United States
 Environmental Protection
 Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EPA-450/3-88-003
October 30 1986
Air
Summary of Emissions
Associated with
Sources of Naphthalene

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                                   EPA-450/3-88-00;
 Summary of Emissions
     Associated  with
Sources of Naphthalene
         Emission Standards Division
                       U.S. r.nyiro'-;;;.,,-^: ,-•
                         .
                       ••' '••' "•: Jack;:' ••'••<
                       thic   , !L of
   U.S. ENVIRONMENTAL PROTECTION AGENCY
         Office of Air and Radiation
   Office of Air Quality Planning and Standards
   Research Triangle Park, North Carolina 27711

           October 30, 1986

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This report has been reviewed by the Emission Standards Division of the Office of Air


         ' ^ """                                              °
       d                                              rae "»™  °
intended to constitute endorsement or recommendation for use Copies of this

the Library Services Offices (MD-35), U.S. Env.ronmenta, Protectio'n A e^^      a       n

2771 1 , or from National Technical Informat.on Serv.ces, 5285 Port Royal Road, Sprmgf.eld VA 221 61

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                           TABLE OF CONTENTS


Section           "                                      Pa5e

LIST OF TABLES	V

LIST OF FIGURES	vi i

1.0    INTRODUCTION AND SUMMARY	1-1

2.0    NAPHTHALENE PRODUCTION AND END USES	2-1

       2.1   Introduction	2-1

       2.2   Naphthalene Production Processes    ....  2-1

            2.2.1   Naphthalene from Coal Tar   ....  2-1

            2.2.2   Naphthalene from Petroleum  ....  2-7

       2.3   Naphthalene Usage   	  2-8

            2.3.1   Phthalic Anhydride  	  2-11

            2.3.2   Carbamate  Insecticides  	  2-13

            2.3.3   2-Naphthol	2-16

            2.3.4   Synthetic  Tanning Agents  	  2-16

            2.3.5   Surface Active Agents   	  2-16

            2.3.6   Moth Repellant .  .	2-21

            2.3.7   Miscellaneous  Uses	2-23

3.0    NAPHTHALENE  EMISSION  SOURCES AND  ESTIMATES  ...  3-1

       3.1   Naphthalene Emission  Sources  	  3-1

       3.2   Air  Impacts	3-2

            3.2.1    Emissions  from Handling and
                     Production of  Naphthalene	3-2

            3.2.2    Emissions  from Naphthalene  End
                     Uses	  3-2

            3.2.3    Naphthalene Emissions  from
                     "Inadvertent  Sources"  	   3-5

            3.2.4   Naphthalene Emission Summary .  .  .   3-5

                                iii

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                           TABLE OF CONTENTS
                              (concluded)
Section                                                 Page

      3.3   Water Impacts	   3-5

      3.4   Solid Waste Impacts 	   3-10

4.0   REGULATIONS AFFECTING THE ENVIRONMENTAL
      RELEASE OF NAPHTHALENE 	  4-1

      4.1   Toxic Substances Control Act 	  4-1

      4.2.   NSPS for SOCMI Equipment Leaks	4-1

5.0   AMBIENT AIR MONITORING DATA FOR NAPHTHALENE. .  .  5-1

6.0   REFERENCES	6-1

Appendix A   Documentation for Human Exposure
             Model  Input DAta	A-l

Appendix B   Procedures for Estimating Naphthalene
             Emissions from Coke By-Product Recovery
             Plants	B-l

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                             LIST OF TABLES   '

Table                         Title                     Page

2-1   U.S. Coke By-product Recovery Plants Handling/
      Processing Naphthalene  	   2-2

2-2   Current and Potential U.S. Naphthalene
      Producers and Capacities, 1985	   2-5

2-3   U.S. Naphthalene Consumption, 1983	   2-10

2-4   Producers of Synthetic Tanning Agents 	   2-18

2-5   Producers of Surface Active Agents  from
      Naphthalene Derivatives 	   2-22

2-6   Miscellaneous Naphthalene Derivatives and
      Producers	   2-24

3-1   Naphthalene Emissions from Coke By-product
      Recovery Plants 	   3-3

3-2   Naphthalene Emissions from Production  of
      Chemical-grade Naphthalene  	   3-4

3-3   Naphthalene Emissions from Major Users  ....   3-6

3-4   Summary of Naphthalene Emissions from All
      Sources	   3-9

A-l   Modeling Parameters  for Naphthalene  Emissions
      from Coke By-product Recovery Plants	   A-27

A-2   Modeling Parameters  for Naphthalene  Emissions
      from Naphthalene Production 	   A-29

A-3   Modeling Parameters  for Naphthalene  Emissions
      from Phthalic Anhydride Production	   A-31

A-4   Modeling Parameters  for Naphthalene  Emissions
      from Carbamate Insecticides 	   A-32

A-5   Modeling Parameters  for Naphthalene  Emissions
      from 2-naphthol Production  	   A-33

A-6   Modeling Parameters  for Naphthalene  Emissions
      from Production of  Synthetic Tanning Agents  .  .   A-34

A-7   Modeling Parameters  for Naphthalene  Emissions
      from Production of  Surface Active  Agents --
      1-naphthalenesulfonic Acid  	   A-35

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                             LIST OF TABLES
                              (concluded)

Table                         Title                     Page

A-8   Modeling .Parameters for Naphthalene Emissions
      from Production of Surface Active Agents —
      2-naphthalenesulfonic Acid  	   A-37

A-9   Modeling Parameters for Naphthalene Emissions
      from Production of Moth Repellant	   A-39

A-10  Modeling Parameters for Naphthalene Emissions
      from Production of Miscellaneous Organic
      Chemicals	   A-40
                                VI

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                            LIST OF FIGURES

Figure                        Title                     Page

2-1   Final  cooler with naphthalene sepa'ration ....  2-4

2-2   Naphthalene production from coal tar	2-6

2-3   Production of naphthalene from petroleum
      fractions	2-9

2-4   End uses of naphthalene	2-12

2-5(a)Flow diagram for oxidation process in production
      of phthalic anhydride  	  2-14

2-5(b)Fow diagram for refining process in production
      of phthalic anhydride  	  2-15

2-6   Flow diagram for carbaryl production using
      naphthalene	2-17

2-7   Selected paths to naphthalenesulfonic acids. .  .  2-20

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                     1.0  INTRODUCTION AND SUMMARY

     The purpose of this document is to identify and quantify, on a
preliminary basis, all emission sources of naphthalene.  These esti-
mates will  be used to estimate public exposure to naphthalene using
EPA's human exposure model  (HEM).  Information used to assemble this
document came from existing information sources, including previously
published EPA documents and reports, general  chemical  and engineering
references, current literature and periodicals, and State agency files.
In addition, information was obtained through telephone conversations
with State air pollution control personnel and/or visits to State
agenci es.
     In most cases there was little information available for indi-
vidual producers and users of naphthalene.  The scope and purpose of
this project did not allow, in many instances, the desired investiga-
tion or follow up to fill information gaps.  Therefore, where informa-
tion was not available, assumptions were made.

SUMMARY
     There are 17 producers of crude and/or refined naphthalene in the
U.S.  Twleve of these producers are coke by-product recovery plants
that may refine naphthalene or manufacture a coal tar product containing
naphthalene.  Two of the 17 producers use coal tar as a raw material to
manufacture chemical-grade naphthalene, and three other producers use
petroleum as a raw material to produce chemical-grade naphthalene.
Naphthalene is used primarily as an intermediate in the production of
organic chemicals, including phthalic anhydride  (mainly), carbamate
insecticides, surface active agents, synthetic tanning agents, and
miscellaneous organic chemicals.  The only direct use of naphthalene is
for moth repellant.   Koppers in  Follansbee, WV, which manufactures
naphthalene from coal tar, is the only producer that uses some of the
naphthalene it produces on-site  for the production of an end-use
chemical, namely, phthalic anhydride.  All other producers sell naphthalene
to various customers  for the manufacture of other end-use chemicals.
      Emission sources from the production and use of naphthalene are
primarily from distillation unit vents, equipment leaks from pump seals

                                   1-1

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and flanges, and naphthalene storage tanks.  Process emissions
may be vented to a flare or other control  device, although informa-
tion was not usually available to indicate what emission controls, if
any, are used.  Total  naphthalene process  emissions from production
and use are estimated to be about 85 Mg/yr.  Fugitive emissions of
naphthalene are approximately 43 Mg/yr, and total storage emissions of
naphthalene are estimated to be about 84 Mg/yr.  Naphthalene emissions to
the atmosphere from all sources are about  213 Mg/yr.  The largest
contributors of naphthalene emissions are  coke by-product recovery
plants and naphthalene users, emitting about 38 and 35 percent of total
naphthalene emissions, respectively.  Naphthalene producers contribute
about 25 percent of the total.  Less than  3 percent of naphthalene
emissions originate from combustion processes, primarily residential
wood and coal heating.
                                  1-2

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                2.0  NAPHTHALENE PRODUCTION AND END USES

2.1  INTRODUCTION
     Naphthalene is produced from either coal  tar or petroleum as raw
materials.  Approximately 55 percent of the total annual capacity of
chemical-grade naphthalene is recovered from coal-tar-based
feedstocks, while the remainder is from petroleum refinery streams.
Crude naphthalene from coal  tar may be produced at one of twelve coke by-
product recovery plants in the U.S.  Five U.S. companies currently
produce chemical-grade naphthalene from either coal tar or petroleum at
facilities operating with a  total annual  capacity of 184 gigagrams (Gg),
based on a January 1985 estimate.1  In addition, two other companies,
U.S.S. Chemicals and Ashland Chemical  Company, have a total of three
facilities to produce chemical naphthalene; however, all three are closed
due to market conditions.1>2
     Since the early 1970's, naphthalene production as a whole has
decreased at an average rate of about 3 percent per year, from 326 Gg
in 1970 to 184 Gg in 1985.1'^  The decline in naphthalene production
primarily resulted from competition with ortho-xylene as the feedstock
for phthalic anhydride, the major chemical  derivative of naphthalene.^
Since ortho-xylene is currently the preferred raw material for
phthalic anhydride manufacture, only about one-fourth to one-third
of phthalic anhydride produced in the United States is based on
naphthalene feed.
2.2  NAPHTHALENE PRODUCTION PROCESSES
2.2.1  Naphthalene from Coal Tar
     2.2.1.1  Coke By-product Recovery Plants.  Coal-tar naphthalene
may be recovered as a crude by-product from the coking of coal at
some coke-oven by-product plants. Table 2-1 lists the twelve U.S.
coke by-product recovery plants that handle and/or process naphthalene.
Naphthalene, which is present as a constituent of coke oven gas, is
removed from the gas stream after the coke oven gas leaves the ammonia
adsorber.  The naphthalene-containing gas is cooled in a tower scrubber
(called a final cooler) by direct contact with water to condense most
                                  2-1

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             Table  2-1.   U.S.  COKE BY-PRODUCT RECOVERY PLANTS
                     HANDLING/PROCESSING- NAPHTHALENE*
Plant
Empire Coke
Republic Steel
National Steel
Interlake
Indiana Gas & Chemical
U.S. Steel
Rouge Steel Co.
National Steel
Bethlehem Steel
Chattanooga Coke &
Chemical
Lone Star Steel
J&L Steel
(LTV Steel )
Location
Holt, AL
Gadsden, AL
Granite City, IL
S. Chicago, IL
Terre Haute, IN
Gary, IN
Dearborne, MI
Detroit, MI
Bethlehem, PA
Chattanooga , TN
Lone Star, TX
Pittsburgh, PA
Coke Production
Capacity
(1,000 Mg/yr)
161
758
570
582
132
4,228
778
1,397
2,253
130
507
1,792
Reference 5.
                                   2-2

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of the naphthalene and any entrained tar and vapors, thus separating
naphthalene from the gas stream before the gas is processed further.6
The condensed naphthalene floats to the top of the water in the final
cooler, is skimmed and collected in open sumps as an impure, yellow-brown
slurry containing about 50 to 60 percent water.5»7  Separation may be
enhanced with a froth flotation separator or similar equipment.  The
naphthalene slurry may be pumped into a tank where water is removed by
gravity separation, which crystallizes the product.  The resulting
crude naphthalene may be dissolved in coal tar after physical  separation
and sold as a commercial feedstock.  A typical dry coal  tar processed
in the United States contains approximately 8 to 10 weight percent
naphthalene.4>8  Although crude naphthalene has little market value,
about 40 percent of coke by-product recovery plants handle and/or
process naphthalene in some manner.
     If the crude naphthalene is further refined on-site, the
crystallized product may be refined through drying when  the crystals
are melted in a separate rectangular tank equipped with  coils for
either cold water or steam circulation.5  After 24 hours in the vessel,
an upgraded (chemical-grade) naphthalene (>78°C crystallization point)
is generated.  Figure 2-1 is a flow diagram of a final  cooler and
recirculating water Circuit with naphthalene collected by physical
separation at a typical coke by-product recovery plant that handles
and/or processes naphthalene.
     2.2.1.2  Coal-tar Naphthalene Producers.  As discussed above, the
naphthalene product that is dissolved in coal tar at coke by-product
recovery plants may be sold as a commercial feedstock to companies that
produce chemical-grade naphthalene as an intermediate product for
various end uses.  Coal-tar naphthalene accounts for about 55 percent
of the total annual chemical naphthalene capacity.  There are only two
U.S. producers of chemical  naphthalene in operation that use coal  tar
as a raw material, namely, Allied Chemical in Ironton, Ohio, and Koppers
Company in Follansbee, West Virginia.  These plants and  their location
and capacities are listed in Table 2-2.
     Figure 2-2 depicts a general process for the production of chemical
naphthalene from coal tar.   To recover naphthalene from  coal tar, the
crude tar is distilled and fractionated.  The crude coal tar is generally

                                  2-3

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                    RECIRCULATING  WATER
COKE OVEN GAS
   50-60*C
                      FINAL
                      COOLER
                          20-30»C
                            NAPHTHALENE
                            SEPARATION
               CRUDE NAPHTHALENE  TO
                FURTHER PROCESSING
  COOLED  COKE  OVEN
  GAS TO LIGHT OIL
  SCRUBBER
                                                      SATURATED  AIR
         ATMOSPHERIC
         COOLING
         TOWER
                                                             T
                                                              AMBIENT AIR
  WATER
SLOWDOWN
                 Figure 2-1.  Final  cooler with naphthalene  separation.
                                          2-4

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           Table  2-2.   CURRENT  AND POTENTIAL  U.S. NAPHTHALENE
                        PRODUCERS  AND CAPACITIES,  1985
      Producer
                                Location
                       Capaci ty
                       (Mg/yr)
                                                                Raw Material  Used/Remarks
Coal-tar  naphthalene

Al 11 ed  Chemical

Koppers Co.


U.S.S.  Chemicals


Petroleum naphthalene

Chemical  Exchange
  Industries  (Advanced
  Aromatics  Chemical Co.)

DuPont


Texaco Chemical

Ashland Chemical
Ironton,  OHa

Follansbee, WVa
Clairton,  PAC
Gary, INC
34,000b    Coal  tar/product is sold.

68,000b    Coal  tar/product is both sold
             and  captively consumed.

90,000d'e  Coal  tar.
   ~e     Coal  tar.
Baytown, TXa



Chocolate Bayou,  TXa     41,000b
14,000°    Petroleum  naphtha stream/
             product  is  sold.
Delaware City,  OEa       27,000b

Ashland, KYC            41,000d
           Petroleum  (ethylene by-product)/
             product  is  sold.

           Petroleum/product  is sold.

           Petroleum/product  is sold.
Total capacity (plants  operating)
               (plants  not  operating)
                        184,000 Mg/yr
                        131,000 Mg/yr
aCurrent producer -  plant  in operation, based on information  obtained in Reference 1.

bSRI  International  estimates as of January 1, 1985 (Reference 1).

cPlant not operating.   This  plant  is on standby and can be  restarted  if market conditions
 warrant (Reference  9).

dEstimates as of October 1984  (Reference 2).

eCombined capacity for facilities  in Clairton, PA, and Gary,  IN.
                                            2-5

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                                          Middle Oil
Coal
tar
              Waste
                                                 Crystallizing
                                                     pan
                                                                  Creosote
                                                                   oil
                    Centri f uge
                             Anthracene
                                oil
Tar acids
and bases
to recovery
                                                Waste
                                            To cresol
                                            and  phenol
                                            plant
                                                                Crude
                                                                Naphthalene
                                                                  Cooling
                                                                   Pan
                                                           Refined
                                                           Naphthalene
                   Figure 2-2.  Naphthalene  production  from  coal  tar.
                                                                    10
                                         2-6

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distilled in pipe stills in either a batch or continuous  process.   The
tar is discharged into a flash tank from which the vapors  pass  to  con-
densers; the still bottom and the pitch are sent to receiving  tanks.
If the total distillate is condensed, the distillate is  fractionated
in four fractions:  light oil, middle oil, heavy oil, and  anthracene
oil.  The middle oil  fraction contains most of the naphthalene  and tar
acids.
     The middle oil  fraction, containing naphthalene, phenols,  and
cresols, is pumped hot into shallow pans where it is cooled,  allowing
the naphthalene to crystallize.  After draining, the crystalline coke
is then broken up and charged into batch centrifuges.  The mother
liquors are combined and sent to phenol and cresol recovery units.
The naphthalene coke is washed with hot water to increase  its  purity
before it is discharged as crude naphthalene.  This material  is suit-
able for phthalic anhydride manufacture and is graded and  sold  according
to its melting point.
     For refined naphthalene, the crude material is further distilled.
The distillate is first washed with a hot caustic soda solution to
remove phenolic compounds and then washed with concentrated sulfuric
acid to remove basic substances.  To yield a refined product,  the  washed
naphthalene is redistilled.  The distillate from the final  still is
either cast into forms or is cooled and subsequently .crushed.   The
refined material is suitable for manufacture of flakes or  pellets  for
insecticide use (i.e., mothballs or flakes).^  However,  the  production
of refined naphthalene from coal tar essentially has ceased in  the
United States due to costs of refining and costs of disposing  signifi-
cant amounts of waste sludge that is generated by the process.^
2.2.2  Naphthalene from Petroleum
     There are three U.S. producers of naphthalene in operation that
use petroleum as a raw material, namely, Chemical Exchange Industries,
Baytown, Texas; duPont, Chocolate Bayou, Texas; and Texaco Chemical,
Delaware City, Delaware.  One potential producer, Ashland  Chemical
Co. in Ashland, Kentucky, is not currently operating, but  may  restart
if market conditions warrant.  These plants and their capacities are
listed in Table 2-2.
                                  2-7

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     The production of naphthalene from petroleum involves two principal
steps.  The first is the production of an aromatic fraction in the
naphthalene-al kylnaphthalene boiling range, usually by hydroaromatiza-
tion or cyclization.  The second step is the dealkylation of the aromatic
fraction either thermally or catalytical ly.  The naphthalene that is
produced is recovered as a high quality product, usually by fractional
distil lation. 4  Suitable feedstocks may be the bottoms distilled from
catalytic reformate or a narrow cut distilled and concentrated from
refractory cycle oils.  Figure 2-3 presents a general  process used to
produce petronaphthalene.
     The feedstock and a hydrogen-rich gas are pumped  to a dealkyla-
tion reactor.  The reactor product is quenched and is  then sent to a
separator from which part of the hydrogen-rich gas is  recycled and
part burned as fuel.  The liquid product is distilled  to separate
naphthalene, gasoline, and fuel oil.  The naphthalene  produced by this
process is usually better than 99 percent pure and is  low in sulfur
content.  Naphthalene may also be recovered from the stream of
naphthalene-methyl naphthalene formed in the cracking  of heavy liquids
for ethylene production.^
2.3  NAPHTHALENE USAGE
     Naphthalene is used almost exclusively as an intermediate in the
manufacture of organic chemicals.  The only direct use of naphthalene
is as a moth repellant.  The U.S. naphthalene consumption by end use
(based on 1983 data) is presented in Table 2-3.  Demand for naphthalene
and consumption patterns are not expected to change significantly
through 1988, according to October 1984 estimates.2
     Naphthalene derivatives are numerous and can be classified as
follows;11
     Al kylnaphthalenes
     Chlorinated naphthalenes
     Hydrogenated naphthalenes
     Naphthalenecarboxylic acids
     Naphthalenesul fonic acids
     Nitronaphthalenes and nitronaphthalenesulfonic acids
     Naphthylamines
                                  2-8

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 Hydrogen make-up
                                                             	^_ Fuel gas
                                                                          Gasoline
                                                                                      Naphthalene
 or other
feedstocks
        Figure  2-3.   Production  of naphthalene  from  petroleum fractions.
                                                                                  10
                                               2-9

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          Table  2-3.   U.S.  NAPHTHALENE  CONSUMPTION, 1983a
Use
Phthalic anhydride
Carbamate insecticides
Surface-active agents
Synthetic tanning agents
Moth repellent
Miscellaneous organic
chemicals
2-naphthol
Total
Naphthalene
consumption
(Gg)
233
23
23
18
13
5
ob
315
% of Total
74
7
7
6
4
2
0
100
aReference 9.

^American Cyanamid, Willow Island,  WV,  the sole  U.S.  producer  of
 2-naphthol, ceased production in 1982  (Reference  9).   All  2-naphthol
 consumed in the U.S.  is now imported.
                                2-10

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     Aminonaphthalenesulfonic acids
     Naphthols
     Hydroxynaphthal enesul fonic acids
     Aminonaphthols
     Aminohydroxynaphtha!enesulfonic acids
     The three major uses  of naphthalene, which represent 88 percent of
naphthalene consumption,  are as feedstocks for the production of phthalic
anhydride, carbarnate insecticides, and surface-active agents.  The
remaining 12 percent of naphthalene consumption is used in a variety of
applications,  including usage as a feedstock in the production of
synthetic tanning agents,  in moth repellant, and in the manufacture of
miscellaneous  organic chemicals.  Figure 2-4 presents a general  diagram
of naphthalene use.  A brief description of each of the major uses and
its processes  is presented  below.
2.3.1  Phthalic Anhydride
     Seventy-four percent  of naphthalene produced is consumed in the
manufacture of phthalic anhydride.  Phthalic anhydride is derived from
one of two raw materials,  naphthalene or ortho-xylene.  For many
years coal tar naphthalene  was the only raw material used for phthalic
anhydride production.  However, ortho-xylene has gradually replaced
naphthalene as the principal feedstock for phthalic anhydride manufacture;
only about 25  to 35 percent of phthalic anhydride is derived from
naphthalene.  Koppers Company, Cicero, Illinois, operates the only
naphthalene-based phthalic  anhydride plant in the U.S., with an
annual production capacity'of 20,400 Mg.^2  Koppers shut down its
Bridgeville, Pennsylvania,  plant upon restarting its Cicero unit in
1985.  The Cicero unit was  idle while more than one-half of its
capacity was converted from orthoxylene to naphthalene feedstock.  Two
other phthalic anhydride  producers, Monsanto and USS, closed their New
Jersey and Pennsylvania units in early 1986 and fall of 1983, respectively.
     The phthalic anhydride plant at Koppers in Cicero, Illinois, is
broken down into two operational areas, oxidation and refining.   Each
of these sections has a dedicated heat transfer oil system used to
regulate temperature during the process.  The facility can use either
naphthalene or ortho-xylene as a raw material.13
                                  2-11

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ro
 i
                       Coal-tar
                        (60*)
Petroleum
  (402)
Naphthalene









                                                           Phthallc anhydride
                                                           (1.2,3.4-)
                                                           Tetrahydronaphthalene
                                                           Decahydronaphthalene
 Plastlclzers
 Alkyd resins

 Polyester resins


	^- 1-naphthol
                                                           Naphthalene sulfonlc add
                                                           Chloronaphthalenes
                                                           Alkylnaphthalenes
                                                                                          carbaryl
                                                                                             2-naphthol
          1-naphthol        ~|_
          1-n1tronaphthaleneJ
                                                                                                 -Dyes  & dye  Intermediates
                                                                                                 -Antloxldants for rubber,
                                                                                                    fats,  and oils
                                                                                                 -Pharmaceuticals

                                                                                                 .Fungicides, rodentlcldes

                                                                                                  Perfumes
                                                                                          	Synthetic tanning agents
               Dyes
               Pharmaceuticals
               Rubber chemicals
               Rodentlcldes
               Perfumes
                                                                                          Mono- and dl-
                                                                                           alkylnaphthalene sulfonlc acids & salts
                                       Surface-active agents
                                                         _ Naphtha]eneacetlc acid
                                                         _Moth repel 1 ant
                                                         *_ Miscellaneous organic chemicals
                                                           Figure 2-4.   End uses  of  naphthalene.
                                                                                                            14-16

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     The oxidation section consists of four production trains,  two of
which are deactivated.  This operation is bro.ken down into seven
subsections:  air compressing and heating, ortho-xylene and naphtha-
lene feed systems, reaction and gas cooling, condensing, scrubbing
and incineration, and Mobil therm oil  system.  A diagram of the  oxida-
tion operation is presented in Figure 2-5(a).  In the oxidation process,
coal tar naphthalene and/or o-xylene is vaporized, mixed with air
and fed to the reactors.  The catalytic oxidation reactors convert
the feedstock to phthalic acid and other by-products.  Reactor  off
gases are cooled and sent to a bank of six switch condensers which
capture and solidify the product.  According to a preset cycle, one of
the condensers is taken out of line and heated to melt out the  crude
acid which is then transferred to storage.  Condenser off gases are
then scrubbed using venturi and packed-bed scrubbers before release
to the atmosphere.  The phthalic anhydride section also has seven sub-
sections consisting of crude storage, decomposing, predistillation,
stripping, refining, refined storage and marlotherm heat transfer oil
system.  A diagram of the refining section is presented in Figure
2-5(b).  Crude phthalic anhydride feed is sent to a series of four
decomposers where some by-products are removed and the acid converted
to phthalic anhydride.  This then goes to predistillation where nonvolatile
by-products are removed.  Light ends are removed in the stripping and
the product polished in the refining step.  Phthalic anhydride  (99.8 percent
pure) is then sent to storage until sold or used in polyester production.^
     Approximately 50 percent of current phthalic anhydride production is
used for plasticizers, 25 percent for al kyd resins, 20 percent for unsatura-
ted polyester resins, and 5 percent for miscellaneous and exports.17
2.3.2  Carbamate  Insecticides
     The second  largest use of naphthalene  is as a raw material for
the manufacture  of carbarmate insecticides, of which carbaryl (Sevin©)
is  the most important.  Carbaryl is used as a substitute for DDT and
other chlorinated compounds that have become environmentally unaccept-
able.   It  is  registered for use on about 70 crops and is used chiefly
in the South  and  West.18  Union Carbide at  Institute, West Virginia,
is  the only domestic  producer of carbaryl. 1
                                  2-13

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ro
i—•
-P.
                                                                    REACTION
                                                                      AND
                                                                   GAS COOLING
                                                                                               SCRUBBING
                                                                                                  AND
                                                                                              INCINERATING
                                                                                          l Am dim
                                             Nlplhilinl (Ulldul  '
                          Figure  2-5(a).   Flow diagram for oxidation  process  in  production of  phthalic anhydride.
                                                                                                                           13

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                                                                                   llol Uiilmhum ON
ro
i
                                                Slum
                                                 I    Innl GII
                                          .....     J_L
                                                 j	x	
                                                   CRUDE
                                                  STORAGE
                                                1       I
                                               Cmidoollll  Vinltd lltlejw
                                          Ciudt Plllhilic ii>h|diillt
                                                            Ciudi Phllulic Anhydlldt
Pilllllh
{jicloi
IllllUll
Slum
Intil Gil i
T 1 '
_K

loilei Ficd WiUi i
C.^undAI, »'l« «»*•'« 1
— - ^ il|
— J
      Rllldu.
     l|Klo< [ihlull
                                                                                      Sciubbll
                                                                                      Iihiuil
                                                                                      Cult
                                                                                                Innl
                                                                                                Gil
                                 Sltira
                                                                                             REFINED
                                                                                             STORAGE
                                                                                              AND
                                                                                             LOADING
                                               (Sludgi)
                                   Figure  2-5(b).   Flow  diagram  for  refining  process  in production  of  phthalic  anhydride.
                                                                                                                                             13

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     Crude or semirefined coal  tar or petroleum naphthalene can be
used for carbaryl  manufacture.   Production involves the following
steps:  (1) hydrogenation of naphthalene to produce 1,2,3,4-tetrahydro-
naphthalene; (2) oxidation of this compound to produce 1-haphthol ; and
(3) reaction of 1-naphthol with methyl  isocyanate to produce 1-naphthyl-
n-methyl carbamate (carbaryl).   Intermediate products of this  process
-- 1,2,3,4-tetrahydronaphthalene and 1-naphthol -- are also used as
insecticides.  Figure 2-6 depicts the production process for carbaryl.
2.3.3  2-Naphthol
     A third major use of naphthalene is for the manufacture of 2-
naphthol (beta-naphthol  or 2-naphthalenol ).  It is an intermediate
primarily used in the manufacture of a variety of dyes or dye  interme-
diates.  Other applications include its use as insecticides; antioxi-
dants for rubber, fats,  and oils; and in the synthesis of fungicides,
Pharmaceuticals, and perfumes.19  American Cyanamid Company in Willow
Island, West Virginia, the only U.S. producer .of 2-naphthol , closed
in 1982.  All 2-naphthol consumed in the U.S. is now imported.9
     The production process uses high quality petroleum naphthalene
as a feedstock, which is reacted with sulfuric acid.  The sodium salt
of the  resulting 2-naphthalenesulfonic acid is treated with sodium
hydroxide.  The product  is then distilled and sub!imed.9.19
2.3.4   Synthetic Tanning Agents
     Synthetic  tanning agents  (syntans) are primarily derivatives of
1- and  2-naphthalenesulfonic acids, their salts, and the sodium
salts of  the  reaction products of the sulfuric acid and formal dehyde.20
Approximately 6 percent  of the U.S. naphthalene supply is consumed in
the manufacture of these  compounds.  Synthetic tanning agents are used
for both  vegetable and chrome  tanned leather.IS  producers of synthetic
tanning agents  and their  locations are listed  in Table 2-4.
2.3.5   Surface  Active Agents (Naphthalenesulfonic acids)
     Surface  active agents (also  known as surfactants) are naphthalene-
sulfonate  compounds consisting primarily of 2-naphthalenesulfonic acid,
its alkyl  derivatives, and their  salts.   Naphthalene  derivatives, how-
ever,  represent a  small  portion  (less than  0.5 percent) of the  total
production  of surface active agents.  The  products  are used as  wetting

                                  2-16

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          Hydrogen

       Naphthalene
ro
                                i
  Tetrdl in
hydrogenation
   unit
   Crude
  naphthol
dehydrogendtton
    unit
1-naphthol
 refining
  unit
                                      Naphthalene
                                                     Naphthalene
Carbaryl
  unit
                                    I =  Pri
         =  Primary naphthalene emission point
                                                                                                        p I
                              Figure 2-6.   Flow diagram for carbaryl production using naphthalene.

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                   Table 2-4.   PRODUCERS OF SYNTHETIC
                           TANNING AGENTS1'18
     Producer                           Location
Morflex, Inc.                           Greensboro,  NC
  (formerly Ciba-Geigy
  Dyes tuff Division)

Diamond Shamrock                        Carlstadt,  NJ
                                        Cedartown,  GA

Georgia Pacific Corp.                   Bellingham,  WA

Rohm and Haas Co.                       Philadelphia, PA
                                  2-18

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agents and dispersants in paints, dyes, pigments, coatings, polymeri-
zation emulsi fiers, and concrete additives, as well  as in a variety
of pesticides  and cleaner formulations.20  The application of naphtha-
lenesulfonate  compounds as surface active agents is  expected to continue
as a low-growth item; however, recent use of these products as
concrete additives (i.e., plasticizers) may alter, this pattern.20
These products, primarily from the sodium and calcium derivatives of
naphthalenesul fonic acid, formaldehyde condensates,  increase the f 1 ow
of concrete without decreasing its strength.
     Naphthalene sufonation leads to a mixture of products.  When the
process is controlled at less than about 100°C, 1-naphthalenesul fonic
acid is predominantly produced.   Sulfonation of naphthalene at above
150°C yields 2-naphthalenesulfonic acid as the main  product.H  At one
time naphthalenesul fonic acid production technology  included only batch
operations but  now emphasizes continuous processes,  removal of excess
sulfonating agent by stripping under vacuum, and the use of chloro-
sulfonic acid  or sulfur trioxide to minimize the need for excess
sulfuric acid.   The improved analytical methods have contributed to the
success of process optimization.
     A schematic diagram of the  main naphthalene sulfonation pathways
is presented in Figure 2-7.
     1-Naphthalenesulfonic acid.  The sulfonation of naphthalene with
excess sulfuric acid at less than 80°C gives some 1-naphthalenesulfonic
acid, while the majority is 2-naphthalenesul fonic acid.H  Older methods,
however, have  been replaced by methods which require less, if any,
excess sulfuric acid.  For example, sulfonation of naphthalene can be
carried out in  tetrachloroethane solution, followed  by separation of
the precipitated 1-naphthal enesulfonic acid; the filtrate can be reused
as the solvent  for the next batch.
     1-naphthalenesul fonic acid  can be converted to  1-naphthalenethiol
by reduction of the related sulfonyl chloride; this  product is used as
a dye intermediate, and is converted by reaction with al kyl isocyanates,
to S-naphthyl-N-alkylthiocarbamates which are used in pesticides  and
herbicides.
     2-Naphthalenesulfonic acid.  The standard manufacture of 2-
naphthalenesulfonic acid involves the batch reaction of naphthalene

                                  2-19

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                                                                      SO,H
                                                              SO3H
                                                              N-l,3,5-tri-SA
                                                                S03H
                                                        SO,H
                                                      N-l,3,5.7-tetra-SA
       Figure 2-7.   Selected  paths to  naphthalenesulfonic  acids

Key:    N   = naphthalene
       SA   = sulfonic acid
       yld = yield
                                                                      11
                                      2-20

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with sulfuric acid at about 160°C for approximately 2 hours.   The
product contains the 1- and 2-isomers in about a 15/85 ratio.H
     Sulfonation can be conducted with a mixture of naphthalene and
sulfuric acid with staged acid addition at 160°C over 2.5 hours to give
a 93 percent yield of the desired product.  Continuous monosulfonation
of naphthalene with sulfuric acid in a cascade reactor at about 160°C
gives 2-naphthalenesulfonic acid and small amounts of by-product naphtha-
lenedisulfonic acids.
     Alkylnaphthalenesulfonic acids and naphthalenesulfonic acid-formal-
dehyde condensates.  The alkylnaphthalenesulfonic acids can be made by
sulfonation of al kylnaphthalenes, e.g., with sulfuric acid at 160°C, or
by alkylation of naphthalenesulfonic acids with alcohols or olefins.H
These products, as the acids or their sodium salts, are commercially
important as textile auxiliaries, surfactants, wetting agents, dispers-
ants, and emulsifying aids, (e.g., for dyes,  wettable powder pesticides,
tars, and clays).  The sodium salts of the condensation products of
naphthalenesulfonic acid with formaldehyde constitute the most important
class of synthetic tanriing agents for hides,  which were discussed in
Section 1.3.4.  The naphthalenesulfonic acid-formaldehyde condensation
products are also used as plasticizers for concrete, as stated earlier.
     Release of naphthalene from the use of surface active agents occurs
indirectly, possibly from their degradation. 18  since 2-naphthalene-
sul fonic acid hydrolyzes to naphthalene in the presence of steam,
naphthalene detected in paint, textile, and ink discharge streams is
most likely a degradation product formed when vats and tanks  are
cleaned by injecting steam.  These industries use both surface active
agents and naphthalene-containing dyes; it is difficult to determine
from which product the naphthalene arises.
     A partial listing of producers of surface active agents  and their
locations is given in Table 2-5.
2.3.6  Moth Repel 1 ant
     Moth repellant accounts for about 4 percent of the U.S.  naphthalene
consumption.  The production of naphthalene-based moth repellant is
decreasing, however, due to the availability of para-dichlorobenzene
and the increased use of synthetic fibers.^  Moth repellant  is the
only consumer product manufactured directly from naphthalene.   The

                                  2-21

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                  Table 2-5.   PRODUCERS OF SURFACE ACTIVE AGENTS
                         FROM NAPHTHALENE DERIVATIVES11'0
Producer
  Location
          Chemical
Al lied Chemical

American Cyanamid


Ciba-Geigy

Morflex, Inc.

DeSoto, Inc.

Diamond Shamrock


DuPont

Emkay Chemical Co,

Georgia Pacific
Claymont, DEa

Linden, NJa
Marietta, OHb

Toms River, NJa

Greensboro, NCa

Fort Worth, TXa

Carlstadt, NJa»c
Cedartown, GAa

Deepwater, NJa

Elizabeth, NJa

Bellingham, WAa
2-naphthalenesulfonic acid

1- and 2-Naphthalenesulfonic acids
2-naphthalenesulfonic acid

1-naphthalenesulfonic acid

1-naphthalenesulfonic acid

1- and 2-Naphthalenesulfonic acids

1-naphthalenesulfonic acid
1-naphthalenesulfonic acid

1- and 2-Naphthalenesulfonic acids

1- and 2-Naphthalenesulfonic acids

1-naphthalenesulfonic acid
Reference 22.

bReference 18.

cReference 23.
                                        2-22

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product is manufactured as a solid flake, powder, or ball,  and  repackaged
for shipment.  All  of the naphthalene contained in moth repel -lant 'is
emitted to the atmosphere.
     There is one U.S.  producer of moth repellant from naphthalene,
Morflex, Inc. (formerly Ciba-Geigy), in Greensboro, NC.^3  Kincaid
Enterprises in Nitro, UV, is believed to be shut down  or no  longer
uses naphthalene in the production of moth repellant.24
2.3.7  Miscellaneous Uses
     Approximately 2 percent of naphthalene consumption is  used in the
manufacture of various  organic chemicals and intermediates.   These
chemicals, some of which are listed below, are produced in  relatively
small amounts and cannot be separately quantified.  Process  descrip-
tions are not available for most of these compounds.  Table  2-6 lists
the miscellaneous chemicals and producers.
     1-naphthol.  1-naphthol (1-naphthalenol,  alpha-naphthol)  is used
as an intermediate in the manufacture of several  agricultural  chemicals,
i.e., Carbaryl (Sevin®), napropamide (Stauffer's Devrinol®),  and 1-
naphthoxyacetic acid).^  In addition, several  drugs are derived from
1-naphthol.  For example, the magnesium salt of 3- (4-methoxy  -1-
naphthoyl) propionic acid (Hepalande®) is used as a choleretic; pro-
pranolol (Inderal®) is  an important adrenergic  blocking agent  used in
the treatment of angina and cardiac arrhythmias; and 1-naphthyl sal icy-
late (Aphol®) has been  used as an antiseptic and antirheumatic.
     1-naphthol is also used in the preparation of dyes and  dye interme-
diates and as an antioxidant for gasoline.  Some of its alkylated deriva-
tives are stabilizers for plastics and rubber.   It is  an intermediate
in the manufacture of synthetic perfumes.25 -
     Union Carbide, the only U.S. producer of  1-naphthol, manufactures
                                  X
the chemical  by the oxidation of 1,2,3,4-tetrahydronaphthalene  (tetralin)
in the presence of a metal catalyst to an intermediate product  which  is
dehydrogenated and aromatized to 1-naphthol.^
     1,2,3,4-tetrahydronaphtha!ene.  This naphthalene  derivative (also
called Tetralin) is used as an insecticide and  as a specialty  solvent.
It is a powerful solvent for oils, resins, waxes, rubber, asphalt, and
aromatic hydrocarbons.   Its high flash point and low vapor  pressure
make it useful in the manufacture of paints, lacquers, and  varnishes;

                                 2-23

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          Table 2-6.  MISCELLANEOUS NAPHTHALENE DERIVATIVES AND PRODUCERS
Chemical
     Producer
   Location
Naphthalenols

   • 1-naphthol
   • Napropamide

1,2,3,4-tetrahydronaphthalene
Decahydronaphthalene

Naphthaleneacetic acids

   • 1-naphthaleneacetic acid


Naphthylamines

   t 1-rraphthylamine
   • Naptalam

1-bromonaphthalene

Alkylnaphthalenes

  •  1-methylnaphthalene
  •  methylnaphthalene


1-naphthaleneacetamide


Chloronaphthalenes"^

  • Dichlone

Nitronaphthalenes

  • 1-nitronaphthalene1
  • 2-nitronaphthalene1

Ni tronaphthalenesul fonic  acids

Aminonaphthalenesulfonic  acids1

Hydroxynaphthalenesul fonic  acids'"

Naphthalenecarboxylic  acids1
Union Carbide3
Stauffer Chemical  Co.1

DuPonta
Union Carbide3

DuPont3

Rorer-Amchem'3

Greenwood Chemical0
Union Carbide0
Sigma Chemical Co.e
Uniroyal , Inc.c

RSA Corp.f
Chemical Exchange9
Koppers Co.S
Crowley Chemicals

Greenwood Chemical Co.c
Union Carbide0

     —d

Uniroyal , IncJ
     ..d
     ..d

Ciba-Geigy Corp.S

     ..d

     ..d

     ..d
Institute, WV
    ..d
Deepwater, NJ
Institute, WV

Deepwater, NJ
Greenwood, VA
Ambler, PA
St. Louis, MO
Gastonia, NC

Ardsley, NY
Houston, TX
Follansbee, WV
Kent, OH

Greenwood, VA
Ambler, PA
    ..d
    ..d

Toms River, NJ

    —d

    __d

    ..d
                                        2-24

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          Table 2-6.   MISCELLANEOUS NAPHTHALENE DERIVATIVES AND PRODUCERS
                                   (concluded)
Chemical
Producer
                                                                Location
Anthraquinone^

Sebacic acid-J
Reference 25.

^Reference 26.

cReference 27.

^Not available.

eReference 23.

fReference 28.

9Reference 29.

"Reference 20.

^Reference 11.

JReference 30.

^Reference 31.

1 Reference 32.
                                        2-25

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for cleaning printing ink from rollers  and type;  in the manufacture of
shoe creams and floor waxes; as a solvent in the  textile industry;  and
for the removal  of naphthalene deposits in gas-distribution systems.33
     Tetrahydronaphthalene is produced  by the catalytic treatment  of
naphthalene with hydrogen.  Nickel  or modified nickel  catalysts  gen-
erally are used commercially; however,  they are sensitive to sulfur,
and only naphthalene that has very  low  sulfur levels  can be used.   Thus,
sodium treatment and catalytic hydrodesulfurization processes  have  been
used to remove the sulfur from naphthalene; the latter treatment is
preferred because of the hazardous  nature of sodium treatment.33
     Decahydronaphthalene.  Decahydronaphthalene  (also called  Decalin)
is used as a solvent for resins and coatings.26  It is produced  commer-
cially by the catalytic hydrogenation of naphthalene  or 1,2,3,4-
tetrahydronaphthalene.   Decahydronaphthalene can  be converted  to
naphthalene by heating  with platinum, palladium,  or nickel  catalyst at
300°C.33
     Naphthaleneacetic acid (naphthylacetic acid).   This naphthalene-
derived chemical is used as a plant growth regulator  to induce rooting
of plant cuttings, as a germination suppressor for potatoes, and an
intermediate for drug manufacture.26,34  i-naphthaleneacetic acid
(NAA®) can be produced by side-chain chlorination of 1-methyl-
naphthalene to 1-chloromethylnaphthalene and formation of naphthalene-
acetonitrile.34  Alternatively, the chemical may  be produced by  the
reaction of naphthalene with chloroacetic acid in the presence of
potassium bromide as a catalyst.32
     Naphthylamines.  Naphthylamines and their derivatives  (e.g.,  1-
naphthylamine) are used in the manufacture of azo dyes, diazo  compo-
nents, and coupling components.H  1-naphthylamine is a dye inter-
mediate and is used as a  raw material in the manufacture of rodenticides,
insecticides, miticides, herbicides, and rubber antioxidants.   1-
naphthylamine can be made from 1-nitronaphthalene by reduction with
iron-dilute HC1 , or by catalytic hydrogenation.  Naptalam (Alanap®), a
herbicide, is a derivative of 1-naphthylamine, prepared by reacting
phthalic anhydride with 1-naphthylamine.32
     2-naphthylamine is recognized as a human carcinogen, producing
bladder cancer  from prolonged exposure.H   Therefore, this chemical is
                                 2-26

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no longer commercially produced or used in the U.S.   It was used at one
time in the production of dyes and rubber antioxidants.
     1-bromonaphthalene.   This is a specialty chemical  used to cali-
brate refractometers.35  It is produced by mixing sodium bromate and
water with naphthalene at room temperature.  It is usually batch pro-
duced (as needed) in relatively small  quantities (50 to 250 kg).
     Alkylnaphthalenes.  Methyl- and dimethylnaphthalenes are contained
in coke-oven tar and in certain petroleum fractions  in significant
amounts.  A methylnaphthalene-rich fraction is usually extracted and
used as solvents for pesticides, sulfur, and various aromatic compounds.
They can  also be used as low freezing, stable heat-transfer fluids.
Mixtures  rich in monoethylnaphthalene content have been_used as dye
carriers  for color  intensification in the dyeing of synthetic fibers.
They also are used  as the feedstock to make naphthalene in dealkylation
processes.  Phthalic anhydride can also be made from methylnaphthalene
mixtures  by an oxidation process that is similar to the one used for
naphthalene.34
     A mixed monomethylnaphthalene-rich material can be produced by
distillation and can be used as feedstock for further  processing.  By
cooling this material to about 0°C, an appreciable amount of 2-
methylnaphthalene crystallizes leaving a mother liquor consisting of
about  equal quantities of 1- and 2-methylnaphthalene.  Pure 2-
methylnaphthalene is used primarily as a raw material  for the produc-
tion of vitamin  K preparations.3^
     •1-methylnaphthalene can  be used as a general solvent because of
its  low melting  point.   It  also is used as a test substance for the
determination of the  cetane number of diesel fuels.   In addition, as
described earlier,  1-methylnaphthalene is used  in the  production of
1-naphthaleneacetic acid,-a pla"nt growth  regulator and an  interme-
diate  for drug manufacture.24
     1-naphthaleneacetamide.   This naphthalene  derivative  is  used as  a
pesticide.  Two  producers of  the compound were  identified,  Greenwood
Chemical  Company, Greenwood,  VA, and Union  Carbide, Ambler, PA.30
However,  no information  on  the chemical,  including process  descriptions,
was  available  in state permit  files.56,37
                                  2-27

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     Chioronaphthalenes.   There are 77 possible chloronaphthalenes,  but
not all  are known or precisely identified materials.31  Some past
commercial uses of this class of compounds have included electrical
insulating materials (mixtures containing tri- to hexachloronaphthalene)
and fungicides, algicides, bactericides, and colorants for plastics
(from mixtures containing octachloronaphthalene).  Technical
octochloronaphthalene has been recommended as an  additive in grinding-
wheel media and cutting-oil  coolants.  Monochloronaphthalene and
mixtures of mono- and dichloronaphthalene have been used or recommended
for chemical-resistant gage  fluids and instrument seals, as heat exchange
fluids, high-boiling specialty solvents, for_color dispersions, as  engine
crank case additives to dissolve sludges and gums, and as ingredients
in motor tuneup compounds.  In addition, monochloronaphthalene has  been
used as a raw material  for dyes and as a wood preservative with fungi-
cidal and insecticidal properties.
     One example of a dichloronaphthalene is dichlone (Phygon®), a
fungicide.32  Dichlone may be manufactured by chlorinating 1,4-
naphthoquinone in a single step in the presence of a catalyst at a
temperature of 80-120°C.  Alternatively, naphthalene may be used as  the
starting material.  The chlorination of naphthalene produces a chlori-
nated tetrahydronaphthalene intermediate, which is hydrolyzed and then
oxidized  by nitric acid to a chlorinated naphthaquinone, which is
further chlorinated to the final product.
     The  trichl oronaphthalenes and higher products have been used as
impregnants for condensers and capacitors as well as dipping compounds
in  electronic and automotive applications; as temporary binders in the
manufacture of ceramic components; in  paper coating and impregnation;
in  precision  ca-sting of alloys; in electroplating stop-off compounds;
as  additives  in gear oils and cutting  compounds; as flame retardants;
as  moisture-proof sealants; and as separators in batteries.
     Chlorinated naphthalenes are currently used only as refractive
index oils and as impregnants  for capaci tors.38  Refractive index oils
are produced  by mixing monochloronaphthalene  with mineral oils to yield
testing oils  with various high  refractive indices.  These refractive
index oils are used  in small  amounts during the  preparation of slides

                                 2-28

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for observation in crime and  petrographic  laboratories.   Chi oronaphtha-
lenes are still  used in some  capacitors,  primarily  for military  appli-
cations.
     Commercial  chloronaphthalenes  are manufactured by the  metal  halide-
catalyzed chlorination of molten  naphthalene  to  the desired chlorination
stage at a temperature slightly above the  melting  point of  the desired
product.31  The hydrogen chloride produced in the  reaction  must  be
treated when used for hydrochloric  acid manufacture due to  the possible
presence of unreacted chlorine and  entrained  or  vaporized organics.
Crude chloronaphthalenes are  treated with  soda ash  or caustic  soda,
fractionated under reduced pressure, and purified  with activated clay.
     Since the 1920's the use of chlorinated  naphthalenes has  declined
steadily.  Domestic production of chloronaphthalenes ceased in  1980.38
Only about 13.6 Mg of these compounds are  imported  and processed
annually, the largest percentage of which  (about 70;percent)  is  for  use
in refractive index oils.  The decline of chloronaphthalenes  in  the
U.S. has been attributed to rising  costs,  competing products,  shifting
markets, and increasingly stringent industrial health and safety regu-
lations.
     Certain manufacturers and importers of 19 chlorinated  naphthalenes
are required under Section 8(a) of the Toxic  Substances Control  Act, 15
U.S.C. 2607(a), to notify EPA of current and  prospective manufacture or
import of the compound.38  The rule requires  current and prospective
manufacturers and importers to notify EPA of  any current or prospective
manufacture or import of chlorinated naphthalenes.   The notice must
state whether a person is manufacturing these compounds, or is
importing or is proposing to  import chloronaphthalenes.  Reporting
requirements include  information on intended  or expected uses,  produc-
tion quantities, chemical composition, and wastes.
     Nitronaphthalenes.  Many of the nitronaphthalene compounds  are  not
formed by direct nitration of naphthalene but are  made by indirect
methods, such as nitrite displacement of diazonium halide groups in  the
presence of a copper  catalyst, decarboxylation of nitronaphthalene-
carboxylic acids, or  decontamination of nitronaphthalene amines.H
     1.  1-nitronaphthalene.   This compound has been used as  a
deblooming agent for  petroleum and oils, for the manufacture of  dyes
                                  2-29

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and i ntennediates, and as a component of commercial  explosives.H
1-nitronaphthalene is important for the manufacture  of 1-naphthylamine.
It  is manufactured by nitrating naphthalene with nitric and sulfuric
acids at 40-50°C.
     2.  2-nitronaphthalene.  This naphthalene derivative is present
in  1-nitronaphthalene (about 3-10 percent by weight).  It is metabolized
to  the carcinogenic 2-naphthylamine in the human body.^  In making
this compound as a by-product, respirators, protective clothing, proper
engineering controls, and medical monitoring programs for workers
should be used.
     Nitronaphthalenesulfonic acids.  These chemicals are primarily
used in the preparation of dye intermediates.  Nitronaphthalenesulfonic
acids are prepared by sulfonization of 1-nitronaphthalene with oleum
at  a low temperature.il
     Aminonaphthalenesulfonic acid's.  Many of these  naphthalene deriva-
tives are used in the manufacture of azo dyes or used to make  interme-
diates for azo acid dyes, direct, and fiber-reactive dyes.^   The
aminonaphthalenesulfonic acids are generally made by either sulfonation
of  naphthylamines, nitration-reduction of naphthalenesulfonic  acids,
amination of naphtholsulfonic acids, or desulfonation of aminonaphthalene
di- or tri-sulfonic acid.
     Hydroxynaphthalenesulfonic acids.  Hydroxynaphthalenesulfonic
acids are important as  intermediates either for coupling components for
azo dyes or azo  components  and for synthetic tanning agents.^  Hydroxy-
naphthalenesulfonic acids can be manufactured either by sulfonation of
naphthols or hydroxynaphthalenesulfonic acids, by acid hydrolysis of
aminonaphthalenesulfonic acids, by fusion of sodium naphthalenepoly-
sulfonates with  sodium  hydroxide, or by desulfonation or rearrangement
of  hydroxynaphthalenesulfonic acids.
     Naphtha!enecarboxylic  acids.  These compounds are generally used
as  intermediates  for azo dyes, pigments, and synthetic tanning.agents.H
The 1- and 2-naphthalenecarboxylic acids are prepared readily  by the
oxidation of 1-  or 2-alkylnaphthalenes with dilute nitric acid, chromic
acid,  or permanganate.   Some  of these acids are useful as herbicides,
plant  growth regulators  and  insecticides.  Tetrahydrozoline  (Visine®,
Tysine®), a nasal decongestant,  is a derivative of these acids.

                                  2-30

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     Anthraquinone.   One new use of naphthalene that could potentially
be produced in significant quantities is the manufacture of anthraqui-
none.20  it -js usecj  as a dyes tuff intermediate and in the wood pulp
industry.   In addition, a by-product of anthraquinone is phthalic
anhydride.   At present, almost all  anthraquinone worldwide is made by
the oxidation of anthracene, an expensive chemical recovered from coal
tar.  The first attempt (joint venture of Bayer and Ciba-Geigy)  to
operate the world's  first naphthalene-based anthraquinone plant  (in
Japan) failed, however, due to clogging of a scaled-up commercial
unit.39  After considering process changes that would have required 3
more years  of study and a costly new investment, the company closed the
plant and planned to use the equipment elsewhere.
     In the process, coal-tar naphthalene is oxidized with air to
naphthoquinone and phthalic anhydride using a vanadium oxide catalyst.20
Without prior separation, the naphthoquinone reacts with butadiene to
form tetrahydroanthroquinone, which is dehydrogenated to anthraquinone.
Subsequent  separation and purification yield the main product,
anthraquinone, and phthalic anhydride as- a by-product.  This
naphthalene-based process is more economical than the conventional
anthracene-based process, reducing production costs by 50 percent
because of lower feedstock costs despite more complex processing and
a  higher investment than the conventional process.20,39
     Sebacic acid.  Another potential market for naphthalene may be
in the production of sebacic acid.  The process uses naphthalene as
a  raw material along with hydroperoxide.30  Decalin hydroperoxide (HPO)
is obtained by autoxidation, and the cleavage reaction of HPO and
subsequent  dehydration reaction results in 5-cyclodecen-l-one.
By reducing and reoxidizing it, sebacic acid is produced.  A Japanese
chemical  company has applied for a patent for this new industrial
process for manufacturing sebacic acid.  Sebacic acid is used in high-
quality plasticizers, engineering plastics, etc.  Other methods  have
been proposed to synthesize sebacic acid from naphthalene, but these
processes have either caused problems in operation and equipment or
have been unable to manufacture sebacic acid on an industrial scale.
                                  2-31

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            3.0  NAPHTHALENE EMISSION SOURCES AND ESTIMATES

     This chapter discussed the types of emission sources that release
naphthalene to the environment and also presents estimates of naphthalene
emissions to the atmosphere.  Section 3.1 describes the general  types
of emission sources (process, fugitive, and storage) of naphthalene.
Section 3.2 discusses naphthalene emissions to the atmosphere from pro-
duction and various end uses; Section 3.3 presents estimates of naphth-
alene discharged to water; and Section 3.4 discusses solid waste impacts
from naphthalene.
3.1  NAPHTHALENE EMISSION SOURCES
     Naphthalene emissions may be released to the environment from
numerous sources.  As discussed in Section 2.2.1.1, naphthalene emis-
sions from coke by-product recovery plants originate primarily from
naphthalene separation and handling in open sumps and naphthalene
melting/drying tanks.  The bulk of naphthalene emissions to the atmos-
phere from production processes is expected from distillation unit
vents, pump seals and flanges, and naphthalene storage tanks.40  For
processes that use a catalyst, catalyst decoking operations can be
expected to release particulates that may contain naphthalene.  In
addition, waste streams resulting from cooling water treatment may
contain  naphthalene.  Spent catalyst and acid-treated clay used in
purification may also contain traces of naphthalene, and these solid
wastes are usually land disposed.
     Little or no information is available on naphthalene emission
sources  from the production of phthalic anhydride, carbamate insecti-
cides, or other naphthalene derivatives.  The major contributor of
phthalic anhydride emissions from the naphthalene-based process is the
reactor  and condenser effluent, which  is vented from the condenser
unit.16  other emision sources of the naphthalene-based phthalic anhy-
dride process  include the control catalyst and product storage in the
liquid phase.  Naphthalene storage emissions are small and are presently
not  controlled.
     In  addition, there are emissions  from "inadvertent" sources such
as combustion  sources, largely due to residential wood and coal heating,
                                  3-1

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and aquatic discharges from cooling water treatment and  various
industries, including wood preserving, paint, ink, and textile.10»41
3.2  AIR IMPACTS
3.2.1  Emissions from Handling and Production of Naphthalene
     Only crude estimates of naphthalene from production sources  are
available from the literature.  According to one source, nationwide
production of naphthalene accounted for approximately 34 Mg annually
(1976 estimate) to the atmosphere, which may be attributed primarily
to distillation unit vents (process emissions), leaks from pump  seals
(fugitive emissions), and flanges.10  Other estimates indicate that 40 Mg
of naphthalene are released annually to the atmosphere (1975 estimate).41
     This section presents estimated atmospheric emissions from  the
handling and production of naphthalene based on limited  data from State
permit files and from January 1985 production capacity estimates  from
Reference 1.  Table 3-1 summarizes process, fugitive, and storage
emissions of naphthalene from coke by-product recovery plants that
handle and/or process crude naphthalene.  Approximately 80 Mg/yr of
naphthalene are emitted to the atmosphere from coke by-product recovery
plants that process crude naphthalene.  Table 3-2 summarizes process,
fugitive, and storage emissions of naphthalene from the five current
U.S. producers of chemical-grade naphthalene.  Naphthalene emissions
from the production of chemical-grade naphthalene are about 50 Mg/yr.
Appendix A, Sections A.2 and A.3, presents the methods and assumptions
used to estimate emissions from coke by-product plants and naphthalene
production  facilities, respectively.  Appendix B includes a memorandum
describing two procedures for estimating naphthalene emissions specifically
from coke by-product plants.  The procedure that was selected is
included in Appendix A.
3.2.2  Emissions from Naphthalene End Uses
     Naphthalene emissions to the atmosphere originate from its  uses in the
manufacture of  phthalic anhydride, carbamate insecticides, synthetic tanning
agents, moth repellant, surface active agents, and miscellaneous organic
chemicals.  In  the manufacture of phthalic anhydride and miscellaneous
organic chemicals, it has been reported that naphthalene may be emitted
to  the atmosphere  from leaks  in column vents,  pump seals, and flanges.42

                                  3-2

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                  TABLE  3-1.   NAPHTHALENE  EMISSIONS  FROM  COKE  BY-PRODUCT
                                      RECOVERY  PLANTS
Plant3
Empire Coke
Republic Steel
National Steel
Interlake
Indiana Gas &
Chemicals
U.S. Steel
Rouge Steel
National Steel
Bethlehem Steel
Chattanooga Coke
& Chemical s
Lone Star Steel
J&L Steel
(TLV Steel)

Location
Holt, AL
Gadsden, AL
Granite City, IL
S. Chicago, IL
Terre Haute, IN
Gary, IN
Dearborne, MI
Detroit, MI
Bethlehem, PA
Chattanooga , TN
Lone Star, TX
Pittsburgh, PA
TOTAL
Emissions
Process
330
1,700
1,000
1,000
330
10,000' '
1,600
2,700
3,300
330
1,000
3,300
26,600
by Type (kg/y
Fugitive
330
1,700
1,000
1,000
330
10,000
1,600
2,700
3,300
330
1,000
3,300
26,600
r)b
Storage
330
1,700
1,000
1,000
330
10,000
1,600
2,700
3,300
330
1,000
3,300
26,600
Plant
Total
(kg/yr)
1,000
5,000
3,000
3,000
1,000
30,000
5,000
8,000
10,000
1,000
3,000
10,000
80,000
Reference 5.

 See Appendix  A, Section A. 2,  for discussion of the method used to estimate emissions
 from handling and/or processing crude naphthalene at coke by-product recovery plants.
                                            3-3

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           Table  3-2.   NAPHTHALENE  EMISSIONS FROM PRODUCTION OF
                       CHEMICAL-GRADE NAPHTHALENE*
Emissions by Type (kg/yr)
Plant Location Process Fugitive Storage
Coal-Tar Naphthalene
Allied Ironton, OH 8,100 580 770
Koppers Co. Follansbee, WV 19,300 580 1,540
Petroleum Naphthalene
Chemical Exchange Baytown, TX 3,300 340 320
Industries
DuPont Chocolate Bayou, TX 9,800 340 930
Texaco Chemical Delaware 'city, DE 6,400 340 610
TOTAL 46,900 .2,180 4,170
Plant -
Total
9,450
21,420
3,960
11,070
7,350
53,200
*S.ee appendix A,  Section A.3,  for discussion  of the method used to estimate
 emissions.
                                   3-4

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     This section presents estimates of process,  fugitive,  and storage
emissions from naphthalene end uses  based on an apportioning  technique
and limited data from State permit files.  A discussion  of  the methods
and assumptions used to calculate these emissions is  presented in
Appendix A, Sections A.4 through A.10.   Table 3-3 summarizes  process,
storage, and fugitive emissions from production of naphthalene end  use
compounds.  Total naphthalene emissions from production  of  these com-
pounds are about 75 Mg/yr.
3.2.3  Naphthalene Emissions from "Inadvertent Sources"
     No estimates are available for  atmospheric naphthalene emissions
from inadvertent sources, such as combustion processes.   One report
indicates, however, that combustion  sources account for  most  of the
annual atmospheric emissions of naphthalene (5,100 Mg),  primarily
attributed to residential wood and coal heating.43  Other inadvertent
sources, such as wood preserving, paint, ink, and textile industries
use naphthalene-containing products (i.e., creosote, dyes,  surface
active agents),  release traces of naphthalene to  waste streams instead
of to the atmosphere.44
3.2.4  Naphthalene Emission Summary
     Total naphthalene emissions  from  all-sources  (i.e., coke by-product
recovery, naphthalene production, naphthalene end uses,  and inadvertent
sources) are  approximately 213 Mg/yr,  This emission summary  is pre-
sented i n Table  3-4.
3.3  WATER  IMPACTS
     Only crude  estimates  of  naphthalene discharges to water  are avail-
able from the  literature.  Annual discharges from naphthalene production
are estimated to be  4.5  Mg, primarily  from  coal  tar production  (extrac-
tion and wash  tank effluents), distillation, and water treatment.10»43>4b
Large amounts  of naphthalene  discharged to  surface waters are expected
to volatize  to  the  atmosphere  and,  to  a  lesser extent, removed  to the
sediment by  adsorption.43
     The only available  estimate  of water  impacts  from naphthalene end
uses is  for  its  use  as carbamate  insecticides, from which 2640  Mg of
naphthalene  is  discharged  (1976  estimate).26  Water impacts  from other
naphthalene  uses are expected  to  be negligible (i.e., less than 1 Mg per
year),  based on EPA  descriptions  of waste  treatment practices and  EPA
                                   3-5

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Table  3-3.  NAPHTHALENE  EMISSIONS FROM  MAJOR USERSC
Naphthalene
End-Use Compound
Phthalic anhydride
Carbamate insecticides
2-naphthol
Synthetic tanning agents
(from l- and i:-napntnaienesul fonic
acids)

Surface active agents
1-naphthalenesulfonic acid
(1-NSA)






2-naphthalenesulfonic acid
(2-NSA)




Plant
Koppers
Union Carbide
American Cyanamid
Morflex, Inc.
Diamond Shamrock
Georgia Pacific
Rohm S Haas
Subtotal Synthetic
American Cyanamid
Ciba-Geigy
OeSoto, Inc.
Diamond Shamrock
Diamond Shamrock
duPont
Emkay Chemicals
Morflex, Inc.
Georgia Pacific
Subtotal 1 - NSA
Allied Chemicals
American Cyanamid
American Cyanamid
OeSoto, Inc.
duPont
Emkay Chemicals
Location
Cicero, IL
Institute, WV
Willow Island, WV
Greensboro, NC
Carlstadt, NJ
Cedartown, GA
Bellingham, WA
Philadelphia, PA
Tanning Agents
Linden, NJ
Toms River, NO
Fort Worth, TX
Carlstadt, NJ
Cedartown, GA
Deepwater, NJ
Elizabeth, NJ
Greensboro, NC
Bellingham, WA

Claymont, DE
Marietta, OH
Linden, NJ
Fort Worth, TX
Deepwater, NJ
Elizabeth, NJ
Emissions
Process
0
1,402
Ob
430
430
430
430
430
2,130
41
41
41
41
41
41
41
41
41
370
350
350
350
350
350
350
by Type
Fugitive
8,470
1,250
0°
430
430
430
430
430
2,130
41
41
41
41
41
41
41
41
41
370
350
350
350
350
350
350
(kg/yr)
Storage
46,300
1,905
Ob
430
430
430
430
430
2,130
41
41
41
41
41
41
41
41
41
370
350
350
350
350
350
350
Plant
Total (kg/yr)
54,770
4,557
0°
1,300
1,300
1,300
1,300
1,300
6,400
120
120
120
120
120
120
120
120
120
1,100
1,050
1,050
1,050
1,050
1,050
1,050
            Subtotal 2 - NSA
2,100    2,100
                                                         2,100
                                                                    6,300
                            3-6

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                     Table  3-3.   NAPHTHALENE  EMISSIONS FROM MAJOR  USERS'
                                              (concluded)
Naphthalene
End-Use Compound
Moth repel 1 ant
Miscellaneous Chemicals
1-naphthol
1 ,2 ,3 ,4-tetrahydronaphthalene
(tetralin)
Qecahydronaphthalene (decalin)
1-naphthaleneacetic acid
1-naphthylamne
Naptalam
1-oromonaphthal ene
1-methylnaphthalene
nethylnaphthalene
1 -napnt ha leneacet amide
Nitronapnthalenesulfonic acids
Plant
Morflex, Inc.
Kincaid Enterprises
Union Carbide
DuPont
Union Carbide
DuPont
Greenwood Chemical
Union Carbide
Sigma Chemical Co.
Uniroyal , Inc.
RSA Corp.
Chemical Exchange
Koppers Co.
Crowley Chemical
Crawl ey Chemical
Greenwood Chemical Co.
Union Carbide
Ciba-Geigy Corp.
Subtotal Miscellaneous
Emissions by Type (kg/yr)
Location Process Fugitive Storage
Greensboro, NC
Nitro, WV
Institute, WV
Deepwater, NJ
Institute, WV
Oeepwater, NJ
Greenwood, VA
Ambler, PA
St. Louis, MO
Gastonia, NC
Ardsley, NY
Houston, TX
Follansbee, WV
Kent, OH
Oklahoma City, OK
Greenwood, VA
Ambler, PA
Toms River, NJ
Chemicals
0"
Oe
50
of
50
09
50
50
50
0.13
50
50
0"
O1
09
50
50
450
Oc
0^
Qe
50
of
50
09
50
50
50
0.13
50
50
O1
09
50
50
450
' Oc
50
of
50
09
50 .
50
50
0.13
50
50
50
50
09
50
50
550
Plant
Total !'
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          TABLE 3-3.  NAPHTHALENE EMISSIONS FROM MAJOR USERS9
                              (concluded)
FOOTNOTES
aSee Appendix A for discussion of procedur-es used to calculate emissions
 from production of each naphthalene end-use compound.

^Z-naphthol is no longer produced in the U.S.  All 2-naphthol consumed
 in the U.S. is now imported (Reference 9).  American Cyanamid closed
 its Willow Island, WV, facility in mid-1982 (Reference 46).  When it
 was in operation, 1981 emissions of naphthalene were reported to be
 about 17 Mg/yr (Reference 47).

cNaphthalene emissions from production and handling of moth repellant
 at Morflex, Greensboro, NC, are included in estimates for general
 production of naphthalene (Table 3-2).  The product is made directly
 from the production of naphthalene at one of the five naphthalene
 producers in Table 3-2 as a solid flake, powder, or ball, and is then
 usually repackaged as a consumer product at another facility (Reference
 17, p. .26).  PES assumes that the Morflex facility only repackages the
 naphthalene product that is already manufactured in a crystallized
 form by one of the naphthalene producers.  Therefore, no emissions of
 naphthalene are expected from the facility.

dBased on information from the West Virginia Air Pollution Control
 Commission that the facility is either no longer in production or does
 not use naphthalene to make moth repel!ant (References 24 and 48), PES
 assumes no emissions of naphthalene from Kincaid Enterprises.

Emissions of naphthalene from 1-naphthol production at Union Carbide,
 Institute, WV, are included in naphthalene emissions from carbaryl
 production (Reference 21):  .process emissions from 1-naphthol produc-
. tion = 0.82 kg/yr; fugitive emissions = 249 kg/yr; and storage emis-
 sions = 17.3 kg/yr.  Total naphthalene emissions from 1-naphthol
 production = 270 kg/yr.

^Emissions of naphthalene from tetralin production (tetralin hydrogena-
 tion and oxidation) at Union Carbide, Institute, WV, are included in
 naphthalene emissions from carbaryl production (Reference 21):  process
 emissions = 1,400 kg/yr; fugitive emissions = 963 kg/yr; and storage
 emissions = 1,844.7 kg/yr.  Total naphthalene emissions from tetralin
 production = 4,207.7 kg/yr, or 4.2 Mg/yr, which represents 92% of
 total emissions from carbaryl production.

9No longer in operation due to explosion and fire destroying facility
 in April 1985; no plans to rebuild (Reference 49).

hStorage emissions only (Reference 50).

^Storage emissions only (Reference 51).
                                  3-8

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            TABLE 3-4.   SUMMARY OF NAPHTHALENE EMISSIONS FROM ALL SOURCES
Emission
Source
Coke by-product recovery
Naphthalene production
Coal tar
Petroleum
Naphthalene end uses
Inadvertent sources*
Total All Sources
Source
Process
26.6

27.4
19.5
6.5
5.1
85.4
Total by Type,
Fugitive
26.6

1.16
1.02
14.8
--
43.0
Mg/yr
Storage
26.6

2.31
1.86
53.4
—
84.2
Source
Total, Mg/yr
79.8

30.8
22.4
74.6
5.1
212.7
NOTE:   Totals may not sum due to rounding.

*Naphthalene emissions from combustion processes, primarily residential wood and
 coal  heating (Reference 43).  For the purposes of this analysis, these emissions
 are classified as process emissions.
                                           3-9

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effluent guidelines.18  Discharges  to POTW's  are  estimated  to  be  about
2 Mg (1976 and 1979 estimates)  from the leather tanning  industry.18,52
Less than 0.1- Mg is directly dicharged from this  industry  (1979 esti-
mate) .18  These  direct dischargers  treat wastewater  streams primarily
by activated sludge or aerated  lagoons.
     Traces of naphthalene contained in creosote,  dyes,  surface active
agents, etc. have also been detected in wastewater streams  from
"inadvertent" sources, such as  the  woodpreserving, paint,  ink, and
textile industries.  Detection  in these waste streams  is most  likely
attributed to the degradation of these compounds.44   Naphthalene  losses
to water from oil spills represents another "inadvertent"  source.   An
estimated 12 Mg  (1976 estimate) of  naphthalene was reported to be
released to the  aquatic environment through crude  oil  spills.53

3.4  SOLID WASTE IMPACTS
     Solid waste from naphthalene production  originates  from spent
catalyst, acid treated clay (from petroleum purification processes),
process sludge,  and onsite wastewater treatment  sludge.40,45  /\n  esti-
mated 32 Mg of naphthalene is generated as solid  waste from production
processes.10
     Solid waste generated from naphthalene end  uses is  estimated to  be
20,240 Mg (1976 estimate).26  Some  solid waste containing  traces  of
naphthalene is expected to originate from process purification activi-
ties.42
     No estimates are available for solid waste  generated  from
"inadvertent" sources of naphthalene.  However,  an estimated 5 Mg (1976
estimate) of naphthalene is reported lost to the  land from crude oil
spills.53
                                    3-10

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              4.0  REGULATIONS AFFECTING THE ENVIRONMENTAL
                         RELEASE OF NAPHTHALENE

     Two environmental  regulations are known to  be in effect specifically
to control  emissions of naphthalene derivatives.   The Toxic Substances
Control  Act specifies certain reporting and recordkeeping requirements
for current and future production or import of chloronaphthalene  com-
pounds.   In addition, emissions of a number of naphthalene derivatives
are regulated under the New Source Performance Standards  (NSPS) for
Equipment leaks of VOC in the Synthetic Organic  Chemical  Manufacturing
Industry (SOCMI).  These environmental  regulations pertaining to  naphth-
alene derivatives are discussed below.  In addition the Occupational
Safety and Health Administration (OSHA) has set  limits for occupational
exposure to naphthalene.  No water criterion has  been established;
however, a Health Advisory is currently being developed.
4.1  TOXIC SUBSTANCES CONTROL ACT
     Section 8(a) of the Toxic Substances Control  Act, 15 U.S.C.  2607(a),
requires certain manufacturers and .importers of  19 chlorinated naphtha-
lenes to notify EPA of current and prospective manufacture or import  of
the compounds.38  These manufacturers and importers are required  to
report to EPA and keep records of information on  intended or expected
uses, production quantities, chemical  composition, and wastes.
4.2  NSPS FOR SOCMI EQUIPMENT LEAKS
     Equipment leaks of certain naphthalene derivatives are regulated
under Subpart VV of the NSPS for Equipment Leaks  of VOC in SOCMI .54
Naphthalene itself'is not regulated by this standard because it is not
a synthetic organic chemical.  Equipment subject  to the standards
include  valves, pumps,  compressors, pressure relief devices, sampling
systems, and open-ended lines in VOC service. The standards require:
(1) a leak detection and repair program for valves in gas/vapor and
light-liquid service and for pumps in light-liquid service; (2) equip-
ment for compressors, sampling systems, and open-ended lines; and
(3) no detectable emissions (500 ppm as determined by Reference Method
21) for  pressure relief devices in gas/vapor service during normal
operation.   Naphthalene derivatives listed in Section 60.489 that are
                                  4-1

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subject to the standards  include  alkylnaphthalene,  anthraquinone,
bromonaphthalane,  chloronaphthalene,  1-  and  2-naphthalenesulfonic  acids,
1-naphthol,  2-naphthol,  phthalic  anhydride,  and  tetrahydronaphthalene.
                                  4-2

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            5.0  AMBIENT AIR MONITORING DATA FOR NAPHTHALENE

     Few ambient air monitoring data for naphthalene are available.  In
one study data were compiled for quarterly naphthalene concentrations
in 13 cities across the United States.55  No annual  estimates are avail-
able.  The highest reported quarterly mean for naphthalene is 12.0
Hig/m3 (2.09 ppb) at Upland, California.
     Other monitoring data show that ambient air concentrations of  •
naphthalene are 3.5 x 10~4 p.g/m3 (6.1 x 10"5 ppb) in an urban area and
5.0 x 10'5 |J.g/m3 (8.7 x 10~6 ppb) in a rural area.43  it was not stated,
however, whether these readings were hourly, daily,  quarterly, or annual
averages.
                                  5-1

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6.0  REFERENCES

1.   1985 Directory  of  Chemical  Producers, United States.  SRI Inter-
     national .   p.  728.

2.   "Chemical  Profile,"  Chemical  Marketing Reporter, October 19, 1984.
     p. 54.

3.   Gerry,  R.T., J. Bakker,  and 0.  Kamatari.  Chemical Economics
     Handbook,  SRI  International.  CEH  Product Review - Naphthalene.
     June 1981, p.  300.7600F.

4.   Kirk-Othmer.  Encyclopedia  of Chemical Technology.  Third
     Edition.   John  Wiley &  Sons.  New  York, NY.  Vol. 15, 1981.
     p. 706-709.

5.   Benzene Emissions  from  Coke By-Product Recovery Plants.  Background
     Information for Proposed  Standards, EPA-450/3-83-016a.  U.S.
     Environmental  Protection  Agency, Office of Air Quality Planning
     and Standards.   Research  Triangle  Park, N.C.  May 1984.  p. 3-31.

6.   Lankford,  W.T., ed.   The  Making, Shaping, and Treating of Steel,
     10th edition.   U.S.  Steel Corporation.  1985.  pp. 242-243.

7.   Van Osdel1, et. al.  Environmental  Assessment of Coke By-product
     Recovery  Plants, EPA-600/2-79-016, Research Triangle Institute,
     Research  Triangle  Park,  NC.  For U.S. Environmental Protection
     Agency, IERL,  Research  Triangle Park, NC.  January 1979.  pp. 40,
     93, 95.

8.   Kirk Othmer, Encyclopedia of  Chemical Technology, Vol. 22, 1983.
     p. 572.

9.   C. Hughes, et.  al.  Chemical  Economics Handbook, SRI Interna-
     tional.  CEH Product Review - Naphthalene.  March 1985, pp.
     300.7600A-300.7600Z.

10.  Production and  Use of Naphthalene.  Versar, Inc., Springfield, VA.
     For U.S.  Environmental  Protection  Agency, Office of Water Planning
     and Standards,  Washington,  D.C. Contract No. 68-01-3852, Task 22,
     Subtask 1.  January  30,  1980.  pp. 7-11.

11.  Reference  4, pp. 720-746.

12.  "Chemical  Profile,"  Chemical  Marketing Reporter, July 7, 1986.
     p. 50.

13.  Letter  with attachments  from  L. Carlson, Koppers Co., Inc.,
     Chicago,  IL, to C. Mata,  Illinois  EPA, Maywood, IL.  July 10,
     1986.

14.  Reference  9, p. 13.
                                  6-1

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REFERENCES (continued)

15.  Synthetic Organic  Chemical  Manufacturing  Industry:  Inputs and
     Product  Uses.   Research  Triangle  Institute.  For U.S. Environ-
     mental  Protection  Agency,  Strategies and  Air Standards Division,
     Research Triangle  Park,  NC.   EPA  Contract No. 68-02-3071.
     February 1980.

16.  Year End Report -  Synthetic  Organic Chemical Manufacturing Indus-
     try Study.  U.S. Environmental  Protection Agency, Office of Air
     Quality  Planning and  Standards, Chemical  and Petroleum Branch.
     December 1977.   p. 158.

17.  Compilation of  Air Pollutant  Emission Factors - Volume 1:  Sta-
     tionary  Point and  Area Sources.   Chapter  5, Chemical Process
     Industry.  Section 5.12.   AP-42.  Fourth  Edition.  U.S. Environ-
     mental  Protection  Agency,  Office  of Air Quality Planning and
     Standards, Research Triangle  Park, NC.  September 1985.  p. 5.12-1
     through  5.12-4.

18.  Polycyclic Aromatic Hydrocarbons  - An Environmental Materials
     Balance.  Acurex Corporation, Rosslyn, VA.  For U.S. Environ-
     mental  Protection  Agency,  Monitoring and  Data Support Division,
     Washington, D.C.  EPA Contract  No. 68-01-6017.  January 1981.
     pp. 41-50.

19.  Reference 9, pp. 15-16.

20.  Reference 4, p. 715.

21.  1984 Emission  Inventory  Summary by Process, Union Carbide,
     Institute, WV.   West  Virginia Air Pollution Control Commission,
     Charleston, WV.

22.  Reference 1, pp. 728  and 900.

23.  Chem Sources,  USA, 1985.

24.  Telecon.  C. Beard, West Virginia Air Pollution Control Commission,
     with D.  Cole,  PES, Inc.  September 22, 1986.

25.  Reference 1, p. 729.

26.  Reference 9, p. 17.

27.  Reference 1, p. 766.

28.  Reference 1, p. 457.

29.  Reference 1, p. 720.

30.  "New Process for Sebacic Acid," Hydrocarbon Processing, October
     1985.  p. 83.
                                  6-2

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REFERENCES (continued)

31.  Kirk-Othmer.   Encyclopedia  of  Chemical Technology.  Third Edition.
     John Wiley &  Sons.   New  York,  NY.   Vol. 5, 1979. pp. 838-843..

32.  Pesticide Manufacturing  and  Toxic Materials Control Encyclopedia.
     Marshall  Sittig, editor.  Noyes Data Corporation, Park Ridge, NJ .
     1980. pp. 277-279,  550-554.

33.  Reference 4,  p.  704.

34.  Reference 4,  p.  716.

35.  Telecon.   T.  McGillick,  New  York State Department of Environ-
     mental  Conservation,  White  Plains,  NY, with D. Cole, Pacific
     Environmental  Services,  Inc.,  Durham, NC.  August 26, 1986.

36.  Letter from D.L. Lesher,  Pennsylvania Bureau of Air Quality Control,
     Harrisburg, PA,  to  D.G.  Cole,  Pacific Environmental Services,
     Inc., Durham,  NC.   August 15,  1986.

37.  Letter from K. Chaudhari,.Virginia  State Air Pollution Control
     Board, Richmond, VA,  to  D.G. Cole,  Pacific Environmental Services,
     Inc., Durham,  NC.   August 20,  1986.

38.  49 FR 33649,  August 24,  1984.  Final Rule.

39.  "A Naphthalene-based  Process Bites  the Dust," Chemical Week.
     September 26,  1984.  p.  41.

40.  U.S. Environmental  Protection  Agency.  Industrial Process Profiles
     for Environmental Use:   Chapter 5.  Basic Petrochemicals Industry.
     January 1977.  pp.  98-101.

41.  Reference 17,  pp. 35-36.

42.  Reference 9,  p.  18.

43.  An Exposure and  Risk  Assessment for Benzo[a]pyrene and Other
     Polycyclic Aromatic Hydrocarbons.   Volume 1.  Summary.  Final
     Draft Report.  EPA  Contract  No. 68-01-6160.  U.S. Environmental
     Protection Agency,  Monitoring  and Data Support Division, Office  of
     Water Regulations and Standards, Washington, D.C.  July 1982.
     p. 2-20,  2-21.

44.  Reference 17,  p. 36.

45.  Reference 17,  p. 35.

46.  Letter from J.L. Noe, American Cyanamid, Willow Island, WV, to  C.
     Beard,  West Virginia  Air  Pollution  Control Commission, Charleston,
     WV.  September 9, 1985.
                                 6-3

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REFERENCES (concluded)

47.  West Virginia Air  Pollution  Control Commission, 1981 Air Emission
     Inventory Summary  by  Process.

48.  West Virginia Air  Pollution  Control Commission  (WVAPCC), Permit
     Files,  Charleston,  WV.   Information obtained from visit to WVAPCC
     office  by K. Meardon,  PES,  Inc., Durham, NC.  October 1-2, 1986.

49.  Letter  from K. Chaudhari, Virginia Air Pollution Control Board,
     Richmond, VA, to D.G.  Cole,  PES, Inc., Durham,  NC.  August 20, 1986,

50.  Telecon.   L. Malcolm,  Ohio  State Air Pollution  Control Agency,
     Akron,  OH, with D.G.  Cole,  Pacific Environmental Services, Inc.,
     Durham, NC.  August 7,  1986.

51.  Telecon.   C. Goeller,  Oklahoma  City Health Department, Oklahoma
     City, OK, with D.G. Cole, PES,  Inc., Durham, NC.  August 7, 1986.

52.  Reference 9, p. 5.

53.  Reference 9, pp. 31-32.

54.  48 FR 48328, October  18,  1983.  Final Rule.

55.  W.F. Hunt, R.B. Faora,  and  G.M. Duggan, Compilation of Air Toxics
     and Trace Metal Summary Statistics.  U.S. Environmental Protection
     Agency, Office of  Air Quality Planning and Standards.  Research
     Triangle Park, NC.  EPA-450/4-84-015.  July  1984. pp. 7, 112.
                                  6-4

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                               APPENDIX  A

           DOCUMENTATION FOR HUMAN EXPOSURE MODEL INPUT DATA
A.I  INTRODUCTION

     This appendix documents the Human Exposure Model  (HEM)  input
parameters for naphthalene.  For each naphthalene source category,
these parameters include:

     SIC code
     plant name
     latitude and longitude
     stack release height (meters)
     cross-sectional downwash area (meters2)
     gas exit velocity (meters/second)
     vent type/diameter (meters)
     gas temperature (degrees, Kelvin scale)
     emission rate (kilograms/year

The sections below cite the references or provide the basis  for the
modeling parameters and describe the methods used to calculate naphthalene
emissions from a given source category (i.e., naphthalene production or
end use).  The source categories are included in the following sections:

     A.2  Naphthalene from Coke By-product Recovery Plants
     A.3  Naphthalene Production
     A.4  Phthal.ic Anhydride End Use
     A.5  Carbamate Insecticides End Use
     A.6  2-naphthol End Use
     A.7  Synthetic Tanning Agents End Use
     A.8  Surface Active Agents End Use
     A.9  Moth Repellant End Use
     A.10 Miscellaneous Organic Chemicals End Use

Tables A-l through A-10 present the modeling parameters described in
this appendix.

A.2  NAPHTHALENE  FROM COKE  BY-PRODUCT RECOVERY PLANTS

A.  SIC  Code

     Reference  1.

R.  Plant Name

     Reference  15, Table 3-3 (revised since  proposal),  is the basis for
the list of coke  by-product recovery plants, which include only
facilities that produce coal tar  naphthalene.

C.  Latitude/Longitude

     Reference  15, Table E-l (revised since  proposal).'
                                  A-l

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D.  Urban

     All  plants are located >n urban areas for modeling purposes.

E.  City, State

     Locations of coke by-product recovery plants from Reference 15,
Table 3-3 (revised since proposal).

F.  Emission Type

     Process (P), storage (S), and fugitive (F) emission points were
based on information in References 15 and 16.   Process emissions are
considered to be emitted from a stack or vent.  Most naphthalene
emissions from coke by-product recovery plants originate from naphtha-
lene processing, specifically separation and drying, which usually
occur in partially open, but vented, tanks; therefore, some emission
points may be both fugitive and process emission sources.  Storage
emissions of naphthalene originate from naphthalene storage tanks and
some coal tar storage tanks (containing a mixture of coal tar and
naphthalene).

G.  Stack Number

     Corresponds to an emission point, either process, fugitive, or
storage.  When stack parameters for different emission points are
identical, they are assigned one number and emissions from these
points are combined.

H.  Stack Parameters

     Reference 15, Table E-2.  Stack parameters for the naphthalene
drying tank were selected for modeling purposes.  Storage tank release
height is based on height of tar storage tank  (containing naphthalene)
also from Table E-2.  For cross-sectional downwash area  (fugitive
"emission points) areas of 200m x 100m for large plants (coke capacity
greater than 1 million Mg/yr), 100m x lOQm for middlesized plants (coke
capacity between 500,000 Mg/yr and  1 million Hg/yr), and 75m x 65m  for
smaller plants (coke capacity less  than 500,000 Mg/yr) are used.

I.   Emissions

     A plant-wide  naphthalene emission factor  is developed for naphthalene-
handling coke  by-product recovery plants.  This  factor  is based  on  a
material balance of a representative coke by-product  recovery  plant  and
the amount of  naphthalene estimated in coal tar  production.  -A naphthalene
emission factor is needed on  a "kilogram  (kg)  of naphthalene per megagram
(Mg) of coke  produced" basis  because coke production  rates are available
for each coke  by-product plant.  To derive this  factor,  the  following
procedure is  used.

1.   Estimate  annual coal tar production  based  on  (1) the amount of
     naphthalene  in coal tar  produced  (1978 estimate) and  (2)  the weight
     percent  of naphthalene  in dry  coal tar:
                                   A-2

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     1978 coal-tar npahthalene production           = 230,000 Mg
                                                      (Reference 10, pp. 27-28)
     Average Weight % naphthalene of dry tar (U.S.) = 8.80%
                                                      (Reference 11, p. 572).

     Coal,Tar Production = 230,000 Mg  =  2.6 Tg
                             0.088

2.   Estimate relative amount of coal tar produced per megagram of coke
     from material balance of a representative coke by-product recovery
     plant:

     380 Mg  Coal  Tar  =  0.052 Mg Coal  Tar per Mg Coke (Reference 16,
       7370  Mg Coke      p. 23)

3.   Estimate annual  coke production based on steps (1)  andf (2) above:

          2.6 Tg coal tar	     = 50 Tg coke production, U.S.
     0.052 Mg coal tar/Mg coke        (1978 estimate)

     Note:   This estimate approximates 1979 U.S. coke production figure
            (48.0 Tg) from Reference 41.

4.   Calculate naphthalene emission factor from estimate of total
     naphthalene emissions to atmosphere from coal tar production
     (Reference 10) and total U.S. coke production from step (3) above:

       300 Mg naphthalene   =  6 Mg naphthalene per Tg coke produced,
      50 Tg  coke produced      or 0.006 kg naphthalene per Mg coke produced.

     A plant-specific emission total was calculated using the above
method.  The total was divided by three to allocate emissions to process,
fugitive, and storage vents.

A.3  NAPHTHALENE PRODUCTION

A.  SIC Code

     Reference 1.

B.  Plant Name

     Plants  1-5 from References 2, 3, 4 represent U.S. producers of
naphthalene  from both coal tar and petroleum.

     Plants  6-9 are on standby or not operating due to market conditions
based on information from References 2, 3, and 4.  Therefore, plants
6-9 are not  modeled.

C.  Latitude/Longitude

     Plant 1    - Reference 5.
     Plants  2,3 - Reference 6.
     Plant 4    - Reference 7.
     Plant 5    - Reference 8.


                                  A-3

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D.  Urban

     This information is  not available from State Permit files or other
available sources.   All  plants are assumed to be located in urban
areas.

E.  City, State

     Location of plant numbers 1-9 from References 2, 3, 4.

F.  Emission Type

     Process (P), storage (S), and fugitive (F)  emission points were
based on information in Reference 9.

G.  Stack Number

     Corresponds to an emission point, either process (P), fugitive (F),
or storage (S).  When stack parameters for different emission points
are identical within a given type, they are assigned one number, and
emissions from those points are combined.  	

H.  Stack Release Height

     A stack release height of 13m from all  process stacks at naphthalene
production facilities was used based  on average  of stack heights from
Reference 9.  Other assigned values are as follows:

     Plant 1  -  Release  height of 3m for  fugitives; release height of
                 7.6m for each of 5 storage tanks (estimated average
                 of heights of 7 tanks from Reference 9).

     Plant 2  -  Three meters for fugitives; 2 storage tanks both
                 having a height of 7.6m (based  on average height of
                 storage  tanks, Reference  9).

     Plant 3  -  Three meters for fugitives; release height of 7.6m for
                 6 storage tanks (based on Reference 9).

     Plant 4  -  Three meters for fugitive releases; storage release
                 height based on 7.6m from storage tank height (Refer-
                 ence 9).

     Plant 5 -   Three meters for fugitives.  Three storage tanks, all
                 having a height of 7.6m (based  on Reference 9).

I.  Cross-Sectional Oownwash Area

     For fugitive emissions, a cross-sectional downwash area of 20,000m2
was used for all naphthalene production facilities, based on model input
parameters for xylene reported in Reference 40.
                                  A-4

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            J.   Vent  Type

                 Vertical  (0)  for  process  and  storage  emission  points,  and  nonvertical
            (1)  for  fugitive  emissions  are assumed.

            K.   Vent  .Diameter

                 For  process  emissions,  Reference  9  (average  of stack diameter).

                 For  storage  emissions,  unless  assigned  plant-specific  infor-
            mation was  available,  a  storage tank  is  assigned  a  diameter of
            0.076m,  based  on  vent  diameters of  0.17  ft,  0.25  ft,  and 0.33  ft.
            reported  in Reference  40, Table 29-20, for xylene vent  parameters.

            L.   Gas  Exit Velocity

                 No  plant-specific information  was available.  Therefore,  PES  used
            an  estimate of 6.3 m/s from  Reference  9  is used as  a  representative  exit
            velocity  for process stacks  at naphthalene production facilities,  and
            0.01 m/sec  for fugitive  and  storage emission points.

            M.   Gas  Temperature

                 An  estimate  of 320°K from Reference 9 is selected  as a representa-
            tive exit gas  temperature for  process  stacks at naphthalene production
            facilities, and 293°K  (ambient) for fugitive and  storage emission
            points.

            N.   Emissions

            Plant 1  - Allied  Chemical,  Ironton, OH.

                 No  plant-specific information  was available  to calculate
            naphthalene emissions  (Reference 12).

                 Naphthalene  Distillation  Process  -  Process,  fugitive,  and  storage
            emissions are  based on plant-specific  information from  the  Koppers
            facility  in Follansbee,  WV  (Reference  9).  Since  no process description
            was available  for Allied, the  process  is assumed  to be  identical  to  the
            one at  Koppers.  Like  Koppers, the  facility  uses  coal  tar as a  raw
            material.

                 a.   Process  Emissions

                      A naphthalene  emission factor  for  process emissions  was
            derived  from the  polycyclic  organic matter (POM)  emissions  reported  in
            the 1984  Emissions Inventory submitted by  Koppers Co.,  Follansbee, WV
            (Reference 9).  The factor  is  expressed  in terms  of kilograms  of
            naphthalene per megagram of  naphthalene  produced.  Based on 20.6  ton
            POM/yr  and  based  on an estimate from  Reference 10 that  87%  of  POM
            emissions from naphthalene  production  are  assumed to  be naphthalene,
            the following  emission factor  for  process  emissions is  calculated:

            ton_   2,000 Ib   0.454 k£          1          0.239  kg naphtha!ene/Mg  produced
0.87 x 20.6 yr   x   ton    x        Ib x  68 x 10-5  Mg/yr =


                                              A-5

-------
Using this emission factor, process emissions of naphthalene from the
Allied facility with production rate of 34,000 Mg (Reference 13) are
calculated as:
             0.239   J<£ x 34,000 Mg_ = 8,100 kg/yr
                J<£
                Mg

b.   Fugitive Emissions
                                 yr
          No information was available on the number of components
containing or contacting naphthalene at the Allied facility.

          Therefore, fugitive emissions at Allied are estimated to be
580 kg/yr as reported for the fugitive emissions .from naphthalene dis-
tillation and desulfurization at the koppers facility (Reference 9).

     c.  Storage Emissions

          Storage emissions of naphthalene from the Allied facility were
based on storage emissions from the Koppers, Follansbee, WV, facility
(Reference 9), and the 1985 production capacity for the Allied facility
from Reference 13.  Storage emissions factor is calculated as follows:
                     1,545 kg
                    68,000 Mg
                           0.0227 k£
                                  Mg
          Therefore, storage emissions from the Allied facility are:

             0.0227 kg          Mg       kg
                    ftg X 34,000 yf = 770 yf

Therefore, total  emissions from the Allied facility are 9,450 kg/yr,
or 9.4 Mg/yr.  As a basis of comparison, nationwide estimates of naphtha-
lene emissions from production (Reference 14) can be apportioned among
the five naphthalene producers.  Reference 14 reports that from 0.0004
to 0.07% of the annual U.S. production of naphthalene is lost from the
plant during its  manufacture, and that 48% of these emissions are
released to the atmosphere.  Using a conservative estimate of 0.0336%
(0.0007 x 0.48) as the percentage of naphthalene production emitted
and the total naphthalene production of 184,000 Mg/yr (Reference 4),
naphthalene emissions to the atmosphere can be calculated as:

                 0.000336 x 184,000 Mg/yr = 61.8 Mg/yr.

Apportioning this total  among the five naphthalene producers based on
production rate,  naphthalene emissions are the following:
                                  A-6

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          Plant 1  -  Allied              11.4 Mg
          Plant 2  -  Chemical  Exchange    4.7 Mg
          Plant 3  -  DuPont              13.8 Mg
          Plant 4  -  Koppers             22.8 Mg
          Plant 5  -  Texaco Chemical       9.1 Mg

                      Total                61.8 Mg

Plant 2 - Chemical  Exchange Industries, Baytbwn, TX.

     No plant-specific information was available from State permit
files from which to calculate naphthalene emissions (Reference 6).

     This plant uses a petroleum-based feedstock (e.g., heavy refor-
mate) in the production of naphthalene.  In a comparison of coal
tar and petroleum-based processes, certain steps are similar, such as
distillation and fractionation.  In addition, some petroleum naphthalene
producers may also process coal-derived material (Reference 33, p. 25).
Although admittedly there are differences in naphthalene contents between
coal tar and petroleum, no information is available on the relative
percentage of naphthalene in petroleum streams or the percentage of
naphthalene emissions of total  polycyclic organic matter.  Therefore, the
only basis for estimating emissions from a petroleum-based naphthalene
process is the estimating procedure used above to estimate coal tar-based
naphthalene emissions.

     a.  Process Emissions

          A naphthalene emission factor (0.24 kg naphthalene/Mg napth-
alene produced) derived from the Koppers- facility, Follansbee, WV
(Reference 9) was used to estimate'process emissions from the Chemical
Exchange faci.lity.  The same procedure was followed as in Plant 1,
assuming 87% of POM emissions are naphthalene (based on Reference 10);
and based on a production rate of 14,000 Mg/yr for the Chemical Exchange
facility.

          Process emissions of naphthalene are calculated as:

                0.239 kg/Mg x 14,000 Mg/yr = 3,300 kg/yr.

     b.  Fugitive Emissions

          No information was available on the number of components
containing or contacting naphthalene at the Chemical Exchange Facility.
Since there is no desul furization section in the petroleum-based process,
only the distillation process information from the Koppers facility
(Reference 9) is used.

         Fugitive emissions af heavy liquid coal tar distillate = 1.26 Ib/hr
         (Reference 9)

         Weight of naphthalene in dry coat tar, (Reference 11)  = 8.8%

         Hours of Operation per year, (Reference 44)            = 6,745
                                   A-7

-------
0.088 x 1.26 Ib/hr x 6,745 x 0.454 k£ = 340 k£
                                   lb       yr
     c.  Storage Emissions

         -Same procedure as Plant 1, Storage Emissions.

          Storage emissions from the Chemical Exchange facility are:

                         0.0227 kg   14,000 Mg
                                MJJ- x        yf = 320 kg/yr.

          Total  naphthalene emissions from Chemical Exchange Industries
are 3,960 kg/yr, or 4.0 Mg, which compares favorably with the emissions
estimate of 4.7 Mg based on the apportioning technique described above.

Plant 3 - E.I. DuPont de Nemours, Chocolate Bayou, TX.

     No plant-specific information was available from State permit
files from which to calculate naphthalene emissions (Reference 6).

     The plant uses a petroleum-based feedstock in the production of
naphthalene.  The same basis that was used to calculate emissions from
the other facilities was used here, based on plant-specific information
from Reference 9.

     a.  Process Emissions

          Same procedure as Plant 1, Process Emissions.

          Process emissions from the DuPont facility are calculated as:

                          0.239 kg   41,000 Mg
                                ^ x        — = 9,800 Kg/yr

     b.  Fugitive Emissions

          Same procedure as Plant 2, Fugitive Emissions.

          Fugitive  emissions from the  OuPont facility are  calculated as:

                          0.0084 k£    41,000 M£       k£
                                 Mg  x        yr =  34° yr

     c.  Storage  Emissions

          Same procedure  as Plant 1, Storage Emissions.

          Storage emissions from the OuPont  facility  are calculated as:

                           0.0227  kg    41,000 Mg       kg
                                  Mj x        y* =  930 J^

                                    A-8

-------
          Naphthalene emissions from the DuPont facility total  11,070
kg/yr, or 11.1 Mg/yr.  This approximates the estimate of 13.8 Mg/yr from
the apportioning technique described above.

Plant 4 - Koppers, Follansbee, WV.

1.  Process #230 (Naphthalene Distillation)

     a.  Process Emissions

          20.6 tpy POM emitted from distillation process (Reference 9).

          87 percent of POM emissions from naphthalene production
assumed to be naphthalene (Reference 10, p.  27), based on an estimate
that 87% of POM emissions to air is naphthalene in coal  tar production.

                      ton   2,000 Ib    0.454 kg          kg
          0.87 x 20.6 -yf x       tfon" *       Tb = 16,200 yp

     b.  Fugitive Emissions

     Fugitive emissions of heavy liquid coal tar distillate = 1.26 Ib/hr,
       Reference 9.

     Ueight percent naphthalene in dry coal  tar,            = 8.8%
        Reference 11.

     Hours of operation per year (1984), Reference 9.       = 7,490

                   1.26 Ib   7,490 hr   0.454 kg       kg
           0.088 x      "hf x       yf x       J£ = 380 yr

     c.  Storage Emissions

          2 naphthalene oil storage tanks for naphthalene distillation
process  (each 60-65% naphthalene Reference  11); the 65% value is used for
calculations.  Tank 1 corresponds to S-l at Koppers in Table A-2 of this
appendix, and tank 2 corresponds to S-2 at  Koppers.

          Tank 1 (S-l) =     Ib      0.454  kg
                         547 yf    x       Tb x 0.65 = 160 kg/yr

          Tank 2 (S-2) =     Ib      0.454  kg
                         590 yf    x       Tb x 0.65 = 170 kg/yr

                                               Total = 330 kg/yr

                                  A-9

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2.  Process 300 - Naphthalene Oesulfurization

     a.   Process Emissions

     Based on (1) POM emissions from naphthalene desulfurization process
     of  3.9 ton/yr (Reference 9)  and (2)  87% of POM is naphthalene
     (Reference 10), naphthalene process  emissions are calculated as:

                ton   2,000 Ib    0.454 kg
     0.87 x 3.9 ~y7 x       ton" x      Tb    = 3,100 kg/yr

     b.   Fugitive Emissions

     Based on:

     (1) Fugitive emissions of total heavy liquid  =  0.77 J_b_ (Refer-
         ence 9);                                          hr

     (2) Weight % of naphthalene in dry coal tar   = 8.8% (Reference 11); and

     (3) Hours of operation per year (1984)        = 6,336 (Reference 9);

      naphthalene fugitive emissions are calculated as:

            0.77 1-b   6,336 hr   0.454 kg
    0.088 x      Tfp x       7F x       Tb      = 20° k9/yr

     c.   Storage Emissions

     5 naphthalene storage tanks for naphthalene desulfurization  process
    (Reference  9):

           Tank    H(m)    D(m)    	Emissions	

           1  (S3)  10.9    6.1     575 Ib    0.454 kg
                                     7F x       Tb"=    261 k9/yp

           2  (S4)   9.1    7.6     610 Ib    0.454 kg
                                     yf x       TF =    277 kg/yr

           3  (S5)*   6.1    7.3     393 jb_    0.454 k£
                                     yr x        15 =    178

           4  (S5)*   6.1    7.3     393 jb_    0.454 kg, _
                                     V P          ID""    J./O

           5  (S6)* 12.8   13.7     697 ]b_    0.454  k£
                                     yr x        Ib =    2L6—

                                              Total =  1,210 kg/yr

                                     A-10

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*Note:  Tanks 3 and 4 are modeled as one tank since parameters are
        identical, and emissions for the two tanks are combined.

     Total  naphthalene emissions from the Koppers plant are 21,420 kg/yr,
or 21.4 Mg/yr, which closely approximates the estimate (22.8 Mg) based
on a nationwide apportioning technique discussed in Plant 1 emissions
documentation above.

Plant 5 - Texaco Chemical, Delaware City, DE.

     No plant-specific information was available from State permit
files from which-to calculate naphthalene emissions (Reference 8).

     The plant uses a petroleum-based feedstock in the production of
naphthalene.  The same procedure as used in other facilities was used
to calculate naphthalene emissions from Texaco Chemical, based on
plant-specific information from Reference 9.

     a.  Process Emissions

          Same procedure as Plant 1, Process Emissions.

          Process emissions from the Texaco Chemical facility are
calculated as:

                    0.239 kg_   27,000 Mg_ _ 6,400 k_g
                          Mg x        yp =       yr

     b.  Fugitive Emissions

          Same procedure as Plant 2, Fugitive Emissions.

     c.  Storage Emissions

          Same procedure as Plant 1, Storage Emissions.

          Storage emissions from the Texaco Chemical facility are
calculated as:

                 0.0227  kg_   27,OOOMg   610 l<£
                         Mg x        yr =     yr

          Naphthalene emissions  from the Texaco Chemical facility
total 7,350  kg/yr,  or 7.3 Mg/yr, compared to 9.1 Mg/yr using the appor-
tioning technique based  on Reference 14.

          Total emissions of naphthalene from production at the ahove
five  facilities are 53.2 Mg.

A.4   PHTHALIC  ANHYDRIDE  END-USE

A.   SIC Code

      Reference 1.
                                 A-ll

-------
B.  Plant Name

     References 18 and 19.  Plant restarted.during May 1985 after
modification to use naphthalene as a feedstock as well as orthoxylene.

C.  Latitude/Longitude

     Derived from zip code conversion to DIM coordinates using computer

program from Office of Toxic Substances.

D.  Urban

     The location of the facility is assumed to be in an urban area.
E.  City, State

     Location of facility from Reference 19.

F.  Emission Type

     Reported as process (P), fugitive (F), or storage (S) based on
information in References 17-19.

G.  Stack Number

     Corresponds to an emission point, either process, fugitive, or
storage.  When stack parameters for different emission points are
identical, they are assigned one number, and emissions from these
points are combined.

H.   Stack Release Height

     A height of 3 m is selected for fugitive emissions; release height
for storage emissions is based on storage tank height from Reference 20.

I.  Cross-Sectional Oownwash Area

     For -fugitive emission points, 100 m x 200 m is selected from
(Reference 40).

J.  Vent Type

     Vertical (0) for storage emission points and nonvertical (0) for
fugitive emissions are chosen.

K.  Vent Diameter

     Process emissions - Reference 20, p. 15.

     Storage emissions type:  same as documentation for naphthalene
production, Section A.3, subsection K.
                                  A-12

-------
L.  Gas Exit Velocity

     A gas exit velocity of 0.01 m/sec for fugitive and storage emission
points is used.

M.  Gas Temperature

     An ambient temperature of 68°F, or 293°K is chosen.

N.  Emissions

Plant 1 - Koppers Co., Bridgeville, PA - not operating.

Plant 2 - Monsanto Co., Bridgeport, NJ - not operating.

Plant 3 - Koppers Co., Stickney, IL - restarted May 1985 (Reference 19).

     The facility uses either orthoxylene or naphthalene as feedstock
for production of phthalic anhydride.  The bulk of total emissions
originate from the catalytic oxidation reactor (Reference 17).   Emis-
sions from other equipment (e.g., switch condensers, distillation
columns, and heat treaters) are negligible.

     a.  Process Emissions from Phthalic Anhydride Formation Process

          One-hundred percent of naphthalene used in the manufacture of
phthalic anhydride is converted to phthalic  anhydride in the reactor.
Therefore, 0 process emissions of naphthalene are assumed (Reference
10, p. 41).  This is supported by raw material  and product informa-
tion from Reference 20, p. 9-10, which states that 4,386 Ib/hr  naphtha-
lene is raw material fed to process and 4,386 Ib/yr is production rate
for crude phthalic anhydride vapor from naphthalene, indicating that
all naphthalene as raw material  is used in the process.

     b.  Fugitive Emissions

          VOC emission factors from Reference 24 for equipment  leaks
from synthetic organic chemical  manufacturing plants (SOCMI) are used.
All VOC is assumed naphthalene to estimate conservatively.

          Number of pumps, valves, and other equipment per process unit
is based on SOCMI process unit counts in Reference 24.  Only equipment
in heavy liquid or gas vapor service is included since naphthalene is
considered a heavy liquid on the basis of its Reid vapor pressure
(0.007 kPa at 20°C).

          Equipment component counts and emission factors for an aver-
age SOCMI unit are used to estimate emissions (Reference 24, pp. 1-4,
3-2, 3-6) as follows:
                                  A-13

-------
   Equipment
   Component
Component
  Count
  Average SOCMI
Emission Factor
(kg/hr/source)
                           Opera-
                        ting hrs
                        per year3
 VOC Emis-
sions'^
(kg/yr)
Heavy Liquid Pumps
          0.0214
                   8,232
                                           881
Heavy Liquid Valves

Heavy Liquid Safety/
  Relief Valves

Heavy Liquid Open-
84
   0.00023         8,232
         Not avilable     8,232
                                           160
ended Valves A Lines
Compressor Seals
Sampling Connections
Flanges

48
1
12C
500

0.0017
0.228
0.0150
0.00083
TOTAL
8,232
8,232
8,232 -
8,232

670
1,880
- 1,480
3,400
8,470
Footnotes from table, previous page:

aOperating hours from Reference 20.

^Assumed to have single mechanical seals.

C25% of open-ended lines used for sampling, based on Reference 24,
 p. 3-4.

dVOC assumed to be 100% naphthalene for conservative estimate.

     c.  Storage Emissions

          Emissions  of naphthalene from phthalic anhydride  production
at  the  facility are  primarily from one storage tank  (Reference 10).

          It is assumed that EPA  emission  factors from  AP-42  (Reference
21) apply for  uncontrolled  stor.age tank losses of naphthalene at  phthalic
anhydride plants.  Emissions from naphthalene storage are presently  not
controlled.

          The  facility has  one  naphthalene storage  tank.

          Emission equations for  estimating breathing  (Lg)  and working
 losses  (Lu)  from  fixed-roof tanks storing  volatile  organic  liquids  are
 calculated  as  follows  (PES  assumes  all organics  in  tank are naphthalene):
                                   A-14

-------
    Total  Loss • LB + Lu                 0_M
            LB . 2.26 x ID"2 HV  P^T       Bl-» H°-»  T'-5° Fp  CKC
    where:
            LB = fixed roof breathing loss (Ib/yr)
            MV = molecular weight of vapor in storage tank (Ib/lb mole)
            PA = average atmospheric pressure at tank location (psia)
            P  = true vapor pressure at bulk liquid conditions (psia)
            D  = tank diameter (ft)
            H  = average vapor space height, including roof volume
                 correction (ft)
              T = average ambient diurnal temperature change (°F)
            Fp  = paint  factor  (dimensionless)
            C  = adjustment factor  for  small diameter tanks .(dinension-
                 less)
            KC  = product  factor  (dimensionless).
Fixed-roof tank  working  losses  can  be estimated  from:
             Lw  =  2.40 x 1(T5  Mv  PVNKN  Kc
     where:
             LW  =  fixed-roof working loss  (Ib/year)
             Mv  =  molecular weight  of vapor  in  storage tank  (Ib/lb mole)
             P  =  true vapor pressure at bulk liquid temperature (psia)
             V  =  tank capacity (gal)
             N  =  number of turnovers per year (dimensionless)
                  N  = Total throughput per year (gal)
                           Tank capacity, V (gal)
             KN = turnover factor (dimensionless)
              Kp = product  factor (dimensionless)
                                  A-15

-------
     From References 20 and 21,  the following  variables  for the equations
are given:

Fixed-roof breathing loss,  LR (Ib/yr):

     Mv  = 128.19 (Reference 22)

     PA  = 14.7 psia (Reference  23)

     P   = 1.84 (Reference  25) true vapor pressure at  60°F

     D   = 66.5 ft (Reference 20)

     H   = 16 ft (assume H  = 1/2 tank height,  Reference  21)

      T  = 20°F (assumed as typical value, Reference 23)

     Fp  = 1.26 (aluminun tank,  based on average of several aluminum
                 tank paint factors, Reference 21)

     C   = 1 (Reference 23, p. 3-26)

     KC  = 1.0 (Reference 21, p. 4.3-8)

      LB = 25,500 Ib   0.454 kg
                  yf x       Tb  = 11.600 kg/yr

Fixed-roof working loss, LU (Ib/yr):

     Mv  = 128.19 (Reference 22)

     P   = 1.84 psia (same  assumptions  as for  breathing  loss above)

     V   = 835,000 gal (Reference 20)

     N   = 16.17 (Reference 21)

     KN  = 1.0 (Reference 21)
     Kc  = 1.0 (Reference 21)

      I     76,400 Ib   0.454 kg
       W =        7F x       Tb  = 34,700 kg/yr

     LB + LW = 46,300 kg/yr.

Total Naphthalene Emissions from Phthalic Anhydride Production = 54,754 kg/yr
                                                               = 54.8 Mg/yr  .

A.5   CARBAMATE INSECTICIDES END USE

A.  SIC Code

     Reference 1.

                                  A-16

-------
8.  Plant Name

     Only one plant,  Union Carbide,  Institute,  WV,  produces  carbamate
insecticides (chiefly carbaryl)  from naphthalene (References 4 and 9).
One other Union Carbide facility,. St.  Louis,  MO, is reported to dilute
the carbaryl product  it receives from another plant, but it  does not
produce carbaryl  directly and there  is no naphthalene storage (Reference
26).

     Corresponds to an emission  point, either.process, fugitive, or
storage.  Uhen stack  parameters  for  different emission points are
identical, they are assigned one number, and  emissions from  these
points are combined.

H.  Stack Parameters

     Reference 9 unless indicated otherwise.

     1.  Process emissions from Unit Number 250 corresponds  to Stack
         Number P-l in Table A-4.  Stack parameters from Reference 9.

     2.  Process emissions from Unit Number 251 correspond to Stacks P-2,
         P-3, and P-4 in Table A-4.   Stack P-3 represents 2  identical
         4.6-meter stacks with reported average velocity of  0.22 m/sec
         Stack P-4 represents 5 15-meter stacks with average
         temperature of 317°K and an average  velocity of 2.4 m/sec.
         Total emissions from Process [251] were apportioned among the
         stacks based on stack sampling data  given in Reference 9.

     3.  Process emissions from Unit No. 252  correspond to Stack Number
         P-5 in Table A-4.  Stack parameters  from Reference  27.

     4.  Process emissions from Unit No. 253  correspond to Stack Number
         P-6 in Table A-4.  Stack parameters  from Reference  9.

     5.  Fugitive emissions from all process  units are reported under
         one "stack number."  Assumptions include a release height of
         3 meters above ground, a cross-sectional downwash area of
         100 x 200 meters, a velocity of 0.01 m/sec, and temperature of
         293°K (ambient).  Values of 0.01 m/sec for velocity and 293°K
         for temperature were assumed.

C.  Latitude/Longitude

    Reference 43.

D.  Urban

     Plant  assumed to be located in an urban area.

E.  City, State

     Reference 4.

                                  A-17

-------
F.  Emission Type

     Process (P), Fugitive (F), or Storage (S)  emission points
are based_on information in Reference 9.

G.  Stack Number

     6.  Storage emissions:

Unit 250 - 3 tanks             H = 12m,  D = 15m (S-l  in Table A-4)
           1 tank              H = llm,  D = 21m (S-2  in Table A-4)

Unit 251 - Estimated 1 tank,   H = 3m,   0 = 3m (S-3 in Table A-4)

Unit 252 - 3 tanks,            H = 9.1m,  D = 7.6m (S-4 in Table A-4)

Unit 253 - 1 tank,             H = 3.4m,  D = 3.5m (S-5 in Table A-4)

Values of 0.01 m/sec assumed for velocity and 293°K (ambient) for
temperature.  Vent diameter of 0.076 m is based on average diameter
of xylene storage tank vents from Reference 40.

I.  Vent Type

     A vertical vent (0) for process and  storage emission points, and
nonvertical  (1) for fugitive emissions is used.

J.  Emissions                      .         • •

Plant 1 - Union Carbide, Institute, WV.

     Emissions information from 1984 Emission Inventory, Summary by
Process, Union Carbide, Institute, WV (Reference 9).  The following
emission estimates are presented by emission type (process, storage,
fugitive, emergency) and by carbaryl process unit (hydrogenation,
oxidation, dehydrogenation, and refining).

     a.  Process'Emissions of Naphthalene from  Carbaryl Production

          No information to indicate emissions  are controlled; therefore,
no controls are assumed to be in place.  The carbaryl  process units  and
reported emissions are listed below:

     1.  #250 - Tetralin hydrogenation unit:

                 1,512 Ib/yr x 0.454 kg/lb = 686 kg/yr

     2.  #251 - Tetralin oxidation unit:

                         1,573.5 Ib   0.454 kg
                                    x          = 714
                                  A-18

-------
    3.  #252 - Crude naphthol dehydrogenation unit:

                  2.8 Ib   0.454 kg
                      7F x       Ib  =  1-3

    4.  #253 - 1-naphthol refining unit:

                  1.8 Ib   0.454 kg
                      yjT x       Tb  =  °-


          TOTAL Process  Emissions = 1,402 kg/yr


    b.  Fugitive  Emissions of Naphthalene  from  Carbaryl  Production

    1.  #250 - Tetralin hydrogenation  unit:

                 1,279 Ib   0.454 kg
                      yp x       TF  =  581  kg/yr

    2.  #251 - Tetralin oxidation  unit:

                  842 Ib   0.454 kg
                      y7 x       TF  =  382  kg/yr

    3.  #252 - Crude naphthol dehydrogenation unit:

                 83.6 Ib    0.454 kg
                     yp x        Tb  =  38-° k9/yp

    4.  #253 - 1-naphthol  refining unit:

                   548 Ib   0.454 kg
                      yf x       Tb  =  249  kg/yr


          TOTAL Fugitive Emissions  =  1,250  kg/yr


    c.  Storage  Emissions  of Naphthalene  from Carbaryl  Production

     1.  #250  - Tetralin hydrogenation  unit (4 storage tanks, 4,046.5
Ib/yr  total  emissions):
             4,046.5 Ib   0.454 kg
                     7 x       Tb = 1,837 kg/yr
     2.   #251 - Tetralin oxidation unit:

                  16.9 Ib   0.454 kg
                                     = 7-67
                                  A-19

-------
     3.   #252 -  Crude  naphthol  dehydrogenation  unit (3 storage tanks,
         31.7 Ib/yr each):

                  95.1 Ib    0.454 kg
                       yF x       Tt>  = 43-2 kg/yr

     4.   #253 -  1-naphthol  refining unit:

                  38.2 ]b_   0.454 k£
                       \ir  X       Ih  = 17.3
          TOTAL Storage Emissions  =  1,905 kg/yr.


     d.   Emergency  Emissions  of Naphthalene from  Carbaryl  Production

     1.   #250 - Tetralin hydrogenation unit:

                     5 ]b_   0.454  J
-------
     (Production of 1- and 2-naphthalenesulfonic acids).

A.  SIC Code

     Reference 1.

B.  Plant Name

     Five producers of synthetic tanning agents from naphthalene were
identified:

     (1)  Diamond Shamrock, Carlstadt, NO (Reference 4)
     (2)  Rohm and Haas, Philadelphia, PA (Reference 4)
     (3)  Morflex, Inc., Greensboro, NC (Reference 10, p. 45)  (formerly
          Ciba-Geigy)
     (4)  Georgia Pacific, Bellingham, WA (Reference in, p. 45)
     (5)  Diamond Shamrock, Cedartown, GA (Reference 10, p. 45)

C.  Latitude/Longitude

     Rased on conversion of zip code obtained from Reference 4 or
U.S. Postal Service Zip Code Directory to UTM coordinates using  com-
puter program from Office of Toxic Substances.

D.  Urban

     All plants are assumed to be located in an urban area.

E.  City, State

     References 4 and  10.

F.  Emission Type

     Process (P), Fugitive (F), and Storage  (S).

G.  Stack/Vent Parameters

     Sane as Section A.8, Surface Active Agents, Part H.

H.  Emissions

     Synthetic tanning agents are produced primarily from 1- and 2-
naphthalenesulfonic acids (NSA), both derivatives of naphthalene.
Plant-specific emissions of naphthalene from the production of 1- and
2-NSA were calculated  on the basis of total  naphthalene consumption by
the method described in Section A.8 for Surface Active Agents.  Calculated
emissions are'based on:  (1) the assumption  that 0.034% of total naphthalene
consumed (315 Gg) is lost to the atmosphere  (based on Reference  3,
assuming this percentage is the same for both production and consumption);
and (2) 6% of total  naphthalene consumption  is from production of synthetic
tanning agents (Reference 3).  From the above, total  naphthalene emissions
from production of synthetic tanning agents  (1- and 2-NSA) are calculated  as:


                                  A-21

-------
     0.06 x 0.00034 x 315 Gg  = 0.0064 Gg
                              = 6.4    Mg.

This total was divided among the five producers  of  synthetic  tanning
agents, or 1.3 Mg naphthalene emissions per plant.

A.8   SURFACE ACTIVE AGENTS END USE

     (Production of 1- and 2-naphthalenesulfonic acids)

A.  SIC Code

     Reference 1.

B.  Plant Name

     References 4 and 31.

C.  Latitude/Longitude

     Based on conversion of zip codes from Reference 4 and U.S.  Postal
Service Zip Code Directory to UTM coordinates using computer  program
from the Office of Toxic Substances.

D.  Urban

     Plants are assumed to be located in an urban area.

E.  City, State

     References 4 and 31.

F.  Emission Type

     Process (P), Fugitive (F), and Storage (S)  emissions.

G.  Stack Number

     Corresponds to an emission point, either process, fugitive, or
storage.  When stack parameters for different emission points are
identical, they are assigned one number, and emissions from those
points are combined.

H.  Stack Parameters

     1.   Process emissions - Unless a specific stack height is known,
     13 m from average of stack heights was selected, Reference 9;
     specific stack heights were available for some of the New Jersey
     plants  (Reference 32).

          Vents are assumed to be  vertical (0) and a stack diameter of
     0.15 m  (average of stack diameters from Reference 9 is used).

                                   A-22

-------
          A stack velocity of 6.3 m/sec is  selected based on average
     velocity from Reference 9.   If  stack velocities  are known  for
     specific plants,  they are reported (Reference 32).

          A stack temperature of 320°K is selected based on  average
     temperatures for  process stacks from Reference 9.

          2.  Fugitive emissions - A height  of 3m, crosssectional  area
     of 200 m x 100 m  (20,000 m2) for Plants 1 and 3 and 100 m  x 50 m
     (5,000 m2) for Plants 2 and 4 are used.  Horizontal venting is
     assumed; a velocity of 0.01 m/sec and a temperature of  293°K
     (ambient) are assumed.

          3.  Storage  emissions  - A  height of 7.7m based on  average
     height of tanks from Reference  9 is chosen;  A vertical  vent,  a
     vent diameter of  0.076 m (Reference 40), a velocity of  0.01 m/sec,
     and a temperature of 293°K  (ambient) are used.

I.  Emissions

     Plant-specific emissions of naphthalene from the production of
1- and 2-naphthalenesulfonic acid were calculated on the basis  of total
naphthalene consumption.   It is  assumed that 0.034% of total naphthalene
consumed as end-use chemicals is lost to atmosphere (based on Reference
14 estimate that a maximum 0.07% of  naphthalene produced is  lost to the
environment and 48% of that amount is lost  to atmosphere).  This gross
estimating procedure is used because of the lack  of usable pl-ant-
specific information.   Based on:  (1) 0.034% of total  naphthalene
consumed (315 Gg, Reference 3) is lost to air and (2)  7% of  total
naphthalene consumption is from  production  of surface active agents
(Reference 3), total naphthalene emissions from production of surface
active agents are calculated as:

                 0.07  x 0.00034  x 315 Gg = 0.0075 Gg

                                         = 7.5 Mg

     1.  1-naphthalenesulfonic acid  (1-NSA)  production - Naphthalene
     emissions from 1-NSA production are calculated by multiplying the
     above total (7.41 Mg) by 15%, the relative percentage of 1-NSA
     in surface active agent compounds (estimate  based on Reference 34):

                          0.15 x 7.5 = 1.1 Mg

     This total was apportioned  among the nine 1-NSA producers  to obtain
     a plant-specific  estimate of 123 kg per plant.  One-third  of
     the plant total (41 kg) was assigned each to process, storage, and
     fugitive emissions.
                                  A-23

-------
 2.  2-naphthalenesulfonlc acid (2-NSA)  production  - Naphthalene
     emissions from 2-NSA production  are calculated  by multiplying
     the total emissions from NSA production (7.41  Mg) by 85%,  the
     relative percentage of 2-NSA in  surface active  agent compounds
     (Reference 34):
                            0.85 x 7.41  = 6.3 Mg

     This total was apportioned among the six 2-NSA  producers to derive
     a plant-specific estimate of 1,050  kg per plant.  One-third of
     the plant total (350 kg each) was assigned to  process,  storage,  and
     fugitive emissions.

A.9   MOTH REPELLANT END USE

A.  SIC Code

     Reference 1.

B.  Plant Name

     Plant 1 - Morflex, Inc. (formerly Ciba-Geigy Corp.), Greensboro, NC
(Reference 31).

     Plant 2 - Kincaid Enterprises,  Inc., Nitro, WV (Reference  31).

     West Virginia Air Pollution Control Commission  reports  no  infor-
mation on Plant 2 and that the plant may no longer be in operation or
not using naphthalene in the production  of moth repellant (Reference
35).

C.  Latitude/Longitude

     Based on  conversion of zip codes from U.S. Postal Service  Zip Code
Directory to UTM coordinates using computer program from the Office  of
Toxic Substances.

D.  Urban

     Plants are assumed to be located in an urban area.

E.  City, State

     Reference 31.

F.  Emissions

     Plant 1  - No  informatioa was available on Morflex,  Inc. from the
North Carolina Department of Natural Resources permit files to  indicate
that the  plant is  manufacturing moth  repellant.

      It  is assumed  that if the plant produced moth repellent from naph-
thalene,  emissions  from production and  handling of moth  repellent would
be  included in estimates for production  of naphthalene because the
product  is made  directly from the production of naphthalene as  a  solid

                                  A-24

-------
flake, powder, or ball, and is repackaged as a consumer product at
another facility (Reference 10,  p. 46).   It is assumed that the Morflex
facility only repackages the product that is already manufactured in a
crystallized form by one of the  naphthalene producers.  Therefore, no
emissions of naphthalene are expected from Morflex.

     Plant 2 - Based on information from the West Virginia Air Pollu-
tion Control Commission, no emissions of naphthalene are estimated from
Kincaid Enterprises (References  35 and 42).

A.10   MISCELLANEOUS ORGANIC CHEMICALS END USE

     No plant-specific information was available on miscellaneous
chemicals except one, RSA Corporation, Ardsley, New York, which produces
1-bromonaphthalene.

A.  SIC Code

     Reference  1.

B.  Plant Name

     The following  organic  chemicals are classified as miscellaneous
in terms of naphthalene end use:
             Source
        Category/Chemical
 1.   1-naphthol
 2.   1-naphthylamine
          Plant
     Name/Location

Union Carbide, Institute, WV
(Emissions included in carbaryl
production)

Sigma Chemical Co., St. Louis,
MO
 3.   1,2,3,4-tetrahydronaphthalene   DuPont, Deepw^ter, NJ
       (tetrali n)
 4.   decahydronaphthalene
       (decalin)

 5.   1-naphthaleneacetic  acid
 6.   1-bromonaphthalene
Union Carbide, Institute, WV
(Emissions included in carbaryl
production)

OuPont, Deepwater, NJ
Greenwood Chemical, Greenwood,
VA
(No longer in operation)
Union Carbide, Ambler, PA

RSA Corp., Ardsley, NY
Refer-
ence

  4

  9


 31

  4
  4
  9
                                                                      4
                                                                     36
                                                                      4
                                    A-2b

-------
7.  1-methylnaphtha!ene            Chemical  Exchange Industries,
                                   Houston,  TX                        4

8.  methylna-phthalene              Koppers,  Follansbee,  WV           4
                                   Crowley  Chemical, Kent, O.H         4
                                   Crowley  Chemical, Oklahoma  City,
                                   OK                                4

9.  1-naphthaleneacetamide         Greenwood Chemical,  Greenwood,
                                   VA                                4
                                   (No longer in  operation)         36

10. nitronaphthalenesulfonic acids Ciba-Geigy,  Toms River, NJ         4

11. naptalam                       Uniroyal, Gastonia,  NC            4

C.  Latitude/Longitude

     Based  on conversion of zip codes from Reference 4 and U.S. Postal
Service Zip Code Directory to DIM coordinates using computer program
from Office of Toxic Substances.

D.  Urban

     All plants are assumed to be located in urban areas.

E.  City/State

     References 4 and  31.

F.  Emission Type

     Reported as process  (P), fugitive  (F),  and storage  (S) emissions.

G.  Stack Number

     Corresponds to  an emission point,  either process, fugitive, or
storage.

H.  Stack Parameters

     1.   Process emissions  -  Unless  a specific stack height is known,
the average of stack heights, 13  m,  is  used, Reference 9;  specific stack
heights  were  available from some  of  the New Jersey  plants (Reference  32)
and from RSA  Corporation  (Reference  37).

     Vents  are  vertical  and a stack  diameter of  0.15 m  is used  (average
of stack diameters  from Reference 9).   Stack diameter for RSA  Corp.  is
 from Reference  37.

     A stack  velocity  of 6.3  m/sec  is used  based  on average velocity
 from Reference  9.   If  stack velocities  are  known  for specific  plants,
 they  are based  on  velocities  from References 32  and 37.


                                    A-26

-------
     A stack temperature of 320°K is used based on average tempera-
tures for process stacks from Reference 9.   Stack  temperature for RSA
Corporation-is from Reference 37.

     2.  Fugitive emissions - A release height of  3 m,  crosssectional
downwash area of 200 m x 100 m for large plants, 50 m x 100 m for medium-
sized plants, and 50 m x 25 m for small plants.  Horizontal  vents are
assumed.  A velocity of 0.01 m/sec and a temperature of 293°K (ambient)
are assumed.

     3.  Storage emissions - A height of 7.7 m is  used based on average
height of tanks from Reference 9.  PES assumes venting  is vertical, a
vent diameter of 0.076 (Reference 40), a velocity  of 0.01 m/sec, and a

temperature of 293°K (ambient).

I.  Emissions

     Except for RSA Corp., plant-specific emissions of naphthalene
from miscellaneous organic chemical production were calculated on the
basis of total naphthalene consumption.  (RSA Corporation reported emis-
sions as "trace," which means <0.001 Ib/hr.)  For other plants, it is
assumed that 0.034% of total naphthalene consumed  as end-use chemi-
cals is lost to atmosphere (based on Reference 14 estimate that a maximum
of 0.07% of naphthalene produced is lost to the environment and 48% of
that amount is lost, to atmosphere).  This gross estimating procedure is
used because of the lack of usable or no plant-specific information.

     Based on (1) 0.034% of total naphthalene consumed (315 Gg, Refer-
ence 3) is lost to air and (2) 2% of total  naphthalene is from produc-
tion of miscellaneous organic chemicals (Reference 3), total naphthalene
emissions from production of miscellaneous  organic chemicals is calcu-
lated as:

     0.02 x 0.00034 x 315 Gg = 0.0021 Gg

                             = 2.1 Mg

This total was divided among all plants for which no specific emission
was available (2.1 Mg * 14 plants = 150 kg each plant).  One-third
of the total plant estimate was assigned each to process, storage, and
fugitive emissions (50 kg each).

     Only storage emissions of methylnaphthalene were estimated for
Crowley Chemicals, Kent, OH, and Oklahoma City, OK, since no chemical
production occurs at either facility (References 38 and 39).
                                  A-27

-------
     Emissions from 1-naphthol  production at  Union  Carbide,  Institute,
WV, are included in naphthalene emissions from carbaryl  production
(Reference 7) (see Section A.5).

     Table A-2 presents the modeling parameters for naphthalene  production.
After completion of the modeling,  a review of the emission estimating
procedures resulted in revised emission estimates.   Overall  emissions  for
the production category increased 0.4 percent, from 52,960 kg/yr to
53,200 kg/yr.  Total fugitive emissions increased from 1,560 kg/yr to
2,180 kg/yr.  Process emissions decreased from 47,200 kg/yr  to 46,900  kg/yr.
Storage emissions decreased from 4,200 kg/yr  to 4,170 kg/yr. EPA determined
that additional  modeling was not necessary.
                                    A-28

-------
                             Table  A-l.  MODELING  PARAMETERS FOR  NAPHTHALENE
                                EMISSIONS  FROM COKE BY-PRODUCT RECOVERY  PLANTS
NJ
Record*
1
2
3
4
j
6
7
a
9
id
11
12
13
14
15
16
17
16
19
20
21
22
23
24
25
26
27
23
29
30
31
32
33
34
35
36
uodate oollutaitt source_cat
10/23/66 taonthaiene Coke by-product
10/26/66
10/26/66
10/26/66
10/28/66
10/28/66
113/28/86
10/28/86
10/26/66
10/28/86
10/28/66
10/26/86
10/26/66
10/28/86
10/26/86
10/28/66
10/28/66
10/28/86
10/28/66
10/26/86
10/28/66
10/28/86
10/28/86
10/28/86
10/28/86
10/28/86
10/26/86
10/26/86
10/28/86
10/28/86
10/28/86
10/28/8b
10/28/66
10/28/66
10/26/66
10/26/86
Dlant_nuub sic_code olant_na«e
       1 3312
       1
       1
       &
       2
       2
       3
       3
       3
       4
       4
       4
       5
       5
       5
       &
       6
       6
       7
       1
       7
       a
       a
       a
       9
       9
      ' 9
       id
       10
       10
       11
       11
       11
       12
       12
       12
                                                                                    latitude longitude urban city
Eaoire Coke


Republic Steel


National Steel


Inter lake

Indiana Gas ( Chen.


U.S. Steel


Rouge Steel Co.


National Steel


Bethlehem Steel


Chattanooga Coke t C


Lone Star Steel


J & L Steel


331425
0
0
340046
0
0
384140
0
0
413922
A
<0
0
392648
0
0
413655
0
0
421619
0
0
421516
0
0
403651
0
0
350216
0
0
325459
0
0
402534
0
0
873011
0
0
860238
0
0
900742
0
0
873732
0
872347
0
0
672003
0
0
630940
0
0
830743
0
0
752113
0
0
851811
0
0
944257
0
0
795747
0
0
• Holt
e
e
0 Gadsden
0
ft '
0 Granite City
0
0
0 South Chicago
0
0 Terre Haute
0
0
0 Gary
0
e
0 Dearborne
0
0
0 Detroit
0
0
0 Bethlehem
0
0
0 Chattanooga
0
0
0 Lone Star
0
0
0 Pittsburgh
0
0

-------
_J 0-
2
o
                                                                                                          II
                                                35 S
                                                                                                 s s a 2 &
                                                                                                 i 8 8 3 I
             OJ
Q. >
is
   LU
             IS iS «9 iS S IS
                                              19 IS iS IS
                                                                                 — IS iS  —. iS IS —t
   o --^
• c
a£ ca o
<    u
O_ LU — »
   2^
ta o
z o
                        19'SSisisiniSis
                              is       r*-
                              is       CO
O Li_
S
   oo
   z
  • o
I— I I— I
 I 1/1

-------
                      Table A-2.   MODELING  PARAMETERS FOR NAPHTHALENE
                                EMISSIONS  FROM NAPHTHALENE  PRODUCTION
Record*  uotiate   pollutant
      1  10/28/66 Nahothalene
      2  10/26/86
      3  10/28/86
      4  10/26/86
      5  10/26/66
      6  10/28/66
      7  ld/26/66
      8  10/28/86
      9  1(9/28/86
     id  10/28/86
     11  10/28/86
     Id  10/28/86
     13  10/26/86
     14  18/28/66
     15  10/26/86
     16  10/28/66
     17  10/28/66
     18  10/28/86
     19  10/28/86
     20  10/26/66
     21  10/06/66
     22  10/06/66
     23  10/08/66
     24  10/08/66
source_cat
Naontiialene arod.
1 2865
1
1
2 2669
2
2
3 2869
3
3
4 2865
4
4
4
4
4
4
4
5 2869
5
5
6 2669,
7 2865
6 2665
9 2865
olant_naue latitude longitude urban city
Allied Chemical Co.


Cheuical Exchange


£. I. duPont de ten.


Hoppers Coupany, Inc







Texaco Chemical


fisnland Chemical
U.S.S. Cheuicals
U.S.S. Cheaicals
Hoppers Conpany, Ire
363016
0
0
294515
0
0
291550
0
0
402013
0
0
0
0
0
0
0
393507
0
0
362736
401736
413600
415100
623942
0
0
950100
0
0
951248
0
0
803620
0
0
0
0
0
0
0
753744
0
0
623818
795230
872006
674742
• Ironton,
0
0
0 BaytoMn
0
0
0 Chocolate Bayou
0
0
0 Follansbee
0
e
0
0
0
0
0
0 Delaware City
0
0
0 Ashland
0 Clairton
0 Gary
0 Stickney

-------
                                Table A-2.   MODELING PARAMETERS FOR NAPHTHALENE
                                        EMISSIONS  FROM NAPHTHALENE PRODUCTION
                                                     (concluded)
T
Record*
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
IB
19
20
21
22
23
24
p i ant _ name
Allied Chemical Co.

!
Chemical Exchange


£. !. duPont de Nem.


Koooers Coiaoany. Inc







Texaco Chemical


Ashland Chemical
U.S. 5. Chemicals
U.S. 5. Cneaicals
Koooers Conoany, Inc
state tyoe stack_nura
OH


TX


TX


UV







DE


KY
PA
IN
IL
P
F
S
P
F
S
P
F
S
P
F
S
S
S
5
S
S
P
f
S




1
1
1
1
1
1
1
1
1
1
1
1
2
3
4
5
6
1
1
1
0
0
0
0
height
13.~00
3.00
7.60
13.00
3.00
7.60
13.00
3.00
7.60
13.00
3.00
6.70
7.60
10.90
9.10
6.10
12. 80
13.00
3.00
7.60
0.00
0.00
0.00
0.00
area vent.type diameter velocity
0.00
20000.00
0.00
0.00
20000.00
0.00
0.00
20000.00
0.00
0.00
20000.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
20000.00
0.00
0.00
0.00
0.00
0.00
0
1
0
0
1
0
0
1
0
0
1
0
0
0
0
0
0
0
1
0
0
0
0
0
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.076
0.076
0.076
0.076
0.076
0.150
0.000
0.076
0.000
0.000
0.000
0.000
6.300
0.010
0.010
6.300
0.010
0.010
6.300
0.010
0.010
6.300
0.010
0.010
0.010
0.010
0.010
0.010
0.010
6.300
' 0.010
0.010
0.000
0.000
0.000
0.000
teno
320
293
293
320
293
293
320
293
293
320
293
293
293
293
293
293
293
320
293
293
0
0
0.
0
en_uax
0~000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0AAA
• vw
0.000
0.000
0.000
Missions
62M.IM
V*. Mft
760.000
3400.000
120.000
320.000
9600.000
340.000
940.000
19300.000
560.000
160.000
170.000
261.000
277.000
356.000
316.000
6500.000
230.000
620.000
0.000
0.000
0.000
0.000

-------
Table  A-3.  MODELING PARAMETERS  FOR NAPHTHALENE
    EMISSIONS  FROM PHTHALIC ANHYDRIDE PRODUCTION
      source_cat
plant nunt) sic code olant name
latitude longituoe urban city
1
2
3
4
5
Recordl
1
2
3
4
5
10/28/86 Naofithalene
10/08/86
10/08/86
10/28/86
10/28/86
olant_riaifie
Kopoers Co. Inc.
Monsanto Co.
Koooers Co. Inc.


Withal ic finyhdriae




state type stack_ria» heignt
PA 0 0.00
MJ 0 0. 00
IL P 1 0.00
F 1 3.00
S 1 9.80
1
2
3
3
3




2869




area
0.00
0.00
0.00
20000.00

0.M
Koooers
Monsanto
KoQoers


vent_tyoe
0
0
0
1
0
Co. Inc.
Co.
Co. Inc.


diameter
0.000
0.000
0.000
0.000
076
402136
394806
415100
0
0
velocity
0.000
0.000
0.000
0.010
0.018
800700
752100
874742
0
0
team eu_
0 0.
0 0.
0 0.
293 0.
293 8.
0
8
0
0
0
•ax
000
000
000
000
808
Bridgeville
Bridgeport
St ickney


emissions
0.000
0.000
0.000
8470.000
46300.808

-------
                                         Table A-4.   MODELING  PARAMETERS  FOR  NAPHTHALENE
                                           EMISSIONS  FROM  CARBAMATE  INSECTICIDES  PRODUCTION
                Record  uoaate   pollutant
                     1  10/14/86 Naonthalene
                     2  10/14/86
                     3  10/14/86
                     4  18/14/86 .
                     5  10/14/86
                     6  10/14/86
                     7  10/14/86
                     8  10/14/86
                     9  10/14/86
                     10  10/28/66
                     11  10/14/86
                     12  10/14/86
                     13  10/14/86
source cat
Dlant_numb sic_code Dlant_riame
latitude longitude urban city
r
LO
                ftecoroi  Dlant_nai,ie
                      1  Union Carbide Corn.
                      2
                      3
                      4
                      5
                      6
                      7
                      8
                      9
                     10
                     11
                     12
                     13  union Caroiae
Carbaryl Proa












state tyoe stacK_
W P
P
P
P
P
P
f
S
S
5
5
5
no













nun
1
^
3
4
5
6
7
8
9
10
11
12
0













height
12.20
16.80
4.60
15.20
13.70
15.20
3.00
12.20
11.00
3.00
9.10
3.40
0.40
1
1
1
1
1
1
1
1
4
'1
1
1
1
2







2879












area
0.00
0.00
0.00
0.00
0.00
0.00
20000.00






0.00
0.00
0.00
0.00
0.00
0.W
Union Carbide











Union Carbide
Corp.












vent _ type Diameter
0
0
0
0
0
0
1
0
0
0
0
0
0
0.150
0.300
0.250
0.040
0.100
0.037
0.000
0.076
0.076
0.076
0.076
0.076
0.000
382258
0
0
0
0
0
0
0
0
0
0
0
383400
velocity
1.200
14.400
0.220
2.400
19.800
0.910
0.010
0.010
0.010
0.010
0.010
0.010
0.W0
814625











0
0
0
0
0
0
0
0
0
0
0
901500
teao
339
313
313
261
313
323
293
293
293
293
293
293
0
E













0
0
0
8
0
0
0
0
0
*
0
8
0
».„»
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.0&3
0.000
Institute



i







St. Louis
euissions
686.000
571.000
72.000
71.0A2I
1.300
0.820
1250.000
1831.000
6.000
7.670
43.200
17.300
0.000

-------
                                         Table A-5.   MODELING PARAMETERS  FOR  NAPHTHALENE
                                               EMISSIONS  FROM 2-NAPHTHOL PRODUCTION
                    Record!  uodate   pollutant      source_cat          plant.nuab sic_code plant.naw          latitude longitude urban city
                          1  10/08/86 Napthalene     Beta-naphthol  prod.          1 2869     flwrican Cyarwuiid Co  392048   811912    0 Willow Island
U)
Ul
                    Recordl  plant nane
                         1  Aterican Cyananid Co WV
state type stack_riu«    height
area vent_type  dianeter   velocity teao
0.00        0     0.000      0.000    0
                                                                                                                          ea vax
                                                                                                                                   emssions

-------
    Table A-6.   MODELING PARAMETERS  FOR NAPHTHALENE
EMISSIONS FROM  PRODUCTION OF  SYNTHETIC TANNING AGENTS
Recorcn
1
2
3
4
5
6
7
6
9
10
11
12
13
14
15
Recora«
1
2
3
4
j
6
7
6
9
10
11
12
13
14
:5
uocate Qoliutan:
10/26/66 Naontfialene
10/28/86
10/28/86
10/28/86
10/28/66
10/28/66
10/28/66
10/26/66
10/28/66
10/28/86
10/28/86
10/26/86
10/26/86
10/28/86
10/28/86
Dlant_name
Diamond SnamrocK


Ronm & Haas Co. ,


florflex. Inc.


Georsu Pacific Coro


DiiBono SnaarocK.


         source cat         plant.nuHti sic_code Dlantjiame
iatituoe longitude urban city
       tyce stacK_nuia
       ?
       F
       S
       P
       r
       S
       P
       f
       5
tanning ag










id
1
1
1
1
1
1
1
1
1
1
l
1
1
i
1










heignt
13.00
3.00
7.70
13.00
3.00
7.70
13.00
3.00
7.70
13.00
3.lM
7.70
:3.0$
3.00
7.7ii
1 2869 Diamond
1
2 Rohu &
2
2
3
3
3
4
4
4
5
5
5
area
0.00
20000.00
0.00
0.00
20000.00
0.00
0.00
20000.00
0.00
0.00
2W0. 00
0.00
o*
20000.00
0.00

Morflex


Georgia


Diamond


Shamrock 405018
0
0
Haas Co. 395954
0

, Inc.


Pacific


0
360516
0
0
Coro 464548
0
0
Snamrock 340048


vent_type diameter
0
1
0
0
1
0
0
1
0
0
1
0
0
1
0
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0
0
velocity teno
6.300 320
0.010 293
0.010 293
6.300 320
0.010 293
0.010 293
6.300 320
0.010 293
0.010 293
6. 300 320
0.010 293
0.010 293
6.388 32(2
0.010 293
0.010 293
740542
0
0
750400
0
0
795324
0
0
1222900
0
0
851518
0
0
eu_uax
0.000
0.000
0.08)0
0.000
0.000
0.000
0.000
0.000
0.00«l
0.000
0.000
0.000
0.000
0.000
0.000
0 Carlstadt
0
«
0 Philadelphia
0
0
0 BreensDoro
0
0
0 BeHingnan
0
ft
0 Cedar tour.
0
0
emssions
430.000
430.000
430.000
430.000
430. 000
430.0021
430. 030
430.020
430. «I0
430. Mtf
430. 00d
t30. 000
430. 000
430.000 '
430. 000

-------
              Table  A-7.   MODELING PARAMETERS FOR NAPHTHALENE  EMISSIONS FROM
                 PRODUCTION OF  SURFACE  ACTIVE  AGENTS  --  1-NAPHTHALENESULFONIC ACID
Record*  uadate   pollutant
     1  10/14/36 Naontnalene
     £  10/14/8&
     3  10/14/86
     4  10/14/36
     5  10/14/86
     6  10/14/86
     7  10/14/86
     8  10/14/86
     9  10/14/86
     10  10/14/86
     11  10/14/86
     12  10/14/86
     13  10/14/86
     14  10/14/86
     15  10/14/86
     16  10/14/86
     17  10/14/66
     18  10/14/86
     19  10/14/86
     £0  10/14/86
     £1  10/14/86
     ££  10/14/86
     23  10/14/86
     £4  10/14/86
     25  10/14/86
     £6  10/14/86
     £7  10/14/86
source_cat
1-nao.sulfonic acid
Dlant_nui»d sic_coae plant_nawe
        1 £843
                           1
                           £
                           2
                           £
                           3
                           3
                           3
                           4
                           4
                           4
                           5
                           5
                           5
                           6
                           6
                           6
                           7
                           7
                           7
                           6
                           a
                           8
                           s
                           9
                           9
latitude longituae urban city
American Cyanauud


Ciba-beigy Corp


DeSoto, Inc.


Diamond Shamrock


Diaaond Shamrock


E.I. duPont de Men.


EsiKay Chen. Co.


Morflex, Inc.


Georgia Pacific


403800
0
0
395£54
0
0
3£4448
0
0
405018
0
0
340048
0
0
394100
0
0
403912
0
0
360518
0
0
464546
0
0
741500
0
0
741048
0
0
972000
0
0
74054£
0
0
851518
0
0
7529£4
0
0
741130
0
0
7953£4
0
0
12E29W
0
0
0 Linden
0
0
0 Tons River-
0
0
0 Fort Worth
0
0
0 Carlstadt
0
0
0 Cedartown
0
0
0 Deepwater
0
0
0 Elizabeth
0
0
0 Greensboro
0
0
0 Bellinghan
0
8

-------
Table A-7.  MODELING PARAMETERS FOR NAPHTHALENE EMISSIONS  FROM
  PRODUCTION OF SURFACE ACTIVE AGENTS — 1-NAPHTHALENESULFONIC ACID
                             (concluded)
Record*
1
£
3
4
5
6
7
6
9
10
11
12
13
14
15
16
17
18
19
£0
£1
££
£3
£4
£5
£b
£7
olant riase
American Cyanatnid


Ciba-Geigy Coro


DeSoto, Inc.


Diamond Snatiroch


Diaaond ShamrocK


E. I. duPont de Nera.


EaiKay Cnew. Co.


Korflex. Inc.


Georgia Pacific


state
NJ


NJ


TX


NJ


GA


NJ


NJ


NC


WA


ty
p
F
S
P
F
S
P
F
S
P
F
S
P
F
3
P
F
S
P
F
S
P
F
S
p
F
5
type stacK_nuw
P
F
S
P
F
S
P
F
S
P
F
S
P
F
3
P
F
S
P
F
S
P
f
S
P
F
5
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
S
1
1
1
1
1
i
i
height
19.60
3.00
7.70
13.00
3.00
7.70
13.00
3.00
7.70
3.00
3.00
7.70
13.00
3.00
7.70
15. 80
3.00
7.70
13.00
3.00
7.70
13.00
3.00
7.70
13.00
3.00
7.70
area vent_tyoe
0.
00
£0000.00
0.
0.
£0000.
0.
00
00
00
00
0.00
5000.
0.
0.
£0000.
0.
0.
00
00
00
00
00
00
£0000.00
0.
0.
£0000.
0.
0.
5000.
0.
0.
20000.
0.
0.
£0000.
0.
00
00
00
00
00
00
00
00
00
00
00
00
00
0
1
0
0
1
0
0
1
0
0
1
0
0
1
0
0
1
0
0
1
0
0
1
0
0
1
0
diameter
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.150
0.000
0.076
velocity
17. £00
0.010
0.010
6.300
0.010
0.010
6.300
0.010
0.010
6.300
0.010
0.010
34.000
0.010
0.010
0.170
0.010
0.010
6.300
0.010
0.010
6.300
0.010
0.010
6.300
0.010
0.010
team
3£0
£93
£93
320
£93
£93
320
£93
£93
3£0
£93
£93
3£0
£93
£93
3£0
£93
£93
3£0
£93
£93
320
£93
£93
3£0
£93
£93
era_
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
max
000
000
000
000
000
000
000
000
000
000
000
0.000
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
000
000
000
000
000
000
000
000
000
000
000
000
000
000
000
en 155 ions
41.000
41.0*1
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000
41.000

-------
                   Table  A-8.   MODELING  PARAMETERS  FOR  NAPHTHALENE EMISSIONS
              FROM  PRODUCTION  OF SURFACE  ACTIVE AGENTS  --  2-NAPHTHALENESULFONIC ACID
Record*  update  pollutant
     1  10/15/86 Naphthalene
     2  10/15/86
     3  10/15/86
     4  10/14/86
     5  10/15/86
     6  10/15/86
     7  10/15/86
     8  10/15/86
     9  10/15/86
    10  10/15/86
    11  10/15/86
    12  10/15/86
    13  10/15/86
    14  10/15/66
    15  10/15/86
    16  10/15/86
    17  10/15/86
    18  10/15/86
source_cat
2-nao.5ulfomc acid
plant_nunb sic_code plant_nai»e latitude longitude urban city
1 2843
1
1
2 2843
2
2
3 2810
3
3
4 2843
4
4
5 2843
5
5
6 2843
6
6
Allied Corp.


Anerican Cyanamid Co


American Cyanamid


DeSoto, Inc.


E. I. duPont de New.


EmKay Chenical Co.


394818
0
0
332830
0
0
403800
0
0
324448
0
0
394100
0
0
403912
0
0
752712
0
0
812748
0
0
741500
0
0
972000
0
0
752924
0
0
741130
0
0
0 Claytnont
0
0
0 Marietta
0
0
0 Linden
0
0
0 Fort Worth
0
*
0 Deepwater
0
0
0 Elizabeth
0
•

-------
    Table A-8.   MODELING  PARAMETERS FOR NAPHTHALENE EMISSIONS
FROM PRODUCTION OF  SURFACE  ACTIVE  AGENTS -- 2-NAPHTHALENESULFONIC ACID
                              (concluded)
Record It
1
£
3
4
5
6
7
8
9
10
11
1£
13
14
15
16
17
18
plant_name
Allied Corp.


American Cyanamd Co


American Cyanamd


DeSoto, Inc.


E. I. duPont de New.

t
EiaKay Chenical Co.


state
DE


OH


NJ


TX


NJ


NJ


t)
P
F
S
P
F
S
P
F
S
P
F
S
P
F
S
P
F
S
type
P
F
B
P
F
S
P
F
S
P
F
S
P
F
S
P
F
S
stack_mui
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
height
13.00
3.00
7.70
13.00
3.00
7.70
19.80
3.00
7.70
13.00
3.00
7.70
15.80
3.00
7.70
13.00
3.00
7.70
area
0.00
20000.00
0.00
0.00
£0000.00
0.00
0.00
£0000.00
0.00
0.00
5000.00
0.00
0.00
£0000.00
0.00
0.00
5000.00
0.00
vent_type
0
1
0
0
1
0
0
1
0
0
1
0
0
1
0
0
1
0
dianeter
0.150
0.000
0.076
0.150
0.00k)
0.076
0.150
0.000
0.076
0.150
0.000
0.076
0.15ID
0.000
0.076
0.150
0.000
0.076
velocity
6.300
0.010
0.010
6.300
0.010
0.010
17. £00
0.010
0.01U
6.300
0.010
0.010
0.170
0.010
0.010
6.300
0.010
0.010
temp
3£0
£93
Z93
3£0
£93
£93
3£ti
£93
d93
3£0
£93
£93
3£0
,£93
• £93
3£0
£93
£93
en.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
max
000
000
00U
000
00m
000
000
000
00k)
000
000
000
00*
000
000
000
000
000
emissions
350.
350.
350.
350.
350.
350.
350.
350.
350.
350.
350.
350.
350.
350.
350.
350.
350.
350.
000
000
000
000
000
000
000
006
1000
000
000
000
00k)
000
000
000
IW0
000

-------
                   Table  A-9.   MODELING  PARAMETERS  FOR  NAPHTHALENE  EMISSIONS
                                  FROM  PRODUCTION OF MOTH  REPELLANT
Records  ideate   ooilutant
     1  10/14/66 Maantnalene
     £  10/14/66
     3  1(2/14/66
     4    /  /
                        source_cat
                        ."loth Reoe 11 ant
oiarit nu«iD sic coce oiant name
        i £879
        1
        1
Morfiex, Inc.
                                                             Kincaid Enterorises
                   latitude longitude uroan city
.6    795324
0        0
0        0
24    615030
0 Greenooro
i
0
0 Nitre-
Secorcs  Dian.
      1  norflex, Inc.
                     state woe
                     NC   P
i     '                    F
3                         5
4  Mttcaici Er.terorises  wV
Id:
*
0
0
0
heicnt
0.00
0.00
0.00
0.00
area vent_tyoe diameter
0. 00
0.00
0.00
0.00
0 0. 000
0 0. 000
0 0. £00
0 0.000
velocity t
0. 000
0.000
0.000
0.000

'3
0
0
0
enijnax
£.000
0. 000
0.000
0.000
emissions
0.000
0. tit
0.000
0. Mi

-------
                                   Table A-10.   MODELING  PARAMETERS  FOR  NAPHTHALENE EMISSIONS
                                         FROM PRODUCTION OF MISCELLANEOUS  ORGANIC  CHEMICALS


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-------
Table A-10.   MODELING  PARAMETERS  FOR NAPHTHALENE EMISSIONS
       FROM  PRODUCTION  OF MISCELLANEOUS ORGANIC  CHEMICALS
                             (concluded)
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-------
REFERENCES

1.   Standard Industrial  Classification  Manual, Office of Management
     and Budget,  1972.

2.   "Chemical  Profile,"  Chemical  Marketing Reporter.  October 29, 1984,
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3.   Hughes, et.  a!.   Chemical  Economics Handbook, Naphthalene.  SRI
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4.   1985 Directory  of Chemical  Producers, United States.  SRI Inter-
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5.   Ohio EPA Emissions Inventory  System for  1985.   April 15, 1986.

6.   Texas Air Pollution  Control Board,  Permit Files, Austin, TX.
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7.   1984 Emission Inventory, Summary by Process, for Koppers Co.,  Inc.,
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8.   Telecon.  J. Cugnini, Delaware Department of Natural Resources
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9.   1984 Emission Inventory, Summary by Process, for Union  Carbide,
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10.  Polycyclic Aromatic Hydrocarbons -  An  Environmental  Materials
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11.  Kirk-Othmer, Encyclopedia of Chemical  Technology,  3rd  edition,
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12.  Letter  from D.R. Cavote, Portsmouth Local  Air  Agency,  Portsmouth,
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13.  1985  Directory of Chemical Producers,  United States.  SRI  Inter-
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14.  Brown,  S.L., et.  al.   Research Program on Hazard Priority  Ranking
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     Washington,  D.C.  PB-263  164.  April 1975.
                                   A-44

-------
15.  Benzene Emissions  from  Coke  By-Product Recovery Plants.  Back-
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16.  Van Osdell,  et.  al.   Environmental Assessment of Coke By-Product
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17.  Project Summary  for Construction Permit  for Modification to a
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18.  "Chemical  Profile,"  Chemical Marketing Reporter.  July 7, 1986.
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19.  Memo  to S. Levine, Illinois  Environmental Protection  Agency, from
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20.  Letter and permit  application  from H.A.  Hegeman, Koppers Company,
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21.  U.S.  Environmental  Protection  Agency.  Compilation of Air Pollu-
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22.  Handbook of Chemistry and Physics.   54th edition, 1973-74.  CRC
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23.  VOC Emissions  from Volatile  Organic  Liquid Storage Tanks - Back-
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24.  Fugitive Emission  Sources of Organic Compounds - Additional Infor-
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     Triangle Park, NC.  April 1982.   p.  3-6.

25.  Perry and Chilton, Chemical  Engineer's Handbook.  Fifth edition.
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26.  Telecon.  D. Knapp, St.  Louis  Air Quality Office. St. Louis, MO,
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27.  Letter from Boggs, F.L.,  Union Carbide,  Institute, West Virginia,
     to C. Beard, West  Virginia Air Pollution Control Commission,
     Charleston, WV.   May 8,  1986.

28.  Hughes, et. al.   Chemical Economics  Handbook, Naphthalene.
     SRI InteTnatTonal.  March 1985.   pp. 300-7600A - 300-7600Z.

                                 A-45

-------
29.  Letter from J.L.  Noe, American Cyanamid, Willow Island, WV, to
     C. Beard,  West  Virginia Air  Pollution Control Commission,
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30.  West Virginia Air Pollution  Control Commission, 1981 Air Emission
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31.  Chemical  Sources  USA, 1985.

32.  Specific  Contaminant Report, dated  September 9, 1986.  New Jersey
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33.  Production and  Use of Naphthalene.  Versar,  Inc., Springfield, VA.
     Contract  No. 68-01-3852,  Task 22.   Prepared  for U.S. Environmental
     Protection Agency, Office of Water  Planning  and Standards,
     Washington, D.C.   January 1980.

34.  Kirk-Othmer.  Encyclopedia of Chemical Technology.  Third edition,
     Vol. 5.  John  Wiley & Sons,  New  York, NY.  1979.

35.  Telecon.   C. Beard, West  Virginia Air Pollution Control Commission,
     Charleston, WV, with  D.G. Cole,  Pacific Environmental Services,
     Inc., Durham,  NC.  September 22, 1986.

36.  Letter from K.  Chaudhari, Virginia  'Air Pollution  Control Board,
     Richmond, VA,  to D.G. Cole,  Pacific Environmental Services,  Inc.,
     Durham, NC.  August 20, 1986.   Subject:  Greenwood  Chemical  Company
     no longer in operation  as manufacturing or emitting source due to
     explosion and fire destroying  facility April  1985;  no plans  to
     rebuild.

37.  Telecon.   T. McGillick, New  York State Department of Environmental
     Conservation, White Plains,  NY,  with  D.G. Cole,  Pacific  Environ-
     mental Services,  Inc.,  Durham,  NC.  .August 20,  1986.

38.  Telecon.    L. Malcolm,  Ohio  State Air  Pollution  Control Agency,
     Akron, OH, with D.G. Cole,  Pacific  Environmental  Services,  Inc.,
     Durham, NC.  August 7,  1986.

39.  Telecon.   C. Goeller, Oklahoma City Health Department, Oklahoma
     City, OK, with D.G. Cole, Pacific Environmental  Services,  Inc.,
     Durham, NC.  August 7,  1986.

40.  Human Exposure to  Atmospheric Concentrations of Selected Chemicals,
     Volume II, SAI.   1982.

41.  Energy Information Administration, U.S.  Department  of  Energy.
     Coke  and  Coal  Chemicals in  1979.  Energy  Data Report.  Washington,
     D.C.  October  31,  1980.  pp. 4-5.

42.  West  Virginia  Air  Pollution Control Commission (WVAPCC), Permit
     Files, Charleston, WV.   Information obtained from visit  to WVAPCC
     office by K. Meardon,  PES,  Inc., Durham,  NC.  October  1-2, 1986.
                                    A-46

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43   Memorandum.   R.  Pandullo,  Radian  Corp., to File.  Documentation of
     HEM Inputs  for Emissions Associated  with Chlorinated Hydrocarbons
     Use in Pesticide Monitoring.   June 3,  1986.

44   Distillation Operations  in Synthetic Organic Chemical Manufacturing -
     Background  Information for Proposed  Standards,  FPA-450/3-83-005a.
     U.S. Environmental  Protection Agency,  Office of Air Quality Planning
     and Standards, Research  Triangle  Park, NC. December 1983.  pp. 8-13.
                                  A-47

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                   APPENDIX B

PROCEDURES FOR ESTIMATING NAPHTHALENE EMISSIONS
      FROM COKE BY-PRODUCT RECOVERY PLANTS

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                        K E M 0 R A N D U M

                                                     October 7, 1986

TO:       Bob Lucas, EPA:ESED:CPB

FROM:     David Cole, PES, Inc.

THRU:     Ken Meardon, PES,
SUBJECT:  Procedures for Estimating Naphthalene Emissions from Coke
          By-Product Recovery Plants (EPA Contract No. 68-02-3887,
          Assignment 43)
     This memorandum describes two procedures for estimating
naphthalene emisions from coke by-product recovery plants.  The
first method uses coke and coal tar production figures coupled
with a coal tar materials balance to derive a plant-wide naphthalene
emission factor.  The second method is based on a process-specific
approach that is derived from limited data from one coke by-product
recovery plant.  Following the descriptions of these methods, an
example calculation is presented to estimate naphthalene emissions
from a specific plant.  Emissions are calculated by using each method
as a basis for comparison.

Method 1:  Development of a Plant-wide Naphthalene Emission Factor

     A plant-wide naphthalene emission factor is developed based on
a material balance of a representative coke by-product recovery
plant and the amount of naphthalene estimated in coal tar production.
A naphthalene emission factor is needed on a "kilogram (kg) of
naphthalene per megagram (Mg) of coke produced" basis because coke
production rates are available for each coke by-product plant.  To
derive this factor, PES used the following procedure:

1.   Estimate annual coal tar production based on (1) the amount of
     naphthalene in coal tar produced (1978 estimate) and (2) the
     weight percent of naphthalene in dry coal  tar:

     1978 coal-tar naphthalene production           = 230,000 Mg (Reference I'
     Average Weight % naphthalene of dry tar (U.S.) = 8.80%      (Reference 2\

     Coal Tar Production =  230,000 Mg  =  2.614 Tg
                              0.088
                                 B-l

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2.   Estimate relative amount of coal tar produced per megagram of
     coke from material  balance of a representative coke by-product
     recovery plant:

      380 MCJ Coal Tar  =  0.05156 Kg Coal Tar per t-ig Coke (Reference 3)
        7370 Kg Coke

3.   Estimate annual coke production based on (1) and (2) above:

         2.614 Tg coal tar	  =  50.7 Tg coke production, U.S.
     0.05156 Mg coal tar/Mg coke     (1978 estimate)

     Note:  This estimate approximates 1979 U.S. coke production
            figure  (48.0 Tg) from Reference 4.

4.   Calculate naphthalene emission factor from estimate of total
     naphthalene emissions to atmosphere from coal  tar production
     (Reference 1) and total U.S. coke production from (3) above:

      300 Mg naphthalene      5.92 Mg naphthalene per Tg coke produced,
     50.7 Tg coke produced =  or 0.00592 kg naphthalene per Mg coke produced

Method 2:  Development of a Process-Specific Emission Estimation Procedure

     Eight specific naphthalene emission sources have been identified at
coke oven by-product recovery plants.  Naphthalene emission factors are
developed as described below for most of these sources based on limited
data from a screening study at one coke by-product plant:

1.   Coke Oven Doors

          A naphthalene emission factor of 0.73 g/hr/oven is reported
     in Reference 1, based on EPA estimates (1977).

2.   Tar Processing

     a.  Decanting

          Based on  estimate of 4.1 g/Mg coal for emissions of polynuclear
     aromatic compounds (PNA) (Reference 3, p. 4) of which the major
     component is naphthalene (Reference 1, p. 28) (PES estimates 70%),
     and based on ratio of 1.42 Mg coal to 1 Mg coke (Reference 3),
     the following  naphthalene emission factor is calculated:

     0.70 x 4.1g/Mg coal  x 1.42 Mg coal    =  4.1 g naphthalene
                              Mg coke          per Mg coke produced

     b.  Dewateri ng/storage

          Naphthalene emissions are negligible based on total PNA
     compound estimates for this source (Reference 3, p. 4)
                                  B-2

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3.   Final  Cooler Unit

          No air emissions of naphthalene are expected since the
     unit is a closed system (Reference 5, p. 3-32).

4.   Naphthalene Separation Tank

          This step involves the separation of naphthalene from
     water by gravity separation (indirect water final cooling
     process), in open basins.   Therefore, fugitive emissions of
     naphthalene are expected.   A total vapor rate of 33.8 vapor
     per sm3 was measured directly above the tank surface in a
     screening study (Reference 3, p. 93-94), but no vent stream
     was at a rate sufficient to be measured.  The total  exposed
     surface area was about 1000 ft^, but the actual surface exposed
     to the wind by the naphthalene slurry was not known  nor was
     the rate of entrained air  flow in the tank available.  Con-
     sequently, because of the  lack of data to quantify naphthalene,
     no emission factor was developed from the naphthalene separation
     tank.  Subjectively, however, the odor of naphthalene in this
     area was reported to be quite strong.

5.   Naphthalene processing (Drying/Melting)

          Each drying tank may  have a vent stack which extends
     about 5m above the tank.  From Reference 3 (pp. 95-96), the
     vent rate from the tank from one plant was estimated to be 2.9
     sm3 vapor/Kg coke by measuring the rate of air entering a
     hatch of a tank due to the chimney effect.  A-naphthalene
     concentration of 533 g/snP was found, or 1.56 kg naphthalene
     per Mg coke.  Since this concentration represented about twice
     the plant's total naphthalene production, the sample was not
     representative of the average emission rate (Reference 3, p. 95,
     99).  However, assuming a  worst-case and for the lack of other
     data, naphthalene emissions can be estimated to be the following:

     533 y/sm3 x 2.9 sm3/Mg coke = 1546 g/Mg coke'

6.   Tar Storage Tanks (containing naphthalene)

          A VOC emission factor of 281 g/Mg coke production is
     based on Reference 5, p. 7-5, for tar storage.  Assuming that
     the percentage of naphthalene in the primary coke tar storage
     tank is between 18 to 32 percent (PES assumes 25% for calculating
     emission factors) from Reference 6, and applying that percentage
     to the VOC emission factor, then the naphthalene emission factor
     can be estimated to be:  0.25 x 281g/Mg coke = 70.25 g/Mg coke

7.   Naphthalene Storage Tanks

          No throughput data are available for naphthalene storage
     tanks at coke by-product recovery plants.  If data were available,
     then the fixed-roof tank equations from EPA Publication AP-42
     for calculating breathing  and working losses could be applied,
     assuming 96% of contents of tank is naphthalene (Reference 6).


                                  B-3

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8.   Equipment Leaks

          Equipment leaks of naphthalene are assumed to originate from
     exhausters, pump seals, valves, relief valves, sampling connections,
     and open-ended lines.  VOC emission factors from coke by-product
     plants (Reference 5, p. 3-43)  are used to approximate naphthalene
     emissions.  Naphthalene constitutes about 96% of crude naphthalene
     produced and 70% of coal  tar produced.  Assuming the naphthalene
     concentration increases as the coke by-products are recovered
     (which is certainly the case when refining the naphthalene), PES
     has assumed that naphthalene emissions throughout the plant represent
     75% of total VOC fugitive emissions.  Number of pieces of equipment
     per model plant is based  on number of units in Reference 5, p.
     6-13.
                                  B-4

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Example Calculation of Plant-Specific and Nationwide Emissions of
Naphthalene

I.   USS-Fairfleld Coke Plant

     Naphthalene emissions from the USS-Fairfield coke plant in
Fairfield, Alabama, were calculated based on each of the above
methods for comparison.  Specific data from this  plant (e.g.,
number of ovens) are used in the calculations when available.

Using Method 1, the naphthalene emissions are calculated as follows:

     0.00592 kg naphthalene x 4324 Me, coke    x  365 days  x    1 Mg
         Mg coke                     day              yr      j x 103|
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     Pump seal  emissions  are  based  on  VOC  emission  factor  of
2.7 kg/source/day (Reference  5,  p.  3-43):

9 pumps x 0.75 x 2.7  kg VOC/pump/day  x 365 days  = 6,652  kg/yr
                                            yr   = 6.7  Hg/yr
Valves

Assume total  of 105 valves  (Reference  5,  p.  6-13);  75% of
VOC is naphthalene:

105 valves x  0.75 x 0.26  kg VOC/valve/day  x  365  days   =   7473  kg/yr
                                              yr
                                                    =7.5  Hg/yr
Re!ief Valves

Assume 5 relief valves (Reference 5,  p. 6-13), 75%  of  VOC  is
naphthalene:

5 relief valves x 0.75 x 3.9 kg  VOC/relief valve/day  x 365 days
= 5338 kg/yr

= 5.3 Mg/yr

Sampli ng connecti ons

Assume 10 sampling connections (Reference 5, p. 6-13), 75%
of VOC is naphthalene:

10 sampling connections x 0.75 x 0.36 kg VOC/sampling connection/day
  x  365 days  = 986 kg/yr

              = 1.0 Mg/yr

Open-ended 1ines

Assume 22 open-ended lines, (Reference 5, p. 6-13), 75% of VOC is
naphthalene:

22 open-ended lines x 0.75 x 0.055 kg VOC/open-ended line/day x
  365 days  = 331 kg/yr

            = 0.33 Mg/yr

Exhausters

Assume 6 exhausters, 75% of VOC  is naphthalene:

6 exhausters x  0.75 x  1.2 kg VOC/exhauster/day x 365 days
                                                      yr
=   1971  kg/yr
                       B-6

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          =  2 Mg/yr naphthalene

          Therefore, equipment leaks of naphthalene at the plant total
          about 23 Mg/yr.

     Total  naphthalene emissions from the Fairfield plant = 2,583 Mg/yr.

II.  Nationwide Naphthalene Emissions from Coke By-Product Plants

     Total  nationwide estimate may be calculated by each method as follows:

          Method 1:

          0.00592 -kg naphthalene          Mg coke nationwide
                 Mg coke         x 51,377        ,jay         x

              days      1 Mg_
          365 -yf- x  i x iQ3 ky  =111 Mg/yr.

          Method 2:

          Using all of the above emission factors for the emission sources
          described in Method 2, nationwide totals are the following:

                                            Nationwide
                 Source                   Estimate, Mg/yr

              Coke Oven Doors                  28.2
              Tar Decanting                    76.9
              Naphthalene Processing       28,991
              Tar Storage Tanks             1,313
              Equipment Leaks                 540.7a

                               Total  =  -   30,949.8 Mg/yr (with naphthalene
                                                           processing)
                                  or        1,958.8 Mg/yr (without naphthalene
                                                           processing)

Summary and Conclusions

     Emissions of naphthalene from the Fairfield plant based on Method  1
total  about 9.34 Mg/yr compared to 2,583 Mg/yr for Method 2.  Even sub-
tracting out the naphthalene processing emissions (which are obviously
overstated), the total naphthalene emissions from the plant based on
Method 2 are 143 Mg.
aFrom Reference 5, calculation  of nationwide equipment leaks  was  based on
 a model  plant approach in which the percent naphthalene in VOC (75%)  was
 multiplied by the appropriate VOC emission factor, the number of  pieces of
 equipment per model  plant, and the total  number of model  plants based on
 coke production.
                                B-7

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     The nationwide estimates of naphthalene from coke by-product  plants
calculated above are much higher than  two other  nationwide  estimates  found
in the literature (i.e.,  34 and 40 Mg/yr from total  naphthalene production,
References 1 and 8, respectively).  Process-specific emissions  derived  from
Method 2 are based in most cases on total organics or vapor emissions due
to the fact that naphthalene was difficult,  or impractical  to sample,
particularly when naphthalene processing tanks were  sampled.  In addition,
the relative percentage of naphthalene in a  VOC  stream is difficult to
quantify in the case of equipment leaks because  naphthalene is  prevalent
throughout most of the coke by-product plant.  Therefore, process-specific
emissions are based on data and assumptions  that may overstate  emissions.
Since both plant-specific and nationwide emissions from Method  1 more
closely approximate the estimates found in the literature than  Method 2,
Method 1 appears to be a  more reasonable procedure for quantifying naphtha-
lene emissions from coke  by-product plants.
                                B-8

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REFERENCES

1.    Polycyclic Aromatic Hydrocarbons - An Environmental  Materials
     Balance.   Acurex Corp., Rosslyn, VA, for U.S. Environmental
     Protection Agency, Monitoring and Data Support Division,
     Washington, DC.  EPA Contract 68-01-6017.  January 1981.
     p. 27-28.

2.    Kirk-Othmer, Encyclopedia of Chemical Technology.  Third
     edition,  volume 22.  John Wiley and Sons:  New York.  1983.
     p. 572.

3.    VanOsdell, D.W., et. al.   Environmental  Assessment of Coke By-
     product Recovery "pTants.   Research Triangle Institute, Research
     Triangle  Park, NC.  For U.S. Environmental  Protection Agency,
     Industrial Environmental  Research Laboratory, Research Triangle
     Park, NC.  EPA-600/2-79-016.  January 1979.  p. 23.

4.    Energy Information Administration, U.S.  Department of Energy.
     Coke and  Coal  Chemicals in 1979.  Energy Data Report.
     Washington, D.C.  October 31, 1980.  pp. 4-5.

5.    Benzene Emissions from Coke By-Product Recovery Plants - Background
     Information for Proposed  Standards.  EPA-450/3-83-016a.  U.S.
     Environmental  Protection  Agency, Office  of Air Quality Planning
     and Standards, Research Triangle Park, NC.   May 1984.  p. 3-1.

6.    Letter from A.A. Spinola, USS; Pittsburgh,  PA, to D.R. Goodwin,
     U.S. Environmental Protection Agency, Office of Air Quality
     Planning and Standards, Research Triangle Park, NC.   July 23, 1979.
     Information at Clairton and Gary Coke plants.  EPA Docket No.
     A-79-16,  II-D-3.

7.    Letter from A.A. Spinola, USS, Pittsburgh,  PA, to D.R. Goodwin,
     EPA.  August 1, 1979.  Emissions from Fairfield, AL, plant.  EPA
     Docket No. A-79-16, II-D-4.

8.    Production and Use of Naphthalene.  Versar, Inc., Springfield,'
     VA.  For U.S.  EPA, Office of Water Planning and Standards,
     Washington, D.C.  Contract No.  68-01-3852, Task 22, Subtask
     1.  January 1980. p. 30.
                                B-9

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                                      TECHNICAL REPORT DATA
                              (Please read Instructions on the reverse before completing)
 1  REPORT NO.

  EPA-450/3-88-003
                                                              3. RECIPIENT'S ACCESSION NO.
 4. TITLE AND SUBTITLE
  Summary of Emissions Associated
  with Sources  of Naphthalene
                                                              5. REPORT DATE
                                                               October 30,  1986
                                                               6. PERFORMING ORGANIZATION CODE
 7 AUTHOR(S)
                                                               8. PERFORMING ORGANIZATION REPORT NO
9 PERFORMING ORGANIZATION NAME AND ADDRESS
 Air Quality Planning and Standards
 Office of  Air and Radiation
 U.S. Environmental Protection Agency
 Research Triangle Park,  NC  27711
                                                               10 PROGRAM ELEMENT NO.
                                                               11 CONTRACT/GRANT NO.
 12. SPONSORING AGENCY NAME AND ADDRESS
  DAA for Air  Quality Planning and Standards
  Office of Air and Radiation
  U.S.  Environmental Protection Agency
  Research Triangle Park.  NC  27711	
                                                              I 13. TYPE OF REPORT AND PERIOD COVERED
                                                              14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
  This report  contains information on  naphthalene emissions sources and current emission
  rates.
                                 KEY WORDS AND DOCUMENT ANALYSIS
                   DESCRIPTORS
 8. DISTRIBUTION STATEMENT
                                                b.IDENTIFIERS/OPEN ENDED TERMS
                                                                            c.  COSATI 1 icId/Group
                                                                             13B
                                                19 SECURITY CLASS jThis Reportl    21. NO OF "AGES
                                               ^Unclassified
                                                20 SECURITY CLASS . r/
                                                Unclassified
                                                                             115
EPA Form 2220-1 {Rev. 4-77)   PREVIOUS EDITION is OBSOLETE

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