude mixed chlorinated benzenes
and purify them.
-------
56
Manufacturing Process
Paradichlorobenzene Is produced almost entirely as a by-product
from the manufacture of monochlorobenzene, which is produced by the
chlorination of benzene. Generally, prolonged chlorination is used to
produce various by-products besides PDCB, as shown in the following reaction
chemistry:
C12
Benzene Chlorine
Monochloro
benzene
(70-75%
yield)
Cl
Cl
Ortho Para
Dichlorobenzenes
(10-207. yield)
Clx + HC1
Polychloro
benzenes
Benzene and chlorine are reacted in a chlorinator. The product
is neutralized by sodium hydroxide with the recovery of dichlorobenzene.
The production and waste material handling are shown in Figure 12.
Beruent or
chlorobenjena
Wat*
•Vtnt
Bcnrene
Chlorine
Hydrochloric
acid *"
Chlorinator
-^Scrubber j
li
•"T Hydrochloric
Sodium «cid *
hydroiuda
Ntutraliiinc ». f
tank "'[
B«nztn« and water
Beniena and cMorobanzan*
CMorobinimi
Oichloro- and
polychlorobantantt
to distillation
DicMorobtntan*
sludft
to f•covwy
FIGURE 12.
PRODUCTION AND WASTE HANDLING x10N
SCHEMATIC FOR PARADICHLOROBENZENE
-------
57
Raw and Waste Material Handling
The essential raw materials used in the manufacture of PDC8
are: benzene, chlorine, and sodium hydroxide. The main toxic materials
that need special handling during PDCB manufacture are chlorine, HC1,
and PDCB. Most firms do adopt some precautionary measures for their em-
ployees such as wearing of plant coveralls, rubber gloves, goggles,
safety glasses, hard hats, and face shields and respirators when necessary.
The material flow within a typical plant is shown in Table 12.
At Dow Chemical, the HC1 by-product is apparently recycled to chlorine
production while trichlorobenzenes are recovered.
At Monsanto, the HC1 is recovered as muriatic acid with only
small amounts escaping through vents or going to a waste treatment plant.
The PDCB work area is ventilated and the exhaust air goes to a wet scrubber.
Monsanto is reported to monitor the PDCB concentration level.
Air Contaminant Emissions, Sources, and Rates
Sources of air emissions are chlorinator, PDCB recovery system,
and the press room. The pollutants emitted are hydrochloric acid, chlorine,
benzene, chlorobenzene, and PDCB. Data are unavailable on the rates of
emission of these compounds, making the nationwide emission status difficult to
estimate. Pollutants emitted from various sources are presented in Table 14.
Minor emissions such as chlorine and HC1 are given off at the
wastewater treatment plant.
Air Contaminant Emission Control
Among the pollution control equipment used to control the gaseous
and particulate emissions are wet scrubbers and absorption columns. An
estimate of control efficiencies at the Standard Chlorine Company is pre-
sented in Table 15.
-------
TABLE 14. AIR POLLUTION EMISSIONS, SOURCES, AND RATES FROM
PARADICHLOROBENZENE MANUFACTURE AND WASTE TREATMENT
Sources of Emissions
Participates
Rates,
Lb/hr
Gases/Vapors
Rates, Rates,
Ib/hr Odor Odor Units/hr
Manufacturing Processes
Chlorinator
P-dichlorobenzene
Recovery
Press Room
PDCB
Chloride
PDCB
(1) HC1
(2) Benzene
(3) Chlorobenzene
(4) C12
Chlorobenzene
Same
Same
Same
Same
Same
Same
oo
Uastewater Treatment
(1) Cl.
(2) HC1
Same
-------
59
TABLE 15. AIR POLLUTION CONTROL AT STANDARD
CHLORINE
Water Device
Efficiency,*
percent
Compound
Controlled
Water Scrubber
Absorption
Column
90
95
(1) HC1
(2) Benzene
(3) Chlorobenzene
(4) Dichlorobenzene
(5) Paradichlorobenzene
(1) HC1
(2) Chlorobenzene
(3) Benzene
* Controlled emission data were not provided by any one
company.
-------
60
borne companies, for example, Allied, Solvent, and Specialty,
with annual capacities around 10 million pounds, do not utilize control devices,
They argue that it will be too restrictive if they are compelled to have all
p-dichlorobenzene operating areas confined and exhaust air sent through a
scrubbing system. The size of the control hood will be too large due to the
extensive area involved.
However, Standard Chlorine has controls in place (water scrubber
and column absorber as given above) and the Monsanto Industries controls by
means of water scrubber only. The press room is not controlled. Emission
from this area is primarily PDCB.~
The acceptable level of paradichlorobenzene used as the Threshold
Limit Value by American Conference of Governmental Industrial Hygienists
(ACGIH) is 75 ppm. It is not known whether the concentration in the press
room exceeds this range, since there are no measured data.
Control Cost
Standard Chlorine provided the following control costs. Standard
has an annual design capacity of 50 million pounds.
Capital Operating
Control System Size Cost($) Cost($/vr)
Water Scrubber^2) 48" & 16" 28,000 40,000
Carbon Absorption 100,000 NA
Columns
Significance of Air Contaminant Emission
The nature of the pollutants emitted during the manufacture of
PDCB requires that these substances be controlled. The control of PDCB
to about 75 ppm in the working area is significantly Important because of
its high toxicity to humans.* There are no source emission standards for
these compounds for the industry. Comparison with standards, if any,
established for similar industries is not possible since the emission rates
are not known. Further study is, therefore, required to be able to adequately
assess the significance of these emissions.
* 75 ppm is the toxic level for humans.
-------
61
SECTION V
REFERENCES
(1) Rumker, Rosetnarie Von, E. W. Lawless, and A. F. Meiners, "Production,
Distribution, Use, and Environmental Impact Potential of Selected
Pesticides", For Council on Environmental Quality, Washington, D.C.,
Contract No. EQC-311 (15 March 1974).
(2) United States Tariff Commission Report - Synthetic Organic Chemicals
(1970, 1971, 1972, 1973).
(3) 1974 Directory of Chemical Producers-Chemical Information Services
Stanford Research Institute, Menlo Park, California, pp 513, 747,
753, 755, 759, and 761 (1974).
(4) Chemical Marketing Reporter, Vol. 203, No. 21, p 9 (1973).
(5) "Controlled-Release Pesticides Attract Interest", Chemical and Engineering
News (September 30, 1974).
(6) Lawless, Edward W., Rosemarie Von Rumker, and Thomas L. Ferguson, "The
Pollution Potential in Pesticide Study Series 5", EPA Technical Studies
Report: TS-00_72-04 (June, 1972).
(7) Stutz, C. N., "Treating Parathion Wastes", Chemical Engineering Progress,
Vol. 62, No. 10 (October, 1966).
(8) Abel, Dorothy J., "Guide to State Stationary Source Emission Standards",
Buyers' Guide Issue, p 27 (1975).
(9) Chemical Marketing Reporter, Vol. 201, No. 12 (March 20, 1972).
(10) U.S. Patents Nos. 2, 131, and 259 (Dow, 1938) and 2,447,790 (Reichhold, 1960),
Also, Chemical Process Review, No. 5, Pesticide Production Processes -(1967).
(11) Chemical Marketing Reporter, Vol. 203, No. 15 (April, 1973).
(12) Faith, W. L., D. B. Keyes, and R. L. Clark, Industrial Chemicals. Third
Edition, John Wiley and Sons, Inc., New York (1965).
(13) Atkins, Patrick R., "The Pesticide Manufacturing Industry-Current Waste
Treatment and Disposal Practice", For Environmental Protection Agency,
Project #12020FYE (January, 1972).
-------
APPENDIX A
SUMMARY OF THE SELECTED PESTICIDES
AND THEIR PRODUCERS
-------
TAIU A-I. 1*1*1 cuua, rtopuauu, ROMCUM vauna A*D normm of SIUCTU
o u Coapouada Producara
1. Inaactlclda Hatbyl paratoloa tarr.HcCaa
Corporation
IHonaanto Conpany
Agricultural
DUlalon
Itauffar Chaaical
Conpany
Agricultural
Chnlc-1 Dl«.
„ Vlckaburg Chaalcal
t Conpany
Vatilcol Chaa.'
Corporation
l.'ln-actlalda Toxaphana Harcula-. Inc.
aalld
a.p. «9-
H a
Claai Mlatioa Solution coacantrati
Agricultural
OlTlaloa
Tlnaland Chaaleal
Coapany
Vlnaland, Waad-Hoa«,
Ha« Jaraay Haad-g-lao*
Dai-l-taJ*
4. Harblclda \ Trlfluralln Ell Lilly and
5 Coapany
*-*
|
1
&
j. pumtclda Pantachlorophanol
and wood 0^ Ch*«lcal
^•••rv«tlv« coSaJIIy
Hoaiatnto tnduit.
ChaHical CoBpcny
•± UlehholdChaic.il
I
K Itutford CtiMtcal
QeBptty
•* • Vulcan lUttriali
Cimptnj. Cl»i-
c«U DlvUlcm
i. Pt-«i,|«i.c Fatrtdichioco* Allied Chmlcal
iMtiMD.* Corpor«clon
InduitrUl Cheat-
1 Chemical Produce*
I Corporation
Dow Ch«ie«l
Coa^Ot
Nonaanto Induat.
Chaalcal Coapany
PP5 Induatrlaa,
loo., Industrial
Chaalcal Dlvialon
tolvant Chealcal
Coapany, Inc.
tpaelalty Organtca ,
Inc.
Standard Chlorlna,
Chanleal Ccmpany
Inc.
tafayatta, TraflaafJ
Indiana
I
Midland, Dowieldaft
Michigan
Saugat,
llllnola
Tacoaa, Chloraphan*
Kaahlngtoa
Houatoa. Taxaa
Ulehlta, bnaaa
Syracuaa,
(Solvay)
Na» York
Cartarrtlla,
Gaorgla
Hldlaad,
Mlchlgm
Saugat.
Illlnota
Hatrla.Uaat
Virginia
Haldan,
Haaiachuaatta
llagarn Falla,
KM York
Irvlndila.'
California
Dalowara City,
D-lawara
23
19
16
16
1*
It
12
1
U
12
21
S
10
I
40
XA Q.iOiorTr-l'taoro.i t-cllnltro-H,*- Yallua ayaaga lanlalflBbla con*
tlanajrl-a-tolaldlna b.p. •»- caatrata, granular
an 17 C
/ (^ «..ctLO. «•»• *••»•
•' \ S**! ^^ 4*C
/ *
HOj "™1 ~»^~J
• M ••••«fci Ha.it* ..... _. ..
aall* caatrata. vatlabla
,0.0 •">. »-» « K-*"
CI CI
«> — v.
>— ?^
ci a
K.7
-•" ' klata aolld CtyaUla
a.p. U C
IA
IA
IA / ^<
• \^ y *•
M
11.0
IA
2.0
24.0
• Hoc -v-lUbla.
-------
APPENDIX B
SUMMARY OF NONPROPRIETARY INFORMATION OBTAINED
FROM THE SURVEY OF PESTICIDE PLANTS
-------
TABLE B-l. SUMMARY OF AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES
Pesticide
Sources
Major Compound Rates,
Emitted Ib/hr
Methyl Parathion
1. Reactor
2. Chlorinator
3. MPT Unit
4. Waste Treatment Incinerator
Wastewater
P2°5
HC1
S
NaCl
P2°5
H2S
Mercaptan
460
420
460
1550
Toxaphene
1. <& -Pinene Production
2. Camphene-Production
3. Chlorination - Toxaphene
4. Toxaphene Granular
Production
5. Wastewater Treatment
N.A.
HC1
Toxaphene
C12
HC1
4350
MSMA
1. Sodium Arsenite Production
2. DMSA
3. MSMA Production
4. MSMA Processing
5. Waste Treatment
As203
CH3C1
(CH3)20
N2S°4
MSMA
MSMA
N.A.
6.44 x 10"8
Trifluralin
1. Nitration
2. Condenser
Salt of Nitrate,
sulfate, chloride
HF
Nitrogen oxides
CHCU
1
3
3
Trifluratin
-------
B-2
TABLE B-l. SUMMARY OF AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES
Pesticide
Sources
Major Compound Rates,
Emitted Ib/hr
Pentachlorophenol
1. Pentachlorophenol
2. Acid System Reactors
Chlorinated
Phenol
C12
HC1
Chlorinated
Phenol
HC1
^fcaradichloro-
^^ benzene
3.
4.
5.
1.
Ingot Casting
Shotting Operation
Wastewater Treatment
Chlorinator
PCP
PCP
N.A.
HC1
2. Recovery
3. Press Room
4. Wastewater Treatment
Chlorobenzene
C12
PDCB
Chlorobenzene
PDCB
C12
HC1
(a) Not available.
-------
TABLE B-2. SUMMARY OF AIR EMISSION CONTROL DEVICES, EFFICIENCY, AND COST
Pesticide
Methyl Par a th ion
Toxaphene
KSMA
Trifluralin
Pen tach lorophenol
Paradichlorobenzene
Source of
Information
Monsanto
Monsanto
Monsanto
Hercules
Hercules
Hercules
Hercules
Diamond
Ansul
Diamond
Eli Lilly
Reichhold
Reichhold
Reichhold
Standard Chlorine
Standard Chlorine
Standard Chlorine
Standard Chlorine
Control Device
(a)
Incinerator (H S, S, mercaptan)
Water Scrubber (P2°5» Hcl>
Brink Mist Eliminator (P20 for visibility)
Alkali and Water Scrubber (solvent vapor, HC1, Cl.)
Stripping (solvent vapor, HC1, Cl )
Limestone Adsorption (solvent vapor, HC1, Cl )
Baghouse (toxaphene)
Baghouse (As 0_)
Water Scrubber (As.O.)
Acidifier Vent Scrubbers
1- and 2-Stage Venturi Scrubber and Tri-mer
Wet Scrubber
Packed and Venturi Scrubber (Cl., Phenol, acids)
Bay Filters (PCP)
Mechanical Seals (for PCP reactor)
Water Scrubbers
(HC1, benzene, chlorobenzene, etc.)
Absorption Column
(HCl, benzene, chlorobenzene)
Efficiency Capital
(b)
95
99.9
100
8,000
500
90 1,000,000
99-100 80,000
95-99 70,000
50,000
90 28,000
95
100,000
Operating
200
100
1,000
6,000
6,200
40,000
(a) Compounds in parentheses are controlled by the preceding control device.
(b) Blanks show data not available.
-------
B-4
TABLE B-3. LIST OF CONTACTS HAVING EXPERTISE AND SOURCES OF
SIGNIFICANT INFORMATION ABOUT SELECTED PESTICIDE INDUSTRIES
Representative, Affiliation, Address
and Telephone Number
Comment on
Usefulness of Contact
The Ansul Company
Alan L. Haase
Marinette, Wisconsin
(715) 735-7411
54143
Diamond Shamrock Chemical Company
W. R. Taylor
1100 Superior Avenye
Cleveland, Ohio
(216) 694-5000
Hercules Incorporated
H. E. Hicks
Brunswick, Georgia 31520
Eli Lilly and Company
Arlie J. Ullrich
Indianapolis, Indiana
46206
Monsanto Industrial Chemicals Company
P. E. Heisler
Sauget, Illinois 62201
(618) 271-5835
Reichhold Chemicals, Inc.
J. C. Manlove
P. 0. Box 1482
Tacoma, Washington 98401
Standard Chlorine Chemical Company, Inc,
P. F. Romano
1035 Belleville Turnpike
Kearny, New Jersey 07032
(201) 997-1700
Stauffer Chemical Company
Dan Simmons
Mt. Pleasant, Tennessee
(203) 226-1511
Vulcan Materials Company
R. A. Bondurant, Jr.
P. 0. Box 545
Wichita, Kansas 67201
(316) 524-4211
Production data and control
given.
Production data, control
method, and costs given.
No production data, simple
statement on process.
No production data.
Emission data given.
No production estimates,
but control methods and
costs were provided.
Very good response.
Estimates of production data,
production and control flow
sheet and costs.
Production data, control
method, and cost given.
Production data only.
Production data, control
method, and cost provided.
-------
APPENDIX C
SAMPLE OF LETTER MAILED TO SELECTED
PESTICIDE MANUFACTURING COMPANIES
-------
August , 1974
Gentlemen:
Battelle's Columbus Laboratories under contract to the Strategic Studies
Unit of the Office of Pesticide Programs, Environmental Protection Agency
is working to develop background information and determine the significance
of emissions from pesticide plants.
For this study, the following six pesticides have been selected:
(1) Insecticides - Methyl Parathion and Toxaphene
(2) Herbicides - MSMA and Trifluralin
(3) Fungicides and Wood Preservative - Pentachlorophenol
(4) Fumigant - P-Dichlorobenzene.
One of the objectives of this information gathering is to obtain factual
information from the manufacturing industries so that determination can
be made of
(1) The extent of ambient emission of the pesticides
(2) The type of compounds emitted
(3) Currently employed methods of emission control.
From the above data, the study will seek to project future emissions, relate
it to similar emission from other sources, and thus obtain a quantitative
estimate for the significance of pesticide emissions from the manufacturing
sector.
Please find attached a list of six questions, which we request you to complete
and return to us at your earliest convenience. We will keep any information
you supply within BCL files so that the confidentality of your data is preserved,
We appreciate your willingness to cooperate and would like to assure you that
any assistance you will provide will be of immense value to this study required
under the Clean Air Act of 1970.
Cordially,
C. N. Ifeadi
Research Scientist
Waste Control and Process
Technology Section
Attachment: Questionnaire
-------
C-2
Manufacturing Company
Address
Name, position, and phone number of person responding
Name of pesticide produced
Question 1. Design Capacity and Production
Design Capacity, Months Actual Production,
Year millions of Ib In Operation millions of Ib .
1970
1971
1972
1973 .
1974 (Estimate)
1975 (Estimate)
Provide details of any technical or economic situation that may affect future
or decreases in your plant production.
Question 2. Process Description
Give a brief description of the processes used to produce the pesticide. Specify
the raw materials, by-products, and waste materials. Amplify with simple production
chemistry and attach simple flow sheets.
-------
C-3
Question 3. Raw and Waste Material Handling with the Plant
Particular attention is generally paid to materials handling within the plant,
since the raw and waste materials may have high toxicity. Briefly descrube the
precautions taken in your plant.
Question 4. Air Contaminant Emissions and Control
Manufacturing Plant
Site
Particulates
^pes
Odor
Waste Disposal Site
Particulates
Gases
Odor
Emission
Sources
Compounds
Emitted
Controlled
Yes or No
Method of
Control
Emissions
(lb/ton)*
Efficien<
(%)
* Or any other unit employed by your facility.
Describe briefly the emission control system used in your plant for particulates,
gases, odor, and visibility control. Describe problems of visibility and odor, if
any, around your plant. Information or nature of odor complaints, if any, from
the public in your area will be useful in obtaining an idea of the odor problems
associated with your plant.
-------
C-4
Question 5. Cost of Emission Control System
Name of Control System Size Capital Cost ($) Operating Cost ($/yr)
Question 6.
Please indicate the status of air emissions from your facility as (a) acceptable
(b) needs improvements? Comment on the economic impact of restricting the
emissions from your plant to levels considered (a) reasonable (b) too restrictive,
State what you think these levels should be.
------- |