PB-244 7 34
SCRCENING STUDY TO DEVELOPMENT BACKGROUND INFORMATION
AND DETERMINE THE SIGNIFICANCE OF AIR CONTAMINANT
EMISSIONS FROM PESTICIDE PLANTS
C. N. Ifeadi
'iattelle Columbus Laboratories
Prepared for:
Environmental Protection Agency
March 1975

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SCREENING STUDY TO DEVELOP
INFORMATION AND DETERMINE THE S
UR CONTAMINANT EMISSIONS FROM P
BACKGROUND
IGNIFICANCE OF
EST ICIDE PLANTS
by
C. N. i'feadi
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 Ken.oter, Project Officer
March, 1975
EPA 540/9-75/026

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BIBLIOGRAPHIC DATA
SHEET
4. licit- .icivl Suht k ]«•
1. Hi port No.
EPA 540/9-75^026
2.
Screening Study to Develop Background Inform,it ior
and Determine the Significance of Air Contaminant Ijnissions
From Pesticide Plant?
X Kecipirni's Accessiav, \o.
5. Kepon P.ut
March l(.>75
7. AUihor.s> C.N. Ifeadi of Battelle , Columbus Laboratories,
Columbus, Ohio 43201		
8. 1 Y r t (»rm i nj; () • u i n i / .i r io n Krpt.
W.
9. IVrli.rnmv	an.) A.UIr.-ss HonC by BattClie for the 1 'PA
Office of Pesticide Programs, Strategic Studies Unit;
Project Officer -- Jeff Kempter
1 0.	¦(•! "I'.i-.k tt tir k I MM \
11. ( ontrjee (irjnt No.
68-n?-0611, Task 12
12.	N t r: < .u.' A.i'r.
Environmental Protection Agency
Office of Pesticide Programs
Strategic Studies Unit
_J01 M Street. SK	Washington. P.:
15. s jpp Irmrn!.»' v N\ ;»-s
13. I \ pr n| Kc| t ¦ f I & ! Vfl<>d
' OV(T'-«i
I 4.
:Q46Q
16 Ai.-ir.ict.-> jn tliis study, available backgrcuid information is developed and the signifi-
cance of air contaminant emissions from the manufacture of six pesticides determined.
Pesticides studies are (1) insecticides: methyl parathion and toxaphene; (2) herbicides):
MSMA and trifluralin; (3) fungicides and wooJ preservatives: pentachlrophenol; and (4)
fumigant: paradichloroben:ene. 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 manu
facturers of each pesticide is presented. Manufacturing processes, wav and waste materi; 1
handling, air contaminant emission sources, quantity or quality, and pollutants, together
with their present practical control methods arc discussed. Significance of air contami-
nant emissions from the pesticide industries is evaluated on the basis of available dat;
on the emission quantities and/or toxicity of the pollutant(s) emitted. Gaps in the date
requirc-d to make a complete evaluation of significance are identified and recommendations
to fill those y.ips are made.	
17. Kr.K • n i IV>cui:K-nt Anilvsis. 17a. IH srnpin
methyl parathion
toxaphene
monosodium acid ;netha:iearsonatc
(MSNtt)
tri fluralin
pent ach1oroohenol
par ad i chl orobenzeTio
air contaminant emission
air contaminant control
raw and waste material handling
17b. Mon'if icr.s op< n*l mil ij 1 trms
insecticides
herbicides
fungicides and wood
preservat ives
fumigants
data collection
future production trends
production inventor)'
manufacturing process
control costs
significance ot air contamin
emission
;.nt
I7e. ( OSATI I it-hi (,r»up
ie. Availability x-urnicnt Copies available from the Nationa
Technical Information Service, Springfield, Va. 2215
19.	'-Co uriiy (l.iss (Thl**
trpoil )
LNLLASS1 Fll-U
20.	I'r.'uriry ( Uss (This
I'NCI ASSlMI;!)
21. No. of
FORM NTIS-11 'REV 'O.731
72.
I'.MIMICS!:!) HY ANSI AM) I \IS< 0.
IMIS HlltM VAV IM KM'Kl'IH't l-.l'
USCOUM.3C «26',-P74

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ABSTRACT
In tins study, iv.'1 i 1 ;ib 11 bukyround Information is developed
.iih) ill. si ,'iu; i c-uicr ol iiir conl .imi ivmt omissions from the manufacture of
•six pesticides determined. Pesticide.* studied are (1) insecticides;
mo11 iy I pnrathion and tox.iplu ne; (2) herbicides: MSHA and ttifluralin;
(3) fungicide and wood preservation: pentachlorophenoi; and (4) fumigant
par.id jcliloi obenz«_no.
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, «ir contaminant
emission sources, quantity or quality, and pollutants, together with their
present practical control methods ore 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 pol 1 utflr/t (s) emitted. Gaps in the
d.it.i required to in.iht a complete evaluation of significance are identified
and recommi nd.'it ions to fill those K;1PS are made.

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SUMMARY
The essential findings of this study con be summarized as
fo 1 1 cws :
lV-sclfies t i c i cies 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, 9uch as aldrin-toxaphene or tiethanearsonic
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 pesiicide frotn 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
Statca is included, including the plant (company) name and location. Estimates
of the design capacity of existing plants and tl^-ir production are provided.
Manufacturing Processes
(1)	One manufacturing process for each pesticide it idertified.
(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.
Row and Wn:tc Material Handling
(1)	hr.sentiai i:aw materials are enumerated. All hazardous
materials are identified.
(2)	Precautionary safety measures taker) by manufacturers
to safeguard the health employees are described.
iii

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(3) Simple flowsheet* (01 wuste handling during the manufacture
of each pesticide are provided, i de:u > fy i r.g the waste disposal technique used.
Air _f'out »ini i nnnt lvm s s i ons , Sources t and Rates
(!) A i. i! 111' of 11 r < i >11i r. iiit en i ?. ¦, j iui.s uml Lheir sources from
muf.n t iir in,', prm-ciiHC'-. «n«l waste distvsal systems is developed.
(2) Where po.-sible, lit Ci>nt.V!iinane emission rates are calculated
mi the basis f simple reaction chemistry or where available are provided
by manufacturing plants.
Air Contaminant Control
(1)	Air contaminants arising from production processes ere
controllable by most of the methods used in the general chemical industries
to prevent dusts, fumes, and gasc-s 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 ie available
from the manufacturers.
(3)	Nationwide air contaminant emission;; and the preaent emission
control situation are estimated.
Control Costs
(1) Cost estimates are presented only for *hoso companies which
submitted such information in response to the survey. While a Icev companies
provided some data on the cost of control in their plants, the operating
conditions necessiry fc»r an adequate evaluation of the same are not provided,
11) i s part of the research, together with the economic impact on the industry
due to the imposition of the best available control technique, ia not
pursued because <*f resource limits for this study.
i v

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Sit-;n I Ilcancc- of I'm i a a i ons frcw I'fitlcldc Plantg
Dcti riTiin.ition of the, aignlficonce of the air contaminant emission
in fuch pesticide industry is made by identifying the candidate pollutant(s),
tlii ir 'pi.iliLy or > mission (wiu-ri.' possible)t and toxicity.
v

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tabu: ok contknts
Page
SKI T ION I
t'i'\i i • '> Ions		1
SEC HON II
RECO.MMENIW 1 IONS		3
SECTION III
INTRODUCTION		4
Objectives of the Study ....... 		5
Hie Study Approach			5
Data Collection		5
Process Description				7
Analysis of Air Contaminant Emission ond Control ....	7
Analysis of Air Contaminant Emission Control Costa ...	8
SECTION IV
BACKi kOl'NlJ IM'.ilC'iA'i ION AND SIGNIFICANCE OF AIR CONTAMINANT
I!M I K5i I ON'S		9
Insecticide- - Methyl Paracliion	13
Product inn Inventory			13
Future Production Trends 	 . 		13
Manufacturing Process	15
Raw and Waste Material Handling			15
Air Couaminant Emissions, Sources, end Rate.®	18
Air Contaminant Emission Control .... 		18
C:mi:rol Coats
Siguiiicance of Air Contaminant Emission 		21
Inst'c tic i dr - Toxaphene			22
Proiuction Inventory					22
rutire Production Trends 	 ...	24
Manufacturing Process	25
vi

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TABU: OF CON'ITNTS (Continued)
l±L£
Raw and Waste Material Handling	25
Air Containin;ir.t Emissions, Sources, and Rates	27
Air Cont an.inant Emission Control	27
Con 11 o 1 •'>) sts	 	29
Significance of Air Cnnutmi'.Mnt l.missions	29
Herbicide - Mo'iosodium Acid Methanear«">nate (MSMA)	29
Production Inventory	30
Future Production Trends	30
Manufacturing Process	32
Haw and Waste Material Handling. 		.	33
Air Contaminant Emissions, Sources, and Rates	33
Air Contaminant Emission Control 		36
Control Costs	36
Significance of Air ContMmlnant 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 Kates. ....	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
FumJgant - Paradichlorobenzt-nc	53
Production Inventory . . . . 		54
Future Production Trends 	 . 		54
Manufacturing Process. 				56
Raw and Waste Material Handling. ....... 		57
Air Contaminant'Emissions, Sources, and Races. .....	57
Air Contaminant Emission Control 	 . 		57
vil

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TABLE OK CONVENTS (Continued)
Control Cost			60
Signlfic.ince uf Air Contaminant Emission	60
slciio;; v
REFERENCES	61
APPENDIX A
SUMMARY OK 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 J.ETTER MAILED TO SELECTED PESTICIDE MANUFACTURING
COMPANIES	C-l
viii

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LIST 01' TABLES
f£Pe.
Table 1. Research Plan	.		 . . 6
Table 2. Production Hst incites - 1970 to 1980	 11
'3. I'rodin'crs of Mi-iiiy ! Par.ithion in tin- United States . . 14
Till) If 4. Air Coutaini nunt Emissions, Sources, and Rates
from Methyl Parathion Manufacture and Waste
Treatment	 19
Tabic 5. Producers of Toxaphcne in the United States	23
Table 6. Air Contaminant Emissions, Sources, and Rates
from Toxaphene Manufacture and Waste Treatment .... 28
Table 7. Producers of MSMA in the United States	31
Table 8. Air Contaminant Emissions, Sources, and Rates
from MSMA Manufacture and Waste Treatment	35
Table 9. Air Contaminant Emissions, Sources, and Rates
from Trifluralin Manufacture and Waste Treatment ... 42
Table 1U. Producers of PCP in the United States	45
Tabic. 11. Air Contaminant Emissions, Sources, and Rates
from PCP Manufacture and Waste Treatment	49
Tab If 12. Air Contaminant Control Methods Used in PCP
Manufacture. ...		52
Table 13. Producers of Paradicnlocobenzene in the
'Jnited States	55
Table 14. Air Pollution Emissions, Sources, and Rates from
Paradichloroben?.ene Manufacture and Waste Treatment. . 58
T<-ble 15. Air Pollution Control at Standard Chlorine	59
Table A-l. Uses, Classes, Producers, Production Volumes, and
Properties of Selected Pesticides	A-l
Tabic H-1. Summary of Air Contaminant Emissions, Sources,
and Rates		 . B-1
Table 8-2. Summary of Air Emission Control Devices, Efficiency,
and Cost	B-3
Table H-3. List of Contacts Having Expertise and Sources of
Significant Information about Selected Pesticide	B-4
Industries

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LIST OP FIGURES
Page
F'. Kii re 1. Mann f.ic I ur i ng Sites of the Selected Pesticides .... 10
Figure 2. Production Estimates (1970-1980) for Selected
Fesr i c i diifi	12
J. Promotion and WasLt> Handling Schematic far Methyl
I'arathion (Monsanto)	16
Fiyuio b, Pararhion Residue and Off-Gas Incinerator	20
Figure 5. Production and Waste Handling Schematic for
Toxaphene	26
Figure 6, Production and Waste Handling Schematic for MSMA ... 34
Figure 7. simple Flowsheet for Trifluralin Manufacture .... 39
Figure ;l. Pro'action and Waste Handling Schematic for
Trifluralin	41
Figure 9. Production and Waste Handllrg Schematic for
Pentacii lorophenol			46
Figure 10. Scrubbing Systems for the Control of HC1,
Enittcd f'on- PCP Reactor			50
Figure 11. !J.ist: Collator Schenuties (or tlie Pen* a Emission
Cent r mi	51
Fi'-iurc 12. Production ind Wante Handling jchtna^ic for
Parcel ich lcrobenze^e. . . . ,			56
x

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1
screen :n<; study to dmvkuop back<"ioi:nd
INFOKMATJ.ON AND UL'lKKMIN'E THE SIGNIFICANCE OF
A1 i 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 tlieir production data to contractors. Published datr 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
proj.tt.r.'d raw material availability and demand in agricultural production
and ot.ier •. nd uses.
(2)	Essential health and safety precautionary measures adopted
by nost flrnu ace transport ot materials in closed systems and requirement
for the use >f 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
wa:- Lc 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 ts^nnse -
variations in the production process.

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2
(5)	The identiliecl in i i ons consist of particulates, gases, and
v;ipors. Mac 11 pesticide plant emits into the atmosphere at least one pollutant
which may require control. Some arc known to create odor nuisance and
visibility problems. In aomc cases, odor nuisance may be experienced, but
the odorous compounds nre not known. Very little information is available
on the emission rc"..:s because lew 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 emersion.'.
(6)	A factual, realistic assessment of the significance of emissions
from pesticides plan' i 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 SO^i tt^S, and NO^, and these are substantially
higher than emission standards in other related process Industries.

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3
SECTION II
RECOMMENDATIONS
(1)	A more effective means of obtaining data than the currently
employed method of it quest in)', inform.11 i on by letter from manufacturer needs
to be developed. Tlus 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 ita 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 authoT 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 reconimcndation on source performance standards
for the pesticide industry. However, the intrinsic toxicity of intermediate
and final products i.i clear. It is, therefore, recommended that a field
emission study be undertaken at the earliest possible date to obtain the
data necessary to fully quant*< pesticides emission standards.

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A
SECTION 111
INTRODUCTION
Pesticides are important to t.lie nation's economic life because
tlii y arc used in liolp in tho prodnc IJ on of food am! fibre and to control
organisms that destroy materials or threaten public health. However, the manu-
facture and uso of the pesticides cun create environmental and health concerna.
Consequently, EPA through its Office of Peaticide Programs, has engaged in
studies of various aspectis of pesticide production, use, and effects on the
environment.
Continuing, in these Important studies, the Strategic Studies Unit
of the Office of Peaticices Programs has noted a need to develop background
information and determine the significance of the air contaminant ealeslons
from the manufacture of acme pesticides, in confo^Tnity with the 1970
Clean Air Act that requires the regulatory agencies to gather information and
develop standards for emissions frotr. stationary sources. Because there axe
larnc numbers* of pesticides manufactured in this country, only one or two
pesticides from each clans were selected for this background atudy. Six
pesticides were selected in total as listed below.
Insecticides - methyl oarathion and toxaphene
Herbicide - monosodium methane arsonate (MSMA) and trifluralin
Fungicide and wood preservative - pentachlorophenol
Fumigant - paradichlorobtnzetie.
The choice of these specific pesticides by EPA vas 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.

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5
Objectives of the Study
The first general objective of this study has been to develop
backtvound information on the manufacture of six pesticides described earlier.
Specific objectives have been: (a) to prepare a list of manufacturerf in the
United liuti'S? s(j«-c i f yinf; the plani .u'init', location, capacity, and production;
(bl to describe the production processes for each pesticide; (c) to describe
the emission sources of air contaninants and their control, an« 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 c'eveloptnent of background information
on tlif manufacture of six selected nuscicides. The study of each pesticide
was divided into four tasks as given in Table 1. The table contains the
spfciiic information desired on each task.
Data Collection
Information gathering was focused on a literature survey of the
manufacture of itu> six pesticides in Che United States. Principal information
sources were froti BCL ln-house data files and government, professional, and
trade association publications. Letters requesting data (see Appendices 3 and C)
were sent to 9 manufacturing plnnts to obtain factual Information on various
aspects af the selected pesticide manufacture. Information sought included
plant capacities and production volumes; processes profiles such as flow
sheets, rew and waste materials handling descriptions; source, kind, aad

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TABLE 1. RESEARCH PLAN
Taske
Desired Information
1. Data Collection
(a) List of Manufacturers
*	Plant name
*	Location
•	Capacity
•	Production
2. Process Description
(b)	Manufacturing Processea
•	Nature of peatlclde produced
•	Raw aaterlala
•	Waate aaterlala
(c)	Air Contaalnant Imissione
•	Control technology
•	Level of control
•	Waate diapoaal involving air
pollution amission
(a)	Description of the oertl^lue
produced
(b)	Description of raw and waate
mate.rlala handling
(c)	Manufacturing methoda and processes
flowsheets
3. Air Contaminant Emijsions and
Control
(a) Types and sources of air
contaminant emiaalons
(b)	Types and levela of control
(c)	Estimate of :he present emiasion
control altuatlon
(d)	Estimate of future emisalana
4. Uc-ntrol Coat
(a) Estimated cvat for best available
control
(b) Economics impact on the industry

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7
quantities of air contaminant emissions, currently applied control methods;
and costa of such controls. Several telephone calls were made to the
manufacturing plants urging them to complete the forma; however, no plant
visits were made.
Process Description
Uaing Che information gathered, flow sheets were developed, and
process profiles employed in the uanufacture of each pesticide ware described.
Each flow sheet identified, where possible, the following:
(1)	Staps of manufacturing processes
(2)	Raw materlftla
(3)	Source* and types of air contaminant amissions
(4)	Waate material disposal methods
(5)	By-products
(6)	Final and 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 contrc*s were described in terms of gaa 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 eatimatea of the present and
future nationwide air contaminant emissions from the plants manufacturing each
pesticide were based on the plant*1 capacities and the air contaminant emissions
rates.
k

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8
Analysis of Air Cont-irol nont Emission Control Costa
Based on the information obtained from the foregoing tusks,
cost estimates were made on the currently employed control methods. Ihe
costs consisted of the operating and capital coat 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, e
discussion of the economic Impact on typical firms in the industry, if such
controls were required, was presented.

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9
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 follmc:
(1)	Production inventor/ in the United States
(2)	Future production trends
(3)	Manufacturing process
(4)	Raw ard 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 peaticidas 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 front the I. S. Tariff Commission published
data; however, some of these production velues are listed in pefttieide groups
instead of individual pesticides utilized in the program. Prevent and
future production information was sought through the manufacturers, but
moBt 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. Ihese
estimated production data are given in Table 2 and are graphically shown
in Figure 2. As will be discussed under aach pesticide, a number of factors
such as availability of raw materials, demani of the pesticide., and other
Influences can significantly alter the forecast, so that its reliability
decreases as the time interval increases.

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PACIFIC
MOUNTAIN
WEST NORTH CENTRAL
Pesticides No.of Pkmfv
•
Methyl parothion
4
T
To jphene
4
¦
MSMA
3
+
Triflurolin
1
X
Pentochlorophenol
6
~
P-die htorobenzene
9
NEW
ENGLA^y^
INDOLE-
ATLANTIC
WEST SO JTH CENTRAL
-h X
EAST NORTH CENTRAL
SOUTH
CENTAL
'south atlantk
FIGURE 1. MANUFACTURING SITES OP THE SELECTED PESTICIDES

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TABLE 2. PRODUCTION ESTIMATES - 1970 TO 1980
Pesticides	1970	1971	1972	1973	1374	1975	1976	x977	1978 1979 1980
tl.4<*> 37.2<*> 5l-'U'	»	«•' »•* 81-5 8e-° »"3
Percent Growth	10(e)	37	4(e)	17	15	13	10	865
(b)
Toxnpncr.a
«(b)	« ,(C) OA t(c)	lftfl(d)
Production, 10 lb«. 50x ' 65x ' 85.1.	94.6x ' 108x ' 124.2 142.2 162.8 185.6 207.9 232.9
Percent Crowth 30 31	11 14 15 15 14	14	12	12
Vbrosodiu-a Methanersonate(HSMAi . . . . .	. .
Production, 10° lb. 30.5 24.51 30.7W	40.1W 50.1 62.6 75.1 90.1 103.6 119.1 131.0
Percent Crowth 20(e) 25	31 25 25 20 20	15	15	10
Trjfluralir -	, .	m
Production, 10 lb. MA 25v ' 2ly '	23.1 25.4 27.9 30.1 32.5	34.5 36.6 38.4
Percent Crowth 16 10	10 10 8 8 8	6	6	5
Pentaclilorophenol (PCP)	, .	(
Production, 10° lb. 47.2**' 50.9^*' 49.7U'	46.6U' 48.9 51.4 54.5 57.8	61.9 68.1 74.9
Percent Crowth 8 2(c*	6(e) 5 5 6 6	5	10	10
Paradichlorobenze(PDCB)	. .	, ^	.
Production, 106 lb. 69.61*' 70.4l*; 77.3W	85.0 93.5 95.4 97.3 ">9.3 103.3 107.4 111.7
Percent Crc-Jth 1 10	10 10 2 2 2	4	4	4
(«) United snter^arlf?CaaiBr«aT^™^^
(b)	55 percent of Toxaphene-Aldrin Croup-quoted by U.S.	Tariff Coaalaalaa.
(c)	65 percent of Toxaphene-Aldrin Croup-quoted by U.S.	Tariff Coaaidioa.
(d)	70 percent of Toxaphene-Aldrln Group-quoted by U.S.	Tariff Coradaaloo.
(e)	Indicate* percent of decrease in production.
(f)	Rumiter at al. Reference 1.

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12
1000
100
Toxophene
POL ,
¦Q.J »--<>
MSMA
—-o
Trif lurolin
1
1370 1971 1972 197 3 1974 1975 1976 1977 1978 1979 1900
FIGURE 2. PRODUCTION ESTI.MATES (1970-iy80) FOR SELECTED PESTICIDES

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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
soybems 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 Mons&nto Company.
The total U. S, capacity for the manufacture of methyl and ethyl
parathic.ns [0,0-dimethyl O-p-nitrophenyI) phosphothioate] is 147 million lb,
but three plants with total capacity of 53 million lb were not producing
m
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14
TAHLt 3. PRODUCERS OK METHYL PAKATHION IN THE UNITED STATES
(3.4)
Company
~ocation
Anaual Capacity
millions of ib
Es timated
1976 Prod uctinn
millions of lb
American Cyonamid Company
Ag ricultrual Division
Hercules Inc.
Synthetics Department
(a)
Kerr-McGee Corporation
Xerr-McGei? Chem. Corp.
Monsanto Company
Agricultural Division
(b)
Stauffer Chemical Company
Agrlcultrual Chem. Div.
Vicksburg Chemical Company
Veleicol Chemical Corp.
(b)
Lindern, N. J.
Plaquemine, La.
Hamilton, Miss.
Ann1bton, Ala,
Mt. Pleasant, Tenn.
Vicksburg, Miss.
Bayport, Texas
Total
2a
15
17
50
30
10
153~
15
30
10
57
(«0
b)
Not operating by 1974.
Volume includes ethyl parathion.
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15
of a more effective and efficient* way of packaging and applying the Insecticide,
such as encapsulation technique* .
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 parathlon is connonly manufactured from sodium p-nitrophenolate
by the reaction with 0,0-dlmethyl phosphorothlochlorldate. There are
three steps involved in zhe synthesis of methyl parachion, One common method
involves the reaction of an appropriate alcohol (methyl alcohol) with phosphorus
pentasulfide, followed by chlorination, and finally, the parathlon formation In
acetone. the three steps are as follows:
S
P2S5 + AR0H	^--2(RO)2 PSH + H2S
Diphoaphoruspentasulfide	Hydrogen aulfide
S	S
(R0)2 PSH + Cl2 	^(R0)2PC1 + H'U + S
ONa
p._Ac»on1.>(R0)^-0_^_ ^ + BaU
0,C-dimethyl
Phosphorothlochlorldate - .2	Parathlon
Sodium p-nltrophenolate
Conditions of these reactions are not available aa 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
parathlon, by-products such as NaCl and HCl are formed along with waaf.«
products such as ll^S, mercaptan, And sulfur. The production and waste
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16
SOj

H.S & RHS
ROH
HCI
Chloridothionot*
NoCI
Trace Quantities
of HjS, RHS, and
HCI emitted to air
(Uoctor —<». DiolkyI
EiNr
Waste
Treatment
Plant
City
Sewer
FIGURE 3. PRODUCTION AND WASTE HANDLING SCHEMATIC FOR METHYL PARATHION
(Monsanto)W
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17
handling schematic is shown In Figure 3. The odorous compounds (HjS and
mercaptan) are flared and the sulfur is incinerated, while liquid waste
effluents are neutralized with Na^O^ and sent to a wastewater treatment
plant.
Since methyl perathion is very toxic, specific handling
precautions are taken. K-'rr-McCee 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 froot the SNP
drum storage area ia to the chemical complex drainage
ditches.
(2)	Processing areas of the plant are curbed bo that spills,
3land 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. TTie parathion is stored in 16 gauge,
tight head crums. In the event of a parathion spill
the following clean-up steps are taken in the order
listed:
« Put absorbent clay on the spill until the
spill is soaked up in the clay.
«• Remove the clay and absorbed parathion.
•	Put .noda ash over the spill area. Vigorously
scrub soda ash into floor with a broom.
•	Remove aoda ash.
•	Repeat Steps 3 and 4 several times .
•	Wipe contaminated area with paper towel.
e Soak paper towel in carbon disulfide to
extract methyl parathion.
•	Check carbon disulfide for methyl parathion
by infrared scan.

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I
18
•	If the test Is positive repeat Steps 3 through 8 until
the tc&t If negative .
•	bury contaminated matter in closed drum.
Air Contaminant Emissions. Sources, nnd Rates
The manufacture of methyl paraihion produces solid, liquid, and
gaseous waste materials.
The main sources of air contaminant emissions are; the reactor,
the chlor inacor, and Che Methyl Pa rath ion iiit (Figure 3). Odorous
riolluCants *rise from vents, liquid wastes, an 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 par'ithion and the estimates by Rawless, et al.(^)

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TABLE 4. AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES FROM
METHYL PARATHION MANUFACTURE AND WASTE TREATMENT
Sources of Emission
Particulates
Ra te s,
Ib/hr
Gases/Vapors
Rates,
lb/hr
Rate,
Odor Odor Unit/hr
Manufacturing Processes





Reactor
None

'J iphosphorus
pentoxide
mercaptan
H2S

rrercaptar.
kvlene
h2s
Chlorlnatlon
Acid Mist,
e.g. HC1
S
460
420
PCI
PSCI3
Methanol
Methyl chloride
HC1


MPT Unit
Baste Mist,
e.g. NaCl
Methyl Mono-
chloride
460



Wajte Treatment Processes





Incinerator and
Flaring
P2°5

S°*
T5
1.55C
Non
Waste Treatment Plant
None

H2S
mercaptan
—
h2s
mercaptan
Lagoonlng
None

H2S
mercaptan
—
H2S r
mercaptan
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20
Practical sulfur dioxide emission control processes for H^S,
rnerca pUn, etc., available for methyl pa rath ion plants are Incineration
la series with scrubbing system and carbon adsorption. Control of visible
fumes created by the emission of diphosphorous pentoxide can be achieved
by a mist elimL rator, while H-.S and mercaptan emission control during the
wastewater fcrc.-iIr.ient can bo achieved by chemical oxidation and deodorizatlon.
Tho air emission control system used by Monsanto is shown in
Figu re 4. Incineration Is used for the control of the off gas'as 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 butter practical control method than recovery because the sulfur that can
be recovered in this process is inescapably contaminated with toxic nethyl
parathlon.
TO ATMOSPHERE
r»-
MI5T EllMlNAiOR
OFF GAS, r?
RESlDufc J
FUEl cr--- ;«
V V
TO St SVC R RECOVERED
LIMESTONE NEUTRALISATION
PRODUCT
FIGURE 4. PARATHION RESIDUE AND OFF-GAS INCINERATOR^
Sulfur dioxide emissions presently are not controlled in methyl
parathlon manufacturing plants. This means that for a plar.t producing
about 30 million lb of methyl parathion per year, the SO2 emission per year
will be about 12.3 million lb or 1,550 lb per hour; that is, by 1980 at the
present control status SO2 omission from MPT plants will be about 21,2
million lb or 2 ,6 il 0 lb per hour.
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21
On the basis of available information, Monsanto it 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 Mi at Kliminator. However, SOj produced during
the incineration of sulfur voir,pounds is not controlled. It was estimated
that about 12.nil lion lb of so^ wt ic emitted in 1974. Both Kerr-McCee
Corporation and Staufier Chemical Company vent their emission into the
atmosphere without any control. According to them, there are occasional
complaints of odor rroblems from H^S, mercaptan, etc., emissions. It was
estimated that	S, and NaCl emissions from these plants were,
respectively, 3.2, 3.0, and 3.2 million lb in 1974.
The future trend in air pollution from the manufacture of methyl
parathion will tend to Increase due tc 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 provHe tta air pollution control coats.
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
rcethyl parathion shows that only Monsanto Company controls the primary
emissions such as H^S, mercaptan, S, and phosphorous pentoxide, while
other companies do not control their emissions. However, in the process
of control lint; the primary emissions, a secondary emission (SC^) is produced
and emir ted without control.
Those companies that are not control:''! g II^S and mercaptan
emissions do have occasional odor problems; her.'.:, control in the industry
is necessary. Kraft pulp mills mny be compare^ vi:h the methyl parathion
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22
plant in terms of odor problems. The emission requirement: in Mississippi
nnd A1 abama fur the total reduced sulfur (TRS) is 1.2 and 2,0 ib/ton of
/y >
pulp, respectively; ' whereas the calculated emission foT HjS alone from the
methyl paratuion plant w:«s t»boi>t 0.12 lb/lb of active ingredient (Al). Also,
SO^ emission standard from sulfur recovery plants may be compared with that
emitted at the Monsanto -mnt. Tn Alabama, the standard is 0.08 lb/lb of
sulfur processed, while the calculated emission from the Monsanto plant was
about 0.41 lb/lb of Al, Consequently, thes« odoious compounds and SOj are
emitted in an amount higher than prevailing state standards for other related
process plants. Thus, the need fcr 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 nondef^nite chemical comjound, is a mixture of
polychloro-bicyc1ic rerpenes with chlorinated camphene. Toxaphene contains
6/ ro 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.
ProducI'.on Inventory
Toxaphene is manufactured in three southern states; namely,
Georgia, Texas, and Mi&scuri, and by three companies, namely, Hercules,
Sanford, and Vicksburg. Table 5 gives the Inventory in the United State*.
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23
TABLE i. PRODUCERS OF TOXAPHLNK IN THE UNITED STATES
O)
Company
Location
Design
Capac Ity
Production
Estimate
1974
Hercules, Int.
Synthetics Dept.
Brunswick, Ga.
50-75
(b)
65
Scmford Chemical Co. Houston, Tex.
Tenneco Cht.nicals
Intermediates Div.
Fords, N. J.
(*)
40
125
(b)
20
20
Vicksburg Chemical
Co.
Vicksburg, Hiss,
220-245
3
108
(a) Produces strobane, a polychlorinated toxaphene-lika
insecticide.
(b) Reference 1.
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24
The distribution conforms wJ Hi the general location of raw material-*
southern pine--and major use nrea--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 ,;ho!e group showed • dramatic Increase
from 1970 to 1972, The U. S, production of toxaphene wao estimated to be
50 million lb in 1970.^ An estimate discussed below for 1974 it 108
million lb, showing that the production has substantially increased.
Future Production Trends
Estimates of toxaphene production are based on the trand in tho
proportion of toxaphene in the aldrin-toxaphene group. In 1970, toxaphene
(2)
was about 55 percent of the group production. In 1973, it was ab^ut
65 percent, and with the recent registration withdrawal of sane
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 ticnd
in production. However, like methyl parathion, new, more efficient, and
effective methods of packaging and application will tend to l>iwer demands/*^
On the basis of these factors, the percentage of incteare 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 h
production volume of 233.0 million lb per year at the end of the decade as
shown in Table 2. The above estimates have been made on the assumption
that no regulacory action will be taken to control the use o£ Ccxaphene or
that no substitute chemicals will be introduced.
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25
ManufncturInn Process
Hid production of toxaphcne 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.


^'h3 UV or cat.
» "" C^gH^QClg + 6 HC1
orPinene
CII3
Camphene
Toxaphene (mixed isomers
and related compounds
67-69% CI)
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 effluont
t reatments.
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 toxaphcne is filtered, stripped, and formulated into marketable forma,
"rtie 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 awl crew on site. Production workers receive annual checkups
and hnvc hid . ua client health record, according to the company, with no
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Southern
Pine Stumps - 1 %
100 Other Products
a Pinene
1
Reactor
Chlorine
Sslvent -
1
r
Camp'iene
t
	i	
Chlo. inotor -
h2o
Lime
NaOH
Lime-_
S tons
Surface^
Waters
rHCI
Go»
Absorber


*
Scrubbers

(2)

V

Main Plant
Waste Stream
• Wastes
J
Mixed
Xylenes
Toxaphene.
Solution
L
Recovered
Stripper -^Toxaphene ¦
Primary
Muriatic Acid
Waste

Treatment

Plant

To Solid
Waste
Baghousc Oust
Collector
T
Atmosphere
90% Toxaphene
Solution
Shipmer>s
fw
a*
Discharge to
Tidoi Creek
FIGURE 5. PRODUCTION AND WASTE HANDLING SCHEMATIC FOR TOXAPHENE^
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correlations of death or LLlnceu with toxaphene handling. The company
stated chat thay 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 Races
Main sources of air contaminant emissions are the reactor, the
chlorlnator, and toxaphene formulations. There is no information on
emissions from c-plnene production.
The main emission fro'.n 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 HCl which is estimated to be 4,350 lb/hr* from a
65-million-lb-capacity plant.
Air Contaminant Emission Control
Most systems available in chemical industries for controlling
acidic gaBe9 are applicable to the control of emissions from the manu-
facture of toxaphene. There are three main control techniques: scrubbing
(alkali cr water), stripping and adsorption.
Hercules uses these control techniques to control HCl, 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 chlorlre. Finally, the effluent
is passed through large towers containing limestone, which Is said to remove
the "balanre" of che 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 lb/lb AI.
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TAtiLE 6.
AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES FROM
TOXAPHENE MANUFACTURE AM) WASTE TREATMENT
Sources of Emission
Particulates
Rate, Gases/ Rate,	Rate,
lb/hr Vapors Ib/hr Odor odor "nits/hr
Manufacturing Steps
^-Pinene Production
NA
NA
NA
Camphene-Production
(Reactor)
NA
NA
NA
Chlorination-Toxaphene
Production
Toxaphem; Granular
Production
None
Toxaphene
Dust
Clo gas
HC1
Solvent
Vapor
None
4350
(6)
NA
None
Waste Treatment Processes
Wastewater Treatment Plant
None
C12
BC1
Possible
candidate
Cl„
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29
In chemical Industries various control technologic® ar« 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 prasent 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, the/ are passed together with emission* from the
manufacture of other pesticides In their class through ths same control
system. Consequently, control coat information ia unavailable.
Significance of Air Contaminant Emission
There is high emission of HCl (about 0.53 lb/lb AI) in the
manufacture of toxaphene. It Is recognized that HCl is a liquid at normal
temperature and pressure. However, fumes of HCl are emitted, although the
rate of emission is not known.
A particularly inportant emission in the manufacture of toxaphene
Js that of toxaphene particulates. Toxaphene Is toxic to manuals; 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 - Monosodlum Acid Methanearaonate (KSMA)
MSMA is a selective herbicide nf the organic arsenical group.
MS MA is not very toxic to aniniaU and it degrades fairly readily in the
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30
•oil. It Is a postemergenc herbicide used Co control hard-to-klll grass
weeds.
Production Invencory
Monosndium acid methancaisonate Is products' in three states-—
Wisconsin, Texas, and New Jersey--and by three companies--"ftie Anaul
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 lb,
respectively. No information is available on the capacity and production
volume of Vineland Chemical Company. However, it is estimated that tha
total production for the methanearsonic acid salts for 1973 and 1974 is about
40 to 50 million lb, respectively.
Future Production Trends
The production of MSMA has been showing an upward trend since
19?1. Anaul 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 haid-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. Hie 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.
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31
TABLE 7. PRODUCERS OF MSMA IN THE UNITED STATES
Production
Design	EatlmfcCe
Plant Capacity million Lb
Company	Location	inilllon lb 1973 1974
The Ansul Co., Chemical
Div.
Marinette, Wise.
Diamond Shamrock Chemical Greens Bayo, Tex.
Co,, Agricultural Dlv.
10
17
16.1 15.7
17.0 16.7
Vine land Chemical Co.
Vineland, N. J.
NA NA
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32
Manufactures Process
Hire..'	steps are Involved In Che manufacture o£ MSMA:
production of sodium arsenide, ms?thylarsonic acid, and MSMA.
The first step In the production of MSMA begins with the formation
of sodium arsrnito by the reaction of arsenic trioxide and 50 percent caustic
soda solution. In il.e next step, 25 pevcenc solution of the sodium arsenite
la Created under pressure with methyl chloride to give the dlaodlum methane
arsenate (DSMA), Some companies sell a portion of the DSMA for herbicide
uses, but since DSi-iA is leaa soluble, it requires a higher application rata.
Moat companies go a step further to prepare MSMA.
in a reactor. The material is centrifuged to remove aalts such as sodium
sulfate and sodium chloride (which are waste by-producta) and the resulting
solution ia concentrated by evaporating the water. Hydrogen peroxide Is
added to oxidize the unroacted trivalent arsenic to the pentavalent form.
The final product is formulated with a wetting agent and packaged into
1-gallon, 5-gallon, 30-gallor, or 55-gallon containers. The active
ingrcidlent of MSMA is sold at a numSer of concentrations, but approximately
38 percent is the maximum concentration that can be prepared without undue
viscosity effects.
MSMA is prepared by adjusting the pH of DSMA with sulfuric acid
The simple process chemistr/ ia given below.
As203 + 6NaPH 	* 2NajAs0-j + 3H20
Arsenic
Trioxide
Sodium
Arsenate
Na3As03 +¦ CH3CI 	> CH3AaO(ONa>2 + NaCl
Methyl
Chloride
DMSA
ONa
2CH3AsO(ONa)2 + H2S0^ 	» 2CII3As<^ + N*2S04
0 0H
DSMA
MSMA
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33
Kaw and Waste Material Handling
Raw materials used to produce MSMA are arsenic trioxlde, sodium
hydroxide, methyl chloride, and sulfuric acid. Arsenic trioxlde la the
must toxic spirits, and it if. Imperative that this compound be handled
with care.
It is unloaded under <1 hood equipped with an exhautt blower that
pulls the dvst through ducts to a dust collector, or scrubber. Employees
use respirators, and frequent employee health screening to check any
health donger is required by most firms.
The production and waste schematic^ js shown in Figure 6.
A major concern in the wastewater treatment is Che disposal of
the mixture of sodium sulfate and sodium chlorate contaminated with arsenic.
Diamond Shamrock handles this by precipitation and centrifugatlon. After
washing, they arc disposed of in a landfill which is registered with the
State of Texas. N'o information on air emissions from the disposal site is
available. Methanol, a aide product of methyl chloride hydrolysis and
water, is recycled.
Air Contaminant Km;ssions. 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 trioxlde. 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	~ g
emission of Aso0j to be 6 x 10 lb/ton or 6.44 x 10 ib/hr. During the
production of UMSA and MSMA, vapors of	1, Na^SO^, and CH^O^ are given off.
Arsenic--contaminated solid materials including NaCl, Na^SO^,
and MSMA arc lindf11 led. No information is available on the emissions from
these disposal sites. The list of the pollutants from various sources is
given in T*'Me 8.
-------
AjjO-j-
NoOH-
h2o -
ch3ci
Dust
Collector
-

Sodium
Arsenite
Unit
-
Vent
H2S04"
25% NojAsO^
Storage
Methylarionic
Acid Unit
V
1
f
Crude

DSMA
i

MSMA

Reactor

Purification
Stripper
T
DSMA Soles

CH3OH
Centifuge
iy- Product
Solts
ch3ok
I
58% MSMA
Recovered
Washer
N02SO4
NoCI
1
	Liquid Tc
	j	l«5rd Fill
FIGURE 6. PRODUCTION AND WASTE HANDLING SCHEMATIC FOR MSMA
(1)
u>
f
-------
TABLE 8. AIR CONTAMINANT EMISSIONS, SOURCES AND RATES
FROM MS MA MANUFACTURE AND WASTE TREATMENT
Sources of Emissions
Particulates
Ra te s,
lb/hr
Cases/
Vapors
Rates,	Rates,
lb/hr	Odor Odor Unit/hr
Manufacturing Steps
Sodium	Production
(Reactor Vents)
As2°3
6.44x10
-8
DMSA Production
(Reactor Vents)
None
CH3C1
CH3OH
(ch3)2o
Same
MS MA Production
(Reactor Vents)
None
NaCl
N2S°4
MSMA
Same
MSMA Processing
(Evaporator and
Centrifuge)
MSMA
Waste Disposal Processes
Lan.df il 1
Ponds
NA
NA
Not Identified
Not Identified --
-------
36
Air Contaminant Km).salon Control
The only air pollutant :ontrollcd In this Industry it As^O^.
The conpound is emitted as particulates and various control techniques
ara available, sucli as oaghouses, scrubbers, and electrostatic precipitators.
Diamond Shamrock operates the As^O^ drum opening and dump bin
under a hood equipped with a blower that will pull the	Into a
bagfilcer for collection. Ansul's plant controls the arsenic trioxlde
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 AsjO^, while the acrubber reaovea 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 lCT15 lb/hr As203, it is estimated that the amount emitted per year
by a plant of 17 million lb capacity is 5.J * 10 * lb.
Ansul Company observed occasional udor nuisance, but no
identification of the odor-producing compounds has aeen made.
A definite statement on the level of emission control is not
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 Che order of the production
projections if the present level of control is maintained. Assuming an
emission rate of Aa^O^ given by Diamond Company as 6.44 x 10"® lb/hr A32O3
emission for the industry by 1980 will be 0.0393 lb/year.
Control Costs
Diamond Shamrock--with design capacity of 17 million lb per year--
gives the cost for controlling As^O, as $8,000 for capital cost, and $200
per year for the operating costs. An acidifier vent scrubber is said to
L
-------
3?
coat $500 fur the capital, and $100 per year a« the operating cost. Air
flow rates and hence sizes and efficiencies of the equipment were not
provided for verification purposes.
Sign!licance of Air Contaminant Emission
Of importance in the industry is the control of As^O^ emissions
because yf their high toxicity and carcinogenic property. As of this date,
the responding firms do control ASjOj emissions but the level of control
is net known.
Herbicide - Trifluralin
Trifluralin is a selective soil-applied or preescrgence
herbicide of the class Nitroaromatic. It is used to control annual grass
weeds and some annuel broad-leaves. Abcut 60 percent of tha trifluralin
is used In the production of soybeans, 30 percent cotton, and 10 percent
others.^
Toxicity of trifluralin to mammals Is low, but it is highly
tcxlc to fish. It le 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, Ell Lilly and
Company, at their Tippecanoe Labs at Lafayette, Indiana. The plant capacity
ia estimated to be 35 million pounda per year. Production voluaes for
1971 and 1972 were estimated respectively as 25 and 21 nillion 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 la difficult to assess because
of many unpredictable influencing factora.
Since trifluralin is mainly used in agricultural production auch
aa cotton, soybeans, etc., the future growth rate of theae crops will
influence the growth in production of trifluralin.
The production of these crops in the years ahead will incraane
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 grovth. By I960, it ia projected that about 38 Billion pounds
will be produced.
Manufacturing Process
The manufacture of trifluralin involves two main steps: nitration
and amination. Hie simple process chemistry is given below while the flow
diagram Is shown in Figure 7.
CF„
HNO,
h2sc4
p-chlorobenzotrifluoride
CF,
0„N /
Dlpropylamine
Sodium Carbonate
Water
3,5-dinltro-4-chloro
benzotrifluoride
n(c3h7)2
trifluralin
Nitration involves the reaction of the following compounds in
reactors! p-chlorobeniotrifluoride, sulfuric acid, and nitric acid. The
product of the reaction is 3,5-dinitro-A-chlorobenzotrifluoride, and the
by-product is spent sulfuric acid which is recycled. The main off-gases
are nitrogen oxides.
Aroinatlon is the second-stage reaction involving the reaction of
3,5-dinitro-A-chlorobenzotrifluoride, dipropyl a,nine, and sodium carbonate
in solution. The product of the reaction is trifluralin and the effluent is
brine solution which is treated for recovery.
-------
39
|)-Ch I orobonzm r 1 f hior 1 tJe
Sulfuric Acid
Nitric Acid
	i	id
NITRATION
Off Gases to Scrubber
f
Spent Sulfuric Acid
3.5-Dinltto-4-chlorobenzotrifluoride
Dipropyl Amine
Sodium Carbonate
Witer
^	i	w i'
AMINATION
.Ir.K.lsMUnj
Brine Solution to
Treatment Facility
FIGURE 7. SIMPLE FLOWSHELI FOR TRIFLURALIN MANUFACTURE
-------
Raw and Waste Material Handllnft
The raw materi. 16 used in the manufacture of trifluralln 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 inform, ticn of the measures adopted to protect
the nealth 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 operutors, and safety and material handling personnel.
Greater detail of the production and waste handling schematic
is shown in Figure 8.
Air Contaminant Kmlsalons. Sources, cqd Rates
The main sources of air contaminant emissions are the nitration
reactor and condenser.
The main gaseous emissions from the nitration reactor are aulfur
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 ate mainlv aerosol
consisting of trichlorometharie and trifluralin. The wastewater from the
plant i6 neutralized, and subjected to the conven ional 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 tha company.
-------
r
Excess Acid
Sold
PCBT
HNO3-
H2SO4/ Oleum.
Waste
Water
Monomtrator
Acid
Recovery
Dinitrator
Dinitro
in CHCI3
Scrubber
CondenserM
NH(C3H7)2
Na2C03
Aminafion
Reactor





Filter


j

Decanter ¦
1

Vacuum


Still

Salt
Woter
Waste
Aromatic
Naptha
I
Triflurolin (e.c.)
FIGURE 8. PRODUCTION AMD WASTE HANDLING SCHEMATIC FOR TRI PLURAL IN (6)
t
-------
TABLE 9. AIR CONTAMINANT EMISSIONS, SOJRCES, AND RATES FROM
TRIFLURALIN MANUFACTURE AND WASTE TREATMENT


Ra te,

Rate,

Rate,
Sources
Particulates
lb/hr
Gases/Vapors
lb/hr
Odor
Odor Unit/hr
Manufacturing Process






Nitration
nitrate
1
sulfur dioxide
3
None


sulfate
1
sulfur tioxide
1



chloride
1
hydrogen fluoride
1





hydrogen chloride
10





nitrogen oxides
3


Condense*-
CHCI3
NA


None


Trifluralin
NA




Wastewater Treatment
None
None
-------
43
Air Contaminnnt Emission Control
Air contaminant emissions from the manufacture of trifJ.uralin
arc 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 consist! of t- and 2-stage
venturi scrubbers and trl-mer wet scrubbers. The total flow through the
system is about 20,000 standard cubic feet per minute. Ell Lilly estimates
that capital cost so far is about one million dollars. Thtjr have no information
on the operating cost.
Si*n ificanc<": of Air Contaminant Emission
The re are a large number of air contaminant emissions in the
industry. The State of Indiana has no stationary source emission standard
fcr sulfur and nitrogen compounds from the process industry. However, the
emission rates of these compounds are small when compared with Che State of
Massachusetts standards which are 10 Ib/hr f.or nitrogen oxides and 25 lb/hr
for the process industry which are 10 lb/hr for nitrugen oxides arid 25 lb/hr
(8 )
for sulfur oxide. The toxic material eriitted to the environment io
trifluralin which, according to present knowledge, is highly toxic only to
fish and not to -nammals. Unfortunately, data art not available on emission rates.
Fungicide and Mood 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 polss, crossarms, and pilings.
-------
44
It Is hazardous to man primarily because It la capable of
causing eye Injuries 6uch as conjunctival redness, iritis, and alight
corneal damage. In solution, it can be absorbed through the akin 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 companler 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 piesent annual U.S. capacity for the manufacture of PCP ie
about 97 million pounds. In 1973, the production waa 46.6 million pound®(3)
and the estimate for 19 74 13 about 48.9 million pounds. The manufacturers
of PCP, their capacities, and estimated production for 1974 ara shown in
Table 10.
Future Production Trends
With the increased cost of other wood preservatlvea 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 tv 1980 are given in Table 3 . A
gradual increase in production Is forecast from the present 5 percent to
10 percent by 1980. The greatest iir.^etua to production appears to be
the lack of a co-npeting, product like crude oil, which ia supported by the
-------
45
(3,9)
TAIiLK 10, PRODUCERS OF PCP IN TRh L'NI'lED STATES
Est. 1974
Annual Capacity, Production,
Compcny	Location	million lb	million lb
Dow Chemical Co.
Midland, Michigan
18
5
Monsanto IndiBt, Chems. Co.
Sauget, Illinois
26
10
Keichhold Cheme., Inc.
Tacoma, Washington
16
10
Sonford Chemical Co,
Houston, Texas
18
5.2
Vulcan Materials Co,
Wichita, Kansas
19
18.7
Chemicals Division
Total



97
48.9
-------
46
estimates of some of the companies who think that their production will
double by 1980, The projected 1980 production Is 74.3 million pounds,
Manufacturing Process
A.' -ujsc all of the PCF produced in the United States is manufactured
by the chlorination of phenol, A simple reaction chemistry of the process
is shown beljw; and the simple schematic in Figure 9.
OH	OH
6 •». w.
Phenol	temperature
XA *
i X ci
ci
ci
PCP
Phenol
Chlorine -
A! uminum ¦
Chloride
(Catalyst)
Chlorine
Scrubber
HCI
Recycle to
Chlorine
Plant
Recovery
(10)
FIGURf 9. PRODUCTION AND WASTE HANDLING SCHEMATIC FOR PENTACHLOROPHENOL
-------
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 V v start is In the range of 65-130°C (preferably 105°C) and
Is held in rn? , tange until the melting point of the product reaches 95°C.
About throe or four atoms of chlorine are combined it this point, and the
temperature is progressively increased to maintain *i temperature of about
I (A: over the product melting point, until the reaction Is completed In
!>-l5 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.
he 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 aaterials used in the manufacture of PCP are phenol, chlorine,
and a catalyst aluminum chloride. Sources of raw oateriala vary fron fina
to firm. Sott3 manufacturers produce these materials on site, while others
purchase the same.
Dow Chemical makes phenol from benzene (via aonoc^lnrobenzene),
but this method of making phenol is being generally replaced by the
cumene 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 polrt out specific precautions euch as handling
chlorine and phenol in closed systems, and the use of plant coveralls, rubber
gloves, safety glasses, goR^I- ;and hard hats. There are occasional face
shields and respirators foi 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 PC? reactor, the following compounds
are emitted: chlorine gas, hydrochloric bcid 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 Che waste-
water treatment. The sources of eminsions 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 arc scrubbers for the
gaseous emissions, and filter bags for the particulates.
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 terns 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
v
and free from odor.
Cost of Control
Reichhold gave the following control costs for their 12-milllon-
pound-ca|>acit.y plant:
-------
TABLE 11. AIR CONTAMINANT EMISSIONS, SOURCES, AND RATES
FROM PCP MANUFACTURE AND WASTE TREATMENT
Rates,	Rates,	Rates>
Sources of Emission	Particulates	lb/hr	Gases/Vapors	!b/hr	Odor Odor Units/hr
Manufacturing Process
PCP Reactor	None
Acid System Reactors
None
Ingot Casting	PCP
Shotting Operation	PCP
Wascewater Treatment
(1)	chlorinated phenol
(2)	chlorine gas
(3)	Hydrochloric acid
vapor
(1)	chlorinated phenol
(2)	chlorine gas
(3)	Hydrochloric acid
vapor
None
None
PCP
PCP
None
-------
Chlorinated phenol feed
reactor
hci + ci2
gas
A
JO
X>
3
»_
U
(ft
PCP

I
4
l
i
HCI gas
Acid cooler
~ phenol
PhenoL	
phenol
Phenol scrut
storoqe
FIGURE 10. SCRUBBING SYSTEMS FOR THE CONTROL OF HCI,
Vent
Vent

o
».»
o
O
X
Water
t
.IT
o
o
m
¦o
-j
<
.Water
spray
7777777
To waste
""treatment
Acid tonk
vent
HO
storage
2 EMITTED FROM PCP REACTOR
-------
Vent
Vent
Oust
collector
From PCP reoctor
Oust
Melt
pot
Vent
Oust
collector
Shot
tower
Molten
PCP
Return to
shot pot
Shotting
operation
Oust I
Fume hood
Forced draft
air
Ingot
casting
To product
packaging
FIGURE 11.
DUST COLLECTOR SCHEMATICS FOR THE PENTA EMISSION CONTROL
-------
52
TABLE 12. AIK CONTAMINANT CONTROL METHODS
USED IN PCP MANUFACTURE
Control
Sys tem
Wet Packed and
Venturi Scrubber
(with water)
Duat Collector
(bay filters) at
Ingot casting
Efficiency,
percent
99-100
99
Compound
Controlled
Controlled
Emiaaion, lb/ton
Cl2
HC1
Phenol
Sodium Penta-
chlcro phenate
PCP
Fume
N.A.
N.A.
2
4.32
0.1 *
at shotting operation
95
PCP
1 b/
(a)	Controlled emission reported by Monsanto based on 1974 production.
(b)	Controlled < russiun reported by Relchhold based on 1974 production.
-------
53
Operating
Name of Control Device	Size	Capital Cost($) Coat ($/vr)
Bag filter (2)	(1) 2000 ft2* $ 70,000	$ 6,000
(2) 450 ft2
Mechanical Seals (for VCP reactor)	50,000	6,250
Phenol and Acid Scrubber	80,000	1,000
*Area of bag filter.
According to Ktlchhold, the greatest problem arose from the dust
colJ'ctors because or the lack of reliability. They consider dust eralsslona
less than the present 1.0 lb/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 lb/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 la desirable as a
method of recovery of materials. Since PCP 16 toxic to human respiratory
tracts and eyes, Its very efficient control is recommended. The present control
method which uses inadequate cloth area of ba« filters ne«ds augmentation.
Fumlaant - Paradlchlorcbenzene
About 50 percent of the paradlchlorobenzene (PDCB) is used as
lavatory space deodorant, about 40 percent in moth control, and the rest
as reactive intermediates in the production of chemicals sue., 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, nonblologlcal, and sunlight degrad-
ation at a moderate to rapid rate.
-------
54
1'roJuc Li on	Inventory
Paradichlorobenz-ene is manufactured by eight companies In nine
states. These companies, their plant design capacities, ar.d estiaated 1974
production arc given in Table 13.
Hie annual U.S. capacity is about ISO million pounds. Capacities are
flexible and throughput depends on demand and available feedstocks. Benzene
hat; been In very short supply recently due to decreased petroleum supplies.
The production for p-dlchlorobenzene 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 hava nor* 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.^^ Projections up to
the year 1980 were provided in Table 1, and the production by tha end of
the decade is estimated at 112 million pounds.
-------
55
rABLE 13. PRODUCERS OF PARADICHLOROBENZENE
IN THE UNITflD STATES (3,4)
Company
Loo
-------
56
Manufacturing Process
Paradichlorobenzene Is produced almost entirely as a by-product
from the manufacture of monochlorobeniene, which is produced by the
chlorination of benzene. Generally, prolonged chlorinatlon ia used to
produce various by-products besides PDCB, as shown in the following reaction
chemistry:
Benzene Chlorine
Monochloro
benzene
(70-75:;
yield)
Para
Ortho
D ich 1 or obenz cries
(10-20*/. yield)
o
CI* + HCl
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.
Wf M
Huoiot>* Mini
Biniint and mtW
ecMsroMn(MMi
M«niiU*wn
DacMorvbtfiltM
|M|«
hnnwqr
FIGURE 12. PRODUCTION AND WASTE HANDLING
SCHEMATIC FOR PARADICHLOROBENZENE
(12)
-------
57
Raw and Waste Material Handling
The essential raw materials usad in the manufacture of FDCB
are: benzene, chlorine, and sodium hydroxide. The main toxic materials
that need special handling during PDCB manuiacture are chlorine, HC1,
and PDCB. Nose firms do edopt some precautionary measures for their em-
ployees Bucb as wearing of plant coveralls, rubber glovea, 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 trlchlorobenzenes are recovered.
At Monsanto, the HCl it, recovered as muriatic add with only
small amounts escaping through vents or going to a waste treatment plaut.
The PDCB work area is ventilated and the exhaust air goes to a wet scrubber.
Monsanto is reported to monitor the PDCB concentration l«vsl.
Air Contaminant Emissions, Sources, and Rates
Sources of air emissions are chlorinator, PDCB recovery system,
and the press room. "Hie pollutants emitted are hydrochloric acid, chlorine,
benzene, chlorooenzene, 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 HCl are given off at the
wastewater treatment plant.
Air outaminant Kmissinn Control
Among the pollution control equipment used to control the gaseous
and particulate emissions are wet scrubbers and absorption columns. An
.-stimate of co-itrol efficiencies at the Standard Chlorine Company is pre-
sented in Table 15.
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TABLE 14. AIR POLLUTION EMISSIONS, SOURCES. AND RATES FuOM
PARADICHLOROBENZENE MANUFACTURE AND WASTE TPEATMENT
Sources of Emissions
Particulates
Rates;
lb/hr
Gases/Vapors
Rates,
Ib/hr
Rates,
Odor Odor L'nits/hi
Manufacturing Processes
Chlorinator
—
--
(1)
(2)
(3)
(4)
HCl
Benzene
Chlorobenzecie
C12
—
Same
Same
Same
Same
P-dJ.chlorobenzene
Recovery-
PDCB
Chloride
—

Chlorobenzene
—
Same
Press Room
PDCB
—

--
—
Same
Wastewater Treatment


(1)
(2)
Si

Sdme
-------
59
TABLE 15. AIR POLLUTION CONTROL AT STANDARD
CHLORINE
Eff l c itnc y , *	Compc und
Water Devi j 3	percent	Controlled
War.er Scrubber
90
0)
HC1


(2)
rtenzi:ne


(3)
Chlorobenzene


W
Dichlorobonzene


(5)
Paradlchlorobonzene
Absorption
95
(1)
HC1
Column

(2)
Ch'orobenzene


(3)
Be tz«ne
* Controlled ertisslun data weir not pi ovidee! 'jy any one
company.
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oO
5ome companies, for example, Allied, Sclvent, 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-dlchlorobenzene 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 irea Involved.
However, Standard Chlorine has controls in place (water scrubber
and column absorber as given above) and the Monsanto Industries controls by
Bearts of water scrubber only. The press room Is not controlled. Emission
from this area Is primarily PDCB.
The acceptable level of paradichloroben.:ene used as the Threshold
Limit Value by American Conference of Governmental Industrial Hygienists
(ACCIH) is 75 ppn. 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($)	CostfS/vr)
Water Scrubber^) 48" & 16" 28,000	40,000
Carbon Absorption 100,000	NA
Columns
SlRnlflcance of Air Cor.taminant Emission
The nature of the pollutants emitted during the tunufacture of
PDCB requires that these substances be controlled. The control of PDC?
to about 73 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, requited to be able to adequately
aseess the significance of these emissions.
* 75 ppm Ls the toxic level for hunans.
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61
SECTION V
REFERENCES
(1)	Kumkor, Roscmarie 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 Conmiaaion Report - Synthetic Organic Chemicals
(1970, 1971, 1972, 1973).
(3)	19V4 Directory of Chemical Producers-Chemical Information Services
Stanford Research Institute, Menlo Park, California, pp 513, 747,
753, 7;S, 759, and 761 (1974).
(4)	Ch.:tnical Marketing Reporter, Vol. 203, No. 21, p 9 (1973).
(h) "Controlled-Releaae Pesticides Attract Interest", Chemical and Engineering
News (September 30, 1974).
(6)	ts.'Iess, Edward W., Rosemarie Von Rumker, ar.d Thomas L. Ferguson, "The
Pollution Potential in Pesticide Study Series 5", EPA Technical Studies
Report: TS-00_72-Q4 (June, 1972),
(7)	Stutz, C, N., "Treating Parathion Waates", Chemical Engineering Progreaa,
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. Paints No*. 2, 131, and 259 (Dow, l')38; and 2,447,790 (Retchhold, 1960)
Also, Chemical Process Review, No. 5, Pesticide Production Processes (1967).
(11)	Chemical ILirketing Reporter, Vol. 2011, Nc. 15 (April, 1973).
(12)	Faith, W. L., D. B. Keyes, and R. L. Clark, Industrial Chemicals. Third
Edition, John Wiicy aid Sons, Inc., New York (1965).
(13)	Atkins, Patrick R., "The Pesticide Manufacturing Indus Cry--Current Waste
Treatment and Disposal Practice", For Environmental Protection Agency,
Project #12020FYE (January, 1972).
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APPENDIX A
SUMMARY OF THE SELECTED PESTICIDES
AND THEIR PRODUCERS
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APPENDIX B
SUMMARY OF NONPROPRIETARY INFORMATION OBTAINED
FROM THE SURVEY OF PESTICIDE PLANTS
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TABLE B-l. SUMMARY OF AIR CONTAMINANT EMISSIONS, SOURCESt AND RATES


Major Compound
Rate*,
Pesticide
Sources
Emitted
lb/hr
Methyl Parathion I.
Reac tor
P2°5



V
460
2.
(Jh Lorinatur
HCi



S
420
3.
MPT Unit
NaCl
460
Ci.
Waste Treatment Incinerator
so2
1550


P„0C



2 5


Wastewater
HjS



Mercaptan

Toxaphene I.
& -Pinene Production
N.A.O

2.
Camphene-Production
N. A,

3.
Chlorination - Toxaphene
HCI



Cl2
4350
A.
Toxaphene Granular
Toxaphene


Produc tion


5.
Wastewater Treatment
C12



HCI

MSMA I.
Sodium Arsenito Production
A82°3
6.44 x 10'
2.
DMSA
CH3C1



CH^OK



(ch3)2o

3.
MSMA Production
V°4



MS Ma

A.
MSMA Processing
MSMA

5.
Waste Treatment
N. A.

Trlfluralin	1. Nitration	Salt of Nitrate,
sulfate, chloride
HF	1
S02	3
Nitrogen oxides	3
2. Condenser
chci3
Trifluratin
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TABLE £i - I. SUMMARY OF A IK CONTAMINANT EMISSIONS, SOURCES, AND KATES
Pesticide
Sources
Major Compound
Emitted
Rates,
Ib/hr
PentacliJ.oropher.oI 1.
Pentachlorophenol
Chlorinated
Phenol
C12
HCI

2.
Acid System foacuir.'
Chlorinated
Phenol
HCI
*
3.
Ingot Casting
C12
PCP

A.
Shotting Operation
PCP

5.
Wastewater Treatment
N.A.

Paradichloro- 1.
bewzenc
Chlorinator
HCI
Benzene
Chlorobenaene

2.
Recovery
Cl2
PDCB
Chlorobencene

3.
Press Room
PDCB

U.
Wastewater Treatment
Cl,

HC1
(a) Not available,
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TABLE B-2. SUMMARY OF AIR EMISSION CONTROL DEVICES, EFFICIENCY, AND COST
Pesticide
Source of
Information
Control Device
Efflclency
Capital
Operating
Methyl Parathlon
Toxaphene
MS HA
Trlfluralln
Pentachlorophenol
Parad1e h1orobencene
Monsanto
Monsanto
Hons sr. to
Hercules
Hercules
Hercules
Hercules
Diamond
Ansul
Diamond
Ell Lilly
Relehhold
Reichl.old
Relehhold
Standard Chlorine
Standard Chlorine
Standard Chlorine
Stcndard Chlorine
Incinerator (H^S, S, nercaptan)^	(b)
Water Sciubber	HCl)	95
Brink Mist Eliminator	99.9
Alkali and Water Scrubber (solvent vapor, HCl, Clj)
Stripping (solvent vapor, HCl, ^1^)
Limestone Adsorption (solvent vapor, HCl, CI 1	100
2
Baghouse (toxaphene)
Baghouse (As^O^)	8,000
Water Scrubber (Aa^O^)
Acldlfler Vent Scrubbers	300
1- and 2-Stage Venturi Scrubber and Tri-«er	90 1,000,000
Wet Scrubber
Packed and Venturi Scrubber (Cl^, Phenol, acids)	99-100 80,000
Bay Filters (PCP)	95-99 70,000
Mechanical Seals (for PCP reactor)	50,000
Uater Scrubbers	90	28,000
(HCl, benzene, chloroboasane, etc.)
Absorption Colusa	95
(HCl, benzene, chlorobeacene)	100,000
(a)	Coapouods in parentheses are controlled by tbo preceding cootrol device.
(b)	Blanks ihw data not available.
200
100
1,000
6,000
6,200
40,000
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••
rABI.E 11-3. LIST OF CONTACTS HAVING EXPERTISE AND SOURCKS 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 54143
(715) 735-7411
Diamond Shamrock Chemical Company
W. R. Taylor
1100 Superior Avenyc
Cleveland, Ohio
(216) 694-5000
Hercules Incorporated
H. E. Hicks
Brunswick, Georgia 31520
Eli Lilly and Company
Arlie J. Ullrich
Indiarapolis, Indiana 46206
Monsanto Industrial Chemicals Company
P. E. Helsler
Sauget, Illinois 62201
(618) 271-5835
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.
Reichhold Chemicals, Inc.
J. C, Man love
P. 0. Box 1482
Tacoma, Washington 98401
Standard Chlorine Chemical Company, Inc.
F. Romano
1035 Belleville Turnpike
Kearny, New Jersey 07032
(201) 997-1700
Very good response.
Estimates of production data,
production and control flow
sheet and costs.
Production data, control
method, and cost given.
Stauffur Chemical Company
Dan Simmons
Mt. Pleasant, Tennessee
(203) 226-1511
Production data only.
Vulcan Materials Company
R. A. Bondurant, Jr.
P. 0. Box 545
Wichita, Kcnsas 67201
(316) 524-4211
Production data, control
method, and cost provided.
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APPENDIX C
SAMPLE OF LETTER MAILED TO SELECTED
PESTICIDE MANUFACTURING COMPANIES"
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August , 1974
Gentlemen:
Bat te lle's Columbus Laboratories under contract to the Strategic Studies
Unit of cbe Office ol 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 Toxaphenc
(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 emlcted
(3)	Currently employed mr.chods of emission control.
From the above data, the study will seek to project future emissions, relate
it to similar emission from other aourcc-a, and thus obtain a quantitative
esti&ate for the significance of pesticide emissions irom the manufacturing
sector.
Please find attached a iisc of six questions, which we request you to complete
and return to up at your earliest convenience. We wii'l keep any information
you supply within BCL files so that the confidentality of vcu': data is preserved.
We appreciate your willingness to cooperate and would liKe co assure you that
any assistance you will provide will be of immense value *.o this study required
undei the Clean Air Act of 1970.
Cordialiy,
C. N. lieadi
Research Scientist
Waste Control .ind Process
Technology Ser.tion
Attachment: Questionnaire
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7A
Nutm- ol Miinuf.ici ur 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 lb In Operation	millions of lb
1970		 			
1971		 			
1972					
1973		 			
1974	(Estimate) ________ —_____	________
1975	(Estimate) 	 			
Provide derails of any t ileal or economic situation that may affect future
increases or decreases in your plant production.
Question 2> Process Description
Give a briaf description of the processes used to produce the pesticide. Specify
»-he raw materials, by-products, and waste materials. Amplify with simple production
chemistry and attach simple flow sheets.
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Question 3. Raw nnd Waste Material Handling with the Plant
Particular attention is gnp.erally paid to materials handling within the plant,
8ir.ee the raw and waste materials may have high toxicity. Briefly describe the
precautions token in your plant.
Question U, Air Contaminant EtnlcBions and Control
Manufacturing Plant
Site
Particulates
Emission
Sources
Compounds
Emitted
Controlled
Yes or No
Method of
Control
Emissions
(lb/ton)*
Efficiency
(7.)






Gaset>






Odor






Wavte Disposal Site
Particulates






Gases






Odor






* Or any ot.ier unit employed by your facility.
Describe briefly the emission control system ured in your plant for particulates,
gases, odor, and visibility control. Describe problems of visibility and odor, if
any, arounJ 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 cdor problems
associated with your plant.
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QuotIon 5. Cost of Emission Control System
Name of Control System Size	Capital Cost ($) Operating Cost ($/vr)

Please Indicate the status of sir emissions from your facility as (a) acceptable
(b) needs Improvements? Comnent on the economic impact of restricting t->.«
emissions from your plane lo levels considered (a) reasonable (b) too cestrlctive.
State what you think these: levels should be.
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