United States
        Environmental Protection
        Agency

        Air   	
Office of Air Quality
Planning and Standards
Research Triangle Park. NC 27711
EPA-454/R-93-044
March 1994
&EPA
     LOCATING AND ESTIMATING
            AIR EMISSIONS
          FROM SOURCES OF
          CHLOROBENZENES
               (REVISED)

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                       EPA-454/R-93-044
ATING AND ESTIMA'
   AIR EMISSIONS
FROM SOURCES OF
 CHLOROBENZENES
     (REVISED)
 Office Of Air Quality Planning And Standards
    Office Of Air And Radiation
  U. S. Environmental Protection Agency
   Research Triangle Park, NC 27711
        March 1994

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This report has been reviewed by the Office  Of Air Quality Planning And Standards

nSr^^T^/f ?Cy' ^ has *"* aPP~ved for publSon3  Any mlndon ofad
names or commercial products is not intended to constitute endorsement or recommendation for use
                                 EPA-454/R-93-044
                                        11

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                             TABLE OF CONTENTS
 Section
                                                                           Page
 DISCLAIMER	
 LIST OF FIGURES	    	*	'	" $
 LIST OF TABLES	'.'.'.'.'.'.'.'.'.'.'.'.'.'. '.'. '.'.'.'.'.'.'.'. \'.'.'.'. ' vi

 1.0    PURPOSE OF DOCUMENT		                    M
       1.1    Reference for Section 1.0	. ....	1-5

 2.0    OVERVIEW OF DOCUMENT CONTENTS	            2-1
       2.1    References for Section 2.0	        	2-5

 3.0    BACKGROUND	 .	  3^
       3.1   . Nature of Pollutant	  3-1
             3.1.1  Properties of Chlorobenzenes	3.5
          -   3.1.2  Properties of Monochlorobenzene	3.5
             3.1.3  Properties of Dichlorobenzenes	         3.5
             3.1.4  Properties of Trichlorobenzenes  	].... 3-7
             3.1.5  Properties of Hexachlorobenzene	         3.7
       3.2    Overview of Production and Use	     .'!.'.'! 3-8
       3.3    References for Section 3.0	           	3_16

4.0    EMISSIONS FROM CHLOROBENZENES PRODUCTION	 4-1
     . 4.1    Equipment Leak Emissions ..	.*.'.'!.'!! 4-1
      4.2    Monochlorobenzene Production .'.....	           4.4
             4.2.1  Process Description	..........]„ 4-4
            4.2.2  Emissions	4.9
      4.3    Dichlorobenzenes Production 	          4_10
            4.3.1  Ortho-  and Para-Dichlorobenzene	.	4_H
            4.3.2  Meta-Dichlorobenzene	4_13
            4.3.3  Emissions	        4_14
      4.4   Trichlorobenzenes Production	   4_14
      4.5   References for Section 4.0	*'	4.13

5.0   EMISSIONS FROM MAJOR USES OF CHLOROBENZENE	5-1
      5.1    Manufacture of Nhrochlorobenzenes from Monochlorobenzene	  5-1
            5.1.1  Process Description	       5_2
            5.1.2  Emissions	  	5_2
      5.2    Manufacture of Diphenyl Oxide from Monochlorobenzene ............  5-3
            5.2.1  Process Description	          5.4
            5.2.2  Emissions	  	5.4
      5.3    Manufacture of Phenylphenols from Monochlorobenzene '.'.'.	5-5
      5.4    Manufacture of 4,4'-Dichlorodiphenylsulfone from Monochlorobenzene ! '. '. 5-5
                                      111

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                         TABLE OF CONTENTS (continued)
 Section
                                                                               Page
              5.4.1  Process Description	         5.5
              5.4.2  Emissions	„	 5-6
       5.5    Manufacture of 3,4-Dichloroaniline from Ortho-Dichlorobenzene ".'.'.'.'.'.'. 5-7
              5.5.1  Process Description	! .' 5-7
              5.5.2  Emissions	                 5.9
       5.6    Use of  Para-Dichlorobenzene in the Production of Polyphenylene
              Sulfide	        5_jQ
              5.6.1  Process Description	5_11
              5.6.2  Emissions	      5.^3
       5.7    Use of Chlorobenzenes in the Manufacture of Toluene Diisocyanate ....  5-13
              5.7.1  Process Description	5-14
              5.7.2  Emissions	                5.47
       5.8    Use of Chlorobenzenes in the Production of Dyes and Pigments	5-17
              5.8.1  Use of Chlorobenzenes in the Synthesis of Intermediates	5-18
              5.8.2  Use of Chlorobenzenes as Process Solvent	5-20
       5.9    Use of Monochlorobenzene and Ortho-Dichlorobenzene as Dye Carriers in
             Textile Dyeing	      5_3Q
       5.10   Use of 1,2,4-Trichlorobenzene as a Dye Carrier in the TExtile Dyeing
             Industry		     5_31
       5.11   Use of Para-Dichlorobenzene as a Pesticide	5-32
       5.12   Use of 1,2,4-Trichlorobenzene in  the  Manufacture of the  Herbicide
             Banvel®	           5,33
             5.12.1 Process Descriptions	             5.33
             5.12.2 Emissions	               5.34
       5.13   Use  of  Ortho-Dichlorobenzene  as   a Solvent  in   Pharmaceutical
             Manufacturing	       5.35
             5.13.1 Process Description	5.35
             5.13.2 Emissions	      5.37
       5.14   Miscellaneous Uses of Chlorobenzenes  	'.['.  5.33
       5.15   References for Section 5.0	'.'.'.'.'.'.'.'.'.  5-39

6.0    EMISSIONS  FROM   THE   USE  OF   MATERIALS    CONTAINING
       CHLOROBENZENES	^
       6.1    Use of para-Dichlorobenzene in Moth Control	 6-1
       6.2    Use of para-Dichlorbbenzene as a Space Deodorant  .	6-2
             6.2.1  Process Description	„	.'.'!!.'.' 6-2
             6.2.2  Emissions	        g_3
       6.3    Use  of  Chlorobenzenes  as  Solvents  in  Organic  Solvent  Cleaning
             Operations	f               g_3
             6.3.1  Process Description	  6-4
             6.3.2  Emissions
                                        IV

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                      TABLE OF CONTENTS (continued)
 Section
                                                                     Page
      6.4   Use of Trichlorobenzenes in Wood Preservatives 	
      6.5   References for Section 6.0	5.7

 7.0   BYPRODUCT EMISSIONS - PROCESSES UNRELATED TO PRODUCTION
      OR USE OF CHLOROBENZENES	7.!
      7.1   Volatilization  of  Chlorobenzenes  from  Wastewater  Treatment
            Operations	           7_j
      7.2   Hazardous and Solid Waste Incineration	7,3
      7.3   Burning of Waste Oil	  	7_/r
      7.4   Hexachlorobenzene Generation During Chlorinated Solvent Production '. '. '. 7-6
            7.4.1  Process Description	..           7.7
            7.4.2  Emissions	   •••••.. ^
      7.5   References for Section 7.0	'.....	'.'.'.'.'.'.'.''"  7-14

 8.0   AMBIENT AIR AND STATIONARY SOURCE TEST PROCEDURES          8-1
      8.1    EPA Method TO-1 	                      	g ,
      8.2   EPA Method TO-14 	  "	'	g~2
      8.3    EPA Method 0030	'	8"5
      8.4   EPA Method 5040	        '	    8~5
      8.5    EPA Method 0010	'.'.	o"g
      8.6    EPA Method 8270	'.'.'.'.'.''.'.'.'.'.'.'.'.'.'.'.'.'.	8-11
      8.7    References for Section 8.0	8-12

APPENDIX A    POTENTIAL SOURCE  CATEGORIES  OF  CHLOROBENZENES
                EMISSIONS	               A_j

APPENDIX B     TEXTILE FIBER  DYEING FACILITIES WITH ANNUAL SALES
                GREATER THAN $1 MILLION	B-l

APPENDIX C     SUMMARY  OF   EMISSION   FACTORS  LISTED  IN  THIS
                DOCUMENT	

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                                LIST OF FIGURES
Number
3-1
                                                                              Page
       End Uses of Monochlorobenzene	. .	          3_U

 3-2    End Uses of o-Dichlorobenzene  	     3_j2

 3-3    End Uses of p-Dichlorobenzene	    3_13

 3-4    End Uses of Trichlorobenzene	3.44

 4-1    Monochlorobenzene Continuous Production Process Diagram	4-7

 4-2    Dichlorobenzene and Trichlorobenzene Continuous Production Diagram  .......  4-12

 5-1    Process Row Diagram of Polyphenylene Sulfide Manufacture	5-12

 5-2    Basic Operations that may be Used in Toluene Diisocyanate Production  	5-16

 5-3    Basic Operations that may be Used in Pharmaceutical Manufacturing	5-36

 7-1    Process Flow for the Production of Carbon Tetrachloride and Perchloroethylene
       by Hydrocarbon Chlorinolysis	7.7

 7-2    Process Flow Diagram for the Production of Perchloroethylene and
       Trichloroethylene by Chlorination	         7_g

 7-3    Process How Diagram for the Production of Perchloroethylene and
       Trichloroethylene by Oxychlorination	  7-9

 8-1    EPA Method TO-1 Sampling System	8-3

 8-2    Tenax® Cartridge Design	         3.4

 8-3    Canister Sampling System  	       g.g

8-4    Schematic of Volatile Organic Sampling Train (VOST)	3.7

8-5    Schematic Diagram of Trap Desorption/Analysis System	8-9

8-6    Modified Method 5 Sampling Train	   g_10
                                       VI

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                                  LIST OF TABLES
 Number
                                                                               Page
 3-1    Synonyms and Trade Names for Chlorobenzenes	3.2



 3-2    Properties of Industrially Significant Chlorobenzenes	3.3


 3-3    End Uses of Chlorobenzenes	                 3-15



 4-1    Average Emission Factors for Fugitive Equipment Leak Emissions   		4-3



 4-2    Control Techniques and Efficiencies Applicable to Equipment Leak Emissions ... 4-5


 4-3    Chemical Producers of Monochlorobenzene - 1989	„	    4.9



 4-4    Emission Factors for a  Hypothetical Monochlorobenzene Production Plant .....  4-10


 4-5    Chemical Producers of o-Dichlorobenzene and p-Dichlorobenzene - 1989  .....  4-13



 4-6    Emission Factors for a  Hypothetical o-Dichlorobenzene Production Plant	4-15



 4-7    Emission Factors for a  Hypothetical p-Dichlorobenzene Production Plant ......  4-15


 5-1   Chemical Producers of  o- and p-Nitrochlorobenzenes - 1989  .....             5.3



 5-2   Pesticides Using 3,4-Dichloroaniline as an Intermediate - 1989 .............. 5-8
                                      o

 5-3   Chemical Producers of  3,4-Dichloroaniline - 1989	      5.9


 5-4   Emission Factors for the Production of 3,4-Dichloroaniline	     5-10


 5-5   Toluene Diisocyanate Production Locations and Capacities	  5-18


 5-6   Dyes and Pigments Utilizing Chlorobenzene Solvents  	5-21


 5-7    Dye and Pigment Names and Manufacturers	          5.22



 5-8    Dye and Pigment Manufacturing Companies	5_26



 5-9    Emission Factors for o-Dichlorobenzene in Dye Synthesis	5-29


7-1    Emission Factors for Wastewater Treatment Operations	          7.3


7-2    Emission Factors for Municipal Waste Combustion ..	        7.5
                                        vu

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                          LIST OF TABLES (continued)
Number
                                                                          Page
7-3   Chemical Producers of Trichloroethylene - 1989 ................. i,        7.10



7-4   Chemical Producers of Carbon Tetrachloride - 1989	7-11



7-5   Chemical Producers of Perchloroethylene - 1989	   7_12
                                     viu

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                               EXECUTIVE SUMMARY

        Emissions of chlorobenzenes into the atmosphere are of special significance because of
 the 1990  Clean Air Act Amendments.   These amendments mandate that chlorobenzenes
 emissions be subject to standards that allow for the maximum degree of reduction of emissions
 and mat, by 1995, a list of source categories be established that accounts for no less than 90
 percent of chlorobenzenes emissions. This document is designed to assist groups interested in
 inventorying air emissions of chlorobenzenes by providing a compilation of available information
 on sources and emissions of these substances.

       The chlorinated derivatives  of benzene are a group of stable, colorless and pleasant
 smelling compounds.  Only the mono-, di-, and trichlorobenzenes have important industrial
 applications. Information on hexachlorobenzene is included due to its past usage and generation
 as a byproduct in other manufacturing processes.

       In the U.S., chlorobenzenes are produced by three companies at three locations.   In
 1989, the production capacity for monochlorobenzene was 168,000 megagrams (371 million
 pounds), for ortho-dichlorobenzene, 36,700 megagrams (80.9 million pounds), and for para-
 dichlorobenzene, 60,000 megagrams (132 million pounds). Few data are available on production
 of more highly chlorinated benzenes.

      Major uses for monochlorobenzene are in the manufacture of phenol and ortho- and para-
 nitrochlorobenzenes, diphenyl oxide, dye and herbicide intermediates, and sulfone polymers.

      Ortho-dichlorobenzene is used primarily in the synthesis of 3,4-dichloroaniline, which
is used in the production of herbicides. It is also used in the manufacture of dyes, as a solvent
m paint removers and engine cleaners, and as a de-inking solvent.

      Para-dichlorobenzene is used in the manufacture of l,2,4-trichlorobenzene,polyphenylene
                                        IX

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 sulfide resins, room deodorants, moth proofing products and as an intermediate in the dye and
 insecticide industries.
       1,2,4-trichlorobenzene is used in pesticide formulation, as a process solvent, chemical
 intermediate, lubricant and heat transfer medium.


       Hexachlorobenzene is no longer produced or imported in the U.S. for commercial use.
It is formed as a process waste byproduct during the manufacture of specific chlorinated solvents
and pesticides.
       At the time of publication of this document, estimates of nationwide chlorobenzenes
emissions were not available.  Updates  to this document will attempt to incorporate any
nationwide emissions information subsequently available.

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                                    SECTION 1.0

                             PURPOSE OF DOCUMENT


       The Environmental Protection. Agency (EPA) and State and local air pollution control
agencies are becoming increasingly aware of the presence of substances in the ambient air that

may be toxic at certain concentrations.  This awareness, in turn, has led to attempts to identify

source/receptor relationships for these substances and to develop control programs to regulate

emissions.  Unfortunately, very little information is available on the ambient air concentrations

of these substances or on the sources that may be discharging them to the atmosphere.


       To assist groups interested in inventorying air emissions of various potentially toxic
substances, the EPA is preparing a series of documents which compiles available information on

sources and emissions of these substances.  The primary purpose of this document is to revise

and update the information presented in the Locating and Estimating Emissions From Sources

of Chlorobenzenes (EPA-450/4-84-007m) document which was originally published in 1984.
Prior documents in the series are listed below:
      Substance

      Acrylonitrile
      Carbon Tetrachloride
      Chloroform
      Ethylene Bichloride
      Formaldehyde (Revised)
      Nickel
      Chromium
      Manganese
      Phosgene
      Epichlorohydrin
      Vinylidene Chloride
      Ethylene Oxide
      Chlorobenzenes
      Polychlorinated Biphenyls (PCBs)
      Polycyclic Organic Matter (POM)
      Benzene
      Organic  Liquid Storage Tanks
      Coal and Oil Combustion Sources
      Municipal Waste Combustors
EPA Publication Number

EPA-450/4-84-007a
EPA-450/4-84-007b
EPA-450/4-84-007c
EPA-450/4-84-007d
EPA-450/2-91-012
EPA-450/4-84-007f
EPA-450/4-84-007g
EPA-450/4-84-007h
EPA-450/4-84-007i
EPA-450/4-84-007J
EPA-450/4-84-007k
EPA-450/4-84-0071
EPA-450/4-84-007m
EPA-450/4-84-007n
EPA-450/4-84-007p
EPA-450/4-84-007q
EPA-450/4-88-004
EPA-450/2-89-001
EPA-450/2-89-006
                                        1-1

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        Substance
        Perchloroethylene and Trichlorethylene
        1,3-Butadiene
        Chromium (supplement)
        Sewage Sludge
        Styrene
        Methylene Chloride
EPA Publication Number
EPA-450/2-90-013
EPA-450/2-89-021
EPA-450/2-89-002
EPA-450/2-90-009
EPA-450/4-91-029
EPA-454/R-93-006
        This document deals specifically with chlorobenzenes.  Its intended audience includes
 Federal, State, and local air pollution personnel and others who are interested in locating potential
 emitters of chlorobenzenes, and making gross estimates of air emissions therefrom.

        Because of  the  limited  amounts of data  available  on some potential sources of
 chlorobenzenes emissions, and since the configurations of many sources will not be the same as
 those described here, this document is best used as a primer to inform air pollution personnel
 about 4L) the types of sources that may emit chlorobenzenes, (2) process variations and release
 points that may be  expected within  these sources, and (3) available emissions information
 indicating the potential for chlorobenzenes to be released into the air from each operation.

       The reader is  strongly cautioned against using the emissions information contained in this
 document to try to  develop an exact assessment of emissions  from any  particular facility.
 Because insufficient  data are available to develop statistical estimates of the accuracy of these
 emission factors, no  estimate can be made of the error that could result when these factors are
 used to calculate emissions from any given facility.  It is possible, in some extreme cases, that
 order-of-magnitude differences could result between actual and calculated emissions, depending
 on differences in source configurations, control  equipment, and operating practices.  Thus, in
 situations where an accurate assessment of chlorobenzenes emissions is necessary, source-specific
information should be obtained to confirm the existence of particular emitting operations, the
types and effectiveness of control measures, and the impact of operating practices.  A source test
and/or  material balance should be considered as the best means to determine air emissions
directly from an operation.
                                          1-2

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        In addition to the information presented in this document, another potential source of
 emissions data for chlorobenzenes is the Toxic Chemical Release Inventory (TRI) form required
 by Section 313 of Title m of the Superfund Amendments and  Reauthorization Act of 1986
 (SARA 313).1 SARA 313 requires owners and operators of certain facilities that manufacture,
 import, process or otherwise use certain toxic chemicals to report annually their releases of these
 chemicals to any environmental media. As part of SARA 313, EPA provides public access to
 the  annual emissions data.   The  TRI data include general facility information,  chemical
 information, and  emissions data.   Air emissions  data are reported as total facility release
 estimates, broken  out into fugitive and point components. No individual process or stack data
 are provided to the EPA.  The TRI requires the use of available stack monitoring or measurement
 of emissions to comply with SARA 313. If monitoring data are unavailable, emissions are to be
 quantified based on best estimates of releases to the environment.

       The reader is cautioned that the TRI will  not likely provide facility, emissions, and
 chemical release data sufficient for conducting detailed exposure modeling and risk assessment
 In many cases, the TRI data are based on annual estimates of emissions (i.e., on emission factors,
 material balances,  engineering judgement).   The reader is urged to obtain TRI data in addition
 to information provided in this document to locate potential emitters of chlorobenzenes, and to
 make preliminary estimates of air emissions from these facilities. To obtain an exact assessment
 of air emissions from processes at a specific facility, source tests or detailed material balance
 calculations should be conducted, and detailed plant site information should be compiled.

       Each L&E document,  as  standard procedure,  is  sent to government,  industry, and
 environmental groups wherever EPA is aware of expertise.  These groups are  given the
 opportunity to review the document, comment, and provide additional data where applicable.
 Where necessary, the documents are then revised to incorporate these comments. Although  these
 documents have undergone extensive review, there may still be shortcomings.  Comments
 subsequent to  publication are  welcome and will be addressed based on available time and
resources.  In addition, any information is welcome on process descriptions, operating parameters,
control measures, and emissions information  that would enable EPA to  improve the contents of
this document  Comments and information may be sent to the following address:

                                         1-3

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Chief, Emission Factor and Methodologies Section
Emission Inventory Branch, (MD-14)
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
                          1-4

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1.1

1.
REFERENCE FOR SECTION 1.0


Toxic Chemical  Release Reporting:   Community Right-To-Know.  Federal Register
52(107): 21152-21208. June 4, 1987.                                    ^
                                     1-5

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                                     SECTION 2.0
             P-
                        OVERVIEW OF DOCUMENT CONTENTS

       As stated in Section 1.0, the purpose of this document is to assist Federal, State and local
 air pollution agencies ,and others  who  are  interested  in locating  potential  air emitters of
 chlorobenzenes and making gross estimates of air emissions therefrom. Because of the limited
 available background data, the Information summarized in this document does not and should not
 be assumed  to represent the  source configuration or emissions associated with any particular
 facility.

       This section provides  an overview of the contents of this document It  briefly outlines
 the nature, extent, and format of the material presented in the remaining sections of this report.

       Section 3.0 of this document briefly summarizes the physical and chemical characteristics
 of chlorobenzenes,  and provides an overview of their production and use. This  background
 section may be useful to someone who needs to develop a general perspective on the nature of
 this substance and how it is manufactured and consumed.

       Section 4.0 of this document focuses on major production source categories that may
 discharge air emissions containing chlorobenzenes. Section 5.0 discusses emissions from major
 uses of chlorobenzenes. Section 6.0 addresses emissions as a result of releases after manufacture
 from products containing chlorobenzenes.  Section 7.0 describes sources of emissions as a result
 of the manufacture of another product, or as a by-product of another process (e.g.,  burning of fuel
 oil). Example process descriptions and flow diagrams are given in addition to available emission
 factor estimates for each major industrial source category described in Sections 4.0,5.0, 6.0, and
7.0.  Individual companies involved with either the  production or use of chlorobenzenes  are
reported  throughout the document  Information reported  is extracted primarily  from trade
publications.
                                         2-1

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        Section 8.0 of this document summarizes available procedures for source sampling and
  analysis of chlorobenzenes,  The summaries provide an overview of applicable sampling and '
  analytical procedures, citing references for those interested in conducting source tests.

        Appendix A identifies potential source categories of chlorobenzenes emissions by Standard
  Industrial Classification (SIC) code and associated description. These potential source categories
  do not necessarily denote significant sources of chlorobenzene emissions. The readers interested
  in cross referencing SICs with Source Classification Codes (SCCs) and associated descriptions
  should consult the Crosswalk/Air Toxic Emission Factor Database Management System, Version
 2.0  (October 1992) and/or the Volatile Organic  Compound (VOC)IParticulate Matter (PM)
 Speciation Database Management System, Version 1.4 (October 1992).1-2 Appendix B lists textile
 dyeing facilities with sales greater than $1,000,000.  Appendix C summarizes, in table format,
 all emission factors listed in this document
        Each emission factor listed in Sections 3.0 through 7.0 has been assigned an emission
 factor grade based on the criteria for  assigning data quality and emission factor ratings as
 required in the document Technical Procedures for Developing AP-42 Emission Factors and
 Preparing AP-42 Sections.3  These criteria for rating test data used to develop emission factors
 are presented below.  The data used to develop emission factors are rated as follows:
       A -
       B  -
       C  -
       D  -
Tests performed by a sound methodology  and reported  in enough detail for
adequate validation.  These tests are not necessarily EPA reference test methods,
although such reference methods are certainly to be used as a guide.
Tests that are performed by a generally sound methodology but lack enough detail
for adequate validation.

Tests that are based on a nonvalidated  or draft methodology or that lack a
significant amount of background data.
Tests that are based on a generally unacceptable method but  may provide an
order-of-magnitude value for the source.
       Because of the almost impossible task of assigning a meaningful confidence limit to
industry-specific variables  (e.g.,  sample size vs. sample  population, industry and  facility
                                          2-2

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 variability, method of measurement), the use of a statistical confidence interval for an emission

 factor is not practical.  Therefore, some subjective quality rating is necessary.   The following

 emission factor quality ratings are applied to the emission factor tables.


        A - Excellent. The emission factor was developed only from A-rated test data taken from
        many  randomly chosen facilities in  the industry population.  The source category' is
        specific enough to minimize variability within the source category population.

        B - Above average.  The emission factor was developed only from A-rated test data from
        a reasonable number of facilities. Although  no specific bias is evident, it is not clear if
        the facilities tested represent a random sample of the industries.  As in the A rating, the
        source category is specific enough to minimize variability within the source category
     .   population.

        C - Average. The  emission factor was developed only from A- and B-rated test data from
        a reasonable number of facilities.  Although  no specific bias is evident, it is not clear if
        the facilities tested represent a random sample of the industry.  As in the A rating, the
        source category is specific enough to minimize variability within the source category
        population.

        D - Below average.  The emission factor was developed only from A- and B-rated test
        data from  a small number of facilities, and  there may be reason to suspect that these
        facilities do not represent a random sample of the industry. There also may be evidence
        of  variability within the  source  category  population.   Limitations on  the use  of  the
        emission factor are footnoted in the emission factor table.
       E " Poor- The emission factor was'developed from C- and D-rated test data, and there
       may be reason to suspect that the facilities tested do not represent a random sample of
       the industry.  There  also may be  evidence of variability  within  the source category
       population.  Limitations on the use  of these factors are always footnoted.

       U - Unrated or Unratable. The emission factor was developed from suspect data with no
       supporting documentation to accurately apply an A through E rating. A "U" rating may
       be applied in the following circumstances:

              - a gross mass balance estimation
              - QA/QC deficiencies found with C- and D-rated test data
              - gross engineering judgement
              - technology transfer
"Source category: A category in the emission factor table for which an emission factor has been calculated; generally a single process.

                                           2-3

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       This document does not contain any discussion of health or other environmental effects
of chlorobenzenes. It does include a discussion of ambient air monitoring techniques; however,
these ambient air monitoring methods may require modifications for stack sampling and may
affect data quality.
                                        2-4

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2.1    REFERENCES FOR SECTION 2.0
 1.
2.
3.
4.
U.S. Environmental Protection Agency, Crosswalk/Air Toxic Emission Factor Database
Management System, Version 2.0,   Office of Air Quality Planning  and Standards
Research Triangle Park, NC, October 1992.

U.S. Environmental Protection Agency, Volatile Organic Compound (VOC)IParticulate
Matter (PM) Speciation Database Management System, Version J.4, Office of Air Quality
Planning and Standards, Research Triangle Park, NC, October 1992.

U.S. Environmental Protection Agency, Technical Procedures for Developing AP-42
Emission Factors and Preparing AP-42 Sections, Draft Document, Office of Air Quality
Planning and Standards, Research Triangle Park, NC, March 1992.

Group discussion meeting on applying "U" rating to emission factors. Anne Pope, EIB;
Robin Baker Jones, Midwest Research Institute; Garry Brooks, Radian Corporation; and
Theresa Moody, TRC Environmental Corporation.
                                       2-5

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                                     SECTION 3.0
                                    BACKGROUND
 3.1  NATURE OF POLLUTANT
       The chlorinated derivatives of benzene, QH^ CL., form a group of stable, colorless,
 pleasant smelling compounds. Chlorine can be substituted for the six hydrogen atoms on the
 benzene ring, forming twelve different chlorinated compounds:
       monochlorobenzene
       ortho-dichlorobenzene
       meta-dichlorobenzene
       para-dichlorobenzene
       1,2,3-trichlorobenzene
       1,2,4-trichlorobenzene
       1,3,5-trichlorobenzene
       1,2,3,4-tetrachlorobenzene
       1,3,4,5-tetrachlorobenzene
       1,2,4,5-tetrachlorobenzene
       pentachlorobenzene
       hexachlorobenzene
       Only the mono-, di-, and trichlorobenzenes have important industrial applications. Thus*
                  *                     #
relevant information on each of these groups is discussed in this report  Although it has no

current commercial applications, information on hexachlorobenzene is included due to its past

usage and generation as a byproduct in other manufacturing processes.  Synonyms and trade

names for these chlorinated products are presented in Table 3-1.  The physical properties of the

industrially significant chlorobenzenes are listed in Table 3-2.
                                         3-1

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                                     TABLE 3-1.
                   SYNONYMS AND TRADE NAMES FOR
                              CHLOROBENZENES
   Pollutant
   Monochlorobenzene
 Synonyms
 •••••••M              	
                                       ••^•V^^Mm^^HH^BB^MI^^Mm
 benzene chloride; chlorobenzene; chlorobenzol; phenyl chloride;
 MCB; Na-C54886                       -
  o-Dichlorobenzene
 orthodichlorobenzene; ortho-dichlorobenzene; ortho-
 dichlorobenzol; 1,2-dichlorobenzene; ODB; ODCB; Dizene®-
 Chloroben®; Dowtherm® E; "Special termite fluid"; Termitidl;
 Dilatin DB
  m-Dichlorobenzene
 metadichlorobenzene; meta-dichlorobenzol; meta-
 dichlorobenzene; 1,3-dichlorobenzene; m-phenylenedichloride
  p-Dichlorobenzene
paradichlorobenzene; para-dichlorobenzene; para-
dichlorobenzol;  1,4-dichlorobenzene; PDB; PDCB;
Di-chloricide®;  Paracide®; Paradi®; Paradow®; Paramoth®;
Santochlor"; Parazene; Paranuggets; jparaCrystals;
p-chlorophenyl chloride; Evola; Persia-Perazol
  1,2,3-Trichlorobenzene
 1,2,3-trichlordbenzol; 1,2,3-TCB; 1,2,6-ttichlorobenzene; vic-
 trichlorobenzene
  1,2,4-Trichlorobenzene
1.2,4-trichlorobenzol;  1,2,4-TCB; unsymtrichlorobenzene
  1,3,5-Trichlorobenzene
1,3,5-trichlorobenzol; 1,3,5-TCB; sym-trichlorobenzene;
s-trichlorobenzene; TCBA
  Hexachlorobenzene
Amatin; Anticarie; Bunt-Cure; Bunt-No-More; Co-op Hexa;
Grariox NM; HCB; HEXA C.B.; Julin's Carbon Chloride; No
Bunt Liquid; pentachlorophenyl chloride; perchlorobenzene;
phenyl perchloryl;  Sanocide; Smut-Go; Snieciotox
Source:  References 1-3.
                                       3-2

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3-3

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below:
       Molecular structures for the chlorobenzenes discussed in this document are presented
                      a
              monochlorobenzene
                                                              a
                                                                    a
                                                      ortho-dichlorobenzene
                      a
                      a
             para-dichlorobcnzene
                                                              a
mcta-dichlorobenzenc
                     a
             1 A3-trichlorobenzene
                                                              a
                                                                    a
        a
1 ,2,4-trichlorobenzene
                     a
             1,3 ,5-tiichlorobenzenc
        a
        a
  hexachlorobenzene
                                           3-4

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 3.1.1  Properties of Chlorobenzenes

        As a group, chlorobenzenes are much less reactive than the corresponding chlorinated
 derivatives of alkyl compounds and are similar in reactivity to the vinyl halides.  They are very
 stable to nucleophilic attack due to resonance in the molecule resulting in a shortening of the
 carbon-chlorine bond distance and an increase in bond strength.1

        At room temperature and pressure, chlorobenzenes are not attacked by air, moisture, or
 light. They are not affected by steam, prolonged boiling with aqueous or alcoholic ammonia,
 other alkalis, hydrochloric acid, or dilute  sulfuric  acid.  Hydrolysis takes place at elevated
 temperatures in the presence of a catalyst to form phenols.1

        Chlorobenzenes are  subject  to attack by  hot concentrated sulfuric  acid  to  form
 chlorobenzene-p-sulfonic acid. Nitric acid will react with chlorobenzenes at the meta- and para-
 positions on the ring to form  chloronitrobenzenes at -30°C to 0°C (-22°C  to 32°F).  At higher
 temperatures, the nitration will either proceed further to  form  a dinitrochloro-compound,
 chloronitrophenol, or a nitrophenol.1   Chlorobenzenes  are  attacked by  electrophilic agents.
 Substitution for monochlorobenzene is predominantly para-; with some ortho-substitution. The
 higher chlorinated benzenes tend to resist electrophilic substitution but can  be substituted under
 extreme conditions.1

       Chlorobenzenes also undergo some free radical reactions.  Formation of organometallic
 compounds  (grignards, aryl-lithium compounds) provides a useful route to many organic
 intermediates. Photochemical transformations occur on irradiation of chlorinated benzenes, which
 are much less stable to radiation than benzene. When subjected to ultraviolet irradiation or pulse
 hydrolysis in solution, chlorobenzenes may polymerize to biphenyls, chloronaphthalenes, or more
 complex products.1   The ability of chlorobenzenes to undergo wide varieties of chemical
reactions makes chlorinated benzenes useful as reactants in numerous commercial processes to
produce varied products.  All chlorinated derivatives of benzene are soluble in lipids. Partition
coefficient data for chlorobenzenes show an increase in partition coefficient with an increase in
                                          3-5

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  the degree of chlorination.  Li general, a positive correlation exists between partition coefficient
  and degree of bioaccumulation.1
 3.1.2  Properties of Monochlorobenzene

        Monochlorobenzene has a high solubility in nonpolar solvents, however,  it is almost
 insoluble in water. If it accumulates in water systems, it tends to sink due to its density.  There
 may be a greater tendency for monochlorobenzene to accumulate in still lake waters rather than
 fast moving streams  and rivers because of its comparatively high volatility.1

        Monochlorobenzene is most likely to enter the atmosphere from fugitive emission sources,
 including solvent evaporation. Monochlorobenzene will exist in the atmosphere in the vapor
 phase and wiU react with hydroxyl radicals, producing chlorophenol byproducts of decomposition.
 The atmospheric half-life of monochlorobenzene is 17 days. Atmospheric half-life will decrease
 in polluted air containing nitric oxide. Products of decomposition will include chloronitrobenzene
 and chloronitrophenols.  Photolysis in the atmosphere  is expected to be slower  (30 days),
 resulting in monochlorobiphenyl production.4

 3.1.3  Properties of Dichlorobenzenes

       Ortho- and meta-dichlorobenzene  are neutral, mobile, colorless  liquids with similar
 characteristics and odors. Para-dichlorobenzene is a pleasant smelling white crystalline  solid.
 The crystals readily sublime at room temperature. Solubilities of the dichlorobenzenes are similar
 to those of monochlorobenzene, and  the dichlorobenzenes also form a number of azeotropes.1

       Solvent evaporation is the major  source of  o-dichlorobenzene  in the atmosphere.
Approximately 25 percent of annual solvent production using o-dichlorobenzene is expected to
be lost to the atmosphere. It will exist in the atmosphere in the vapor phase and will react with
hydroxyl radicals for an estimated half-life of 24 days.4  Meta-dichlorobenzene is most likely
to enter the atmosphere from fumigation products application,  as well as chemical intermediate
and solvent use.  It exists in the atmosphere in the vapor phase and can react with hydroxyl

                                          3-6

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 radicals for an estimated half-life of 14 days.4  Para-dichlorobenzene is most likely to enter the
 atmosphere  from  the  volatilization  of  household  deodorant products  and  moth  flakes.
 Approximately  70  to 90 percent of p-dichlorobenzene's annual production may eventually be
 released to the atmosphere.  It exists in the atmosphere  in the vapor phase and reacts with
 hydroxyl radicals for an estimated half-life of 31 days.  Byproducts  of decomposition in the
 presence of smog include dichloronitriphenol, dichloronitrobenzene, and dichlorophenol.4

 3.1.4   Properties of Trichlorobenzenes

        The trichlorinated benzenes are white crystalline solids, except for 1,2,4-trichlorobenzene,
 which is a colorless liquid.  Solubilities are similar, with insolubility in water, generally good
 solubility in alcohol, ether, benzene, and chloroform, and relatively high lipid solubility.1

        1,2,4-Trichlorobenzene may enter the atmosphere through its use in the manufacture of
 dye carriers, herbicides, chlorinated benzenes, dielectric fluids, and a variety of other applications.
 It exists in the atmosphere in the vapor phase and reacts with hydroxyl radicals for an estimated
 half-life of 18.5 days.  Byproducts of phdtodegradation in the atmosphere include 1,3- and 1,4-
 dichlorobenzene.4  1,3,5-Trichlorobenzene may enter the atmosphere through  its use as an
 industrial chemical, chemical intermediate, solvent, and emulsifier.  It exists in the atmosphere
 in the vapor phase and will  react with hydroxyl radicals for an  estimated half-life of 6.17
 months.4

 3.1.5  Properties of Hexachlorobenzene

       Hexachlorobenzene is a colorless crystalline solid at normal temperatures which slowly
degrades in the environment  Although insoluble in water, it is slightly soluble in cold alcohol
and soluble in benzene, chloroform, and ethyl ether.  Rapid sublimation of the crystals occurs
in the temperature range of 0°C to 30°C (32° to 86°F).6

       Hexachlorobenzene may enter the atmosphere through waste incineration or chlorinated
hydrocarbon manufacture.  Hexachlorobenzene is extremely resistant to biodegradation and is

                                          3-7

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 therefore very persistent in the environment  It exists in the atmosphere in the vapor phase and
 the adsorbed phase.  Hexachlorobenzene degradation in the atmosphere has an estimated half-life
 of 2 years. Due to the stable characteristics  of hexachlorobenzene, long range transport in the
 atmosphere is likely.4

 3.2  OVERVIEW OF PRODUCTION AND USE

        Twelve chlorinated benzenes can be formed by replacing some or all of the hydrogen
 atoms on the benzene ring with chlorine atoms.  With the exceptions of 1,3-dichlorobenzene,
 1,3,5-trichlorobenzene, and 1,2,3,5-tetrachlorobenzene, the chlorinated benzenes are produced in
 the presence of a Friedel-Crafts catalyst The usual catalyst is ferric chloride (FeCl3), which can
 be added to the reaction mixture or generated in situ by exposing a large iron surface to the
 liquid being chlorinated.  Each compound, except hexachlorobenzene, can be chlorinated further;
 hence, the product is always a mixture of chlorinated benzenes.  Pure compounds are obtained
 by distillation and crystallization.8

       Currently, there are three known domestic producers of chlorobenzenes, each operating
 at a  single location.  Individual  plants producing chlorobenzenes vary in capacity from 0.5
 million to 80 million kilograms (1 to 176 million pounds). In 1989, the total production capacity
 for monochlorobenzene was 168 million kilograms (371 million pounds), for o-dichlorobenzene
 it was  36.7 million kilograms (81 million pounds),  and for p-dichlorobenzene, 60  million
 kilograms  (132 million  pounds).9  Few data  are  available  on  production  of  more highly
 chlorinated benzenes.

       Processes for the manufacture of chlorobenzenes include various chemistry and product
 separation methods. The process currently used by industry is direct chlorination of benzene in
 the presence of a FeCla catalyst to produce monochlorobenzene.  The monochlorobenzene reacts
with the remaining chlorine to form dichlorobenzenes. Hydrogen chloride is a byproduct in both
reactions.  In addition to the two major isomers of dichlorobenzene, ortho- and para-, a very
small amount of the meta-isomer is formed.  As chlorination is continued, tri-, tetra-, penta-, and
hexachlorobenzenes are formed. Usually, trichlorobenzene is the only highly chlorinated product

                                          3-8

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 found in significant amounts.  The degree of chlorination of benzene can be controlled by the
 choice of the catalyst, temperature, and benzene:chlorine ratio in the reactor feed.  Hydrogen
 chloride, a byproduct of the reaction, is  processed under  anhydrous conditions before it is
 absorbed in water. The reaction and the recovery operations, in most cases, are continuous.

        Demand for monochlorobenzene as a feedstock comes mostly from the synthetic organic
 chemical manufacturing industries.  Accordingly, the simple manufacturing process often allows
 monochlorobenzene to be manufactured in the same plant in which it is consumed.  Historically,
 the two major markets for monochlorobenzene have been  in the manufacture of phenol and o-
 and p- nitrochlorobenzenes.  However, the use of monochlorobenzene as a feedstock in phenol
 manufacturing  has been phased out and  replaced by  cumene.10   Other feedstock uses for
 monochlorobenzene  include use in the manufacture of  diphenyl  oxide, dye  and herbicide
 intermediates, and sulfone polymers.

       Ortho-dichlorobenzene is used primarily in organic synthesis of 3,4-dichloroaniline, which
 is used as an intermediate in the production of herbicides.  Demand for o-dichlorobenzene as a
 solvent carrier  in  the manufacture  of toluene diisocyanate for polyurethane manufacture has
 increased, and is expected to grow faster than any other use. It is also used as a solvent in paint
 removers and engine cleaners, in de-inking solvents, and in dye manufacture."
                                        »

       Para-dichlorobenzene is used predominantly in the manufacture of polyphenylene sulfide
 resins.  In 1988, polyphenylene sulfide resin manufacturing  consumed 22  percent of aU the
 p-dichlorobenzene manufactured for that year. In addition to the manufacture of polyphenylene
 sulfide, p-dichlorobenzene is used  in  the  manufacture  of room deodorants, moth proofing
 products, and l,2,4,trichlorobenzene.  Para-dichlorobenzene is also used as an intermediate in the
 dyes and insecticide industries.12

       1,2,4-Trichlorobenzene is primarily used in pesticide formulation.  The manufacture of
the pesticide Banvel® consumed approximately 15 million pounds of trichlorobenzene in 1988.
 1,2,4-Trichlorobenzene is also used as a process solvent, chemical intermediate, lubricant, and
a heat transfer medium.13
                                          3-9

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       Hexachlorobenzene is no  longer  produced or  imported into  the  United States  for
 commercial usage.  Formerly, hexachlorobenzene was used as an active ingredient in fungicidal
 preparations, but this use has been nearly eliminated due to the cancellation of registry of HCB-
 containing fungicides.  Currently, hexachlorobenzene is formed as a process waste byproduct
 during the manufacture of specific chlorinated solvents and pesticides.13

       Meta-dichlorobenzene,    1,2,3-trichlorobenzene,   and    1,3,5-trichlorobenzene,
pentachlorobenzene, and all three tetrachlorobenzenes are not discussed here due to their limited
production and  use.  Summaries of the current uses of each  of  the industrially significant
chlorobenzenes are presented in Figures 3-1  through 3-4, along with the percentage of total
product devoted to each use.

       Table 3-3 shows some of the end products  from chlorobenzenes.  These products and
some of their production processes will be covered  in detail in Sections 5.0 and 6.0.
                                        3-10

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Benzene  +  Chlorine
Monochlorobenzene
 Production of
- niirochlorobenzene
   (42 percent)

 Use  cs solvent  in
 toluene diisocyanate
_ manufacture, herbicide
 formation, and as
 a degreasing agent
   (28 percent)

 Production of diphenyl
. ether and phenyi
 phenols
   (15 percent)


. Sulfone  polymers
   (5  percent)

 Other uses
   (10  percent)
                   Figure 3-1.  End uses of nionochlorobenzene12
                                       3-11

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Benzene  -f Chlorine
o—Dichlorobenzene
                                                            Chemical  manufacturing
                                                            (86  percent)
Solvent  uses
(10 percent)
                                                            Other uses
                                                            (4 percent)
                  Figure 3-2.  End uses of o-dichlorobenzene12
                                     3-12

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Benzene  4- Chlorine
p—Dichiorobenzene
                                                             Exports
                                                               (30 percent)
                                                             Polyphenyiene suifide
                                                             resin
                                                               (22 percent)
                                                             Other uses
                                                               (22 percent)
                                                             Space deodorant
                                                               (16 percent)
                                                             Moth  repellant
                                                               (10 percent)
                 Figure 3-3.  End uses of p-dichlorobenzene"
                                     3-13

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Benzene -f  Chlorine
Trichlorobenzene
                                                           Production of herbicides
                                                           (75 percent)
                                                           Use as a  dye carrier
                                                           and other uses
                                                            (25 percent)
                   Figure 3-4. End uses of trichiorobenzene11
                                      3-14

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                             TABLE 3-3.
                    END USES OF CHLOROBENZENES
Chlorobenzene Isomer and Use
Monochlorobenzene
Nitrochlorobenzenes
Solvents
Diphenol ether and phenylphenols
Sulfone polymers
Dichlorobenzenes
p-Dichlorobenzene
Deodorant
Moth repellant
Resins
o-Dichlorobenzene
Chemical manufacture
Solvents
Trichlorobenzenes
Chemical manufacture
Dye carrier
End Use

Used as intermediates in the manufacture of rubber
chemicals, agricultural chemicals, antioxidants,
dyes and pigments
Used as a solvent in processes to produce rubber
products, pesticides, Pharmaceuticals, and resins
Used as an intermediate for dyes, optional
bleaches, ultraviolet stabilizers for plastics,
Pharmaceuticals and pesticides
Used in engineering plastics


Used as a space and sanitary deodorant
Used as moth repellant
Used as an intermediate in polyphenylene sulfide
resins for high performance plastics

Used as an intermediate for the production of
pesticides
Used in formulated paint strippers and cleaners and
as a heat transfer agent

Used as an intermediate for the production of dyes,
pesticides and dielectric fluids
Used as a dye carrier in the textile fabric dyeing
industry
Source: References 10-12.
                                3-15

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3.3

1.




2.




3.



4.



5.



6.



7.


8.



9.


10.



11.


12.
 REFERENCES FOR SECTION 3.0
                   p"
 U.S. Environmental Protection Agency, Investigation of Selected Potential Environmental
 Contaminants:  Halogenated Benzenes, EPA-560/2-77-004, Office of Toxic Substances,
 Washington DC, July 1977, pp. 6-43.

 U.S. Environmental Protection Agency, Health Assessment Document for Chlorinated
 Benzenes, EPA-600/8-84-015a, Office of Research and Development, Cincinnati, Ohio,
 April 1984, pp. 3-6.


 Sax, N.I. and R.J. Lewis, Dangerous Properties of Industrial Materials, Seventh Edition,
 Volumes I & II, Van Nostrand Reinhold, New York, NY, 1989.

 Handbook of Environmental Fate and Exposure Data for Organic Chemicals, Volume /,
 Lewis Publishers, Inc., Chelsea, Michigan, 1990.

 Reid, R.C., Prausnitz, J.M., and T.K. Sherwood, The Properties of Gases and Liquids,
 Third Edition,  McGraw-Hill Book Company, New York, NY, 1977, p.  184.

 Windholz, M. (ed.), The Merck Index, Tenth Edition, Merck and Company, Rahway, NJ,
 1984. pp. 298, 444, 677, 1377.

 Weast, R.C. (ed.), CRC Handbook of Chemistry and Physics, 59th Edition, CRC Press
 Inc., West Palm Beach, FL, 1978, pp. C-153, 157, 171.

 Kirk-Othmer Encyclopedia of Chemical Technology, Volume 5, Third Edition,  Wiley-
 Interscience Publication, New York, NY, 1980, pp. 797-808.

 7990 Directory of Chemical Producers, United States of America,  SRI International
 Menlo Park, CA, 1990.

 "Chemical  Profile: Monochlorobenzene,"   Chemical Products Synopsis, Mannsville
 Chemical Products Corporation, Ashbury Park, NJ, July 1990.

 "Chemical Profile: Dichlorobenzenes," Chemical Products Synopsis, Mannsville Chemical
Products Corporation, Asbury Park, NJ, March 1983.

SRI Chemical and Economics Handbook, "Chlorobenzene  Production," Menlo Park, CA
 1989.
13.    Brooks, G.W. and G.E. Hunt, Source Assessment for Hexachlorobenzene, Final Report,
      U.S. Environmental Protection Agency, Pollutant Assessment Branch, Research Triangle
      Park, NC, 1984, pp. 9-18.
                                       3-16

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                                     SECTION 4.0
                EMISSIONS FROM CHLOROBENZENES PRODUCTION

       Production of chlorobenzenes and the associated air emissions are described in this
 section.  Process flow diagrams are included as appropriate, with specific streams or vents labeled
 to correspond with the discussion in the text Emission factors for the production processes are
 presented when available and  control technologies  are described.   Subsection 4.1 presents
 potential problems  and solutions in determining fugitive emissions from  equipment leaks.
 Subsections 4.2 through 4.4 detail production processes by which monochlorobenzene (MCB),
 m-,   o-,  and   p-dichlorobenzenes  (DCS),  isomers   of   trichlorobenzenes  (TCB),   and
 hexachlorobenzene are isolated and processed. The reader should contact the specific facility to
 verify the nature of the process used, production volume, and controls that are in place before
 applying any of the emission factors presented.

       Chlorobenzenes are currently produced by four companies at four locations in the United
 States.   In  1989,  production  capacity for monochlorobenzene was 168 million kilograms
 (371 million pounds), for o-dichlorobenzene it was 36.7 million kilograms (80.9 million pounds),
 and for p-dichlorobenzene, 60 million kilograms (132 million pounds).1
            *:
 4.1 EQUIPMENT LEAK EMISSIONS

       Although the production of chlorobenzenes and other chemicals (discussed in Section 5)
 involves varied processes, all of these processes are known to release fugitive emissions. For this
 reason, equipment leak emissions are discussed before detailed specific process descriptions; are
 referenced hi these descriptions; and, where applicable, are referenced hi the discussion of end
 uses of chlorobenzenes in Section 5.
       Emission factors for fugitive emissions are presented in some of the following subsections
and in Section 5.   However, these  emission factors should be used cautiously  and are only
recommended for obtaining very crude emission estimates. They do not take into account the
actual number of various leaking and nonleaking components within a facility, but are only a

                                         4-1

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  general estimate based on a hypothetical plant  The discussion below presents a more credible
  approach to determining fugitive emissions.

         Emissions occur from process equipment components whenever the liquid or gas streams
  leak from the equipment  Equipment leaks can occur from the following components:  pump
  seals, process valves, compressor seals and safety relief valves, flanges, open-ended lines, and
  sampling connections. Emission estimates can be calculated in the five ways described in the
  EPA publication Protocols for Generating Unit-Specific Emission Estimates for VOC and VHAP
  (EPA-450/3-88-010).2  The methods differ in complexity; however, greater complexity usually
  yields more accurate emission estimates.

        The simplest methodology requires the following input data: number of each component
  type, chlorobenzenes percent weight  of the stream, and  the  number  of hours per year the
  component is in service. These data are then multiplied by EPA's average emission factors for
  the Synthetic Organic Chemical Manufacturing Industries (SOCMI) shown in Table 4-1.  This
  method should be used only if no other emissions data are  available, as it may result in
  overestimating equipment leak emissions.  Emissions can be estimated by  using the formula
  shown below.2
       \No.of     I  I"    Weight percent    1  \Component-speciftc] v ["  No. hrs/yr in    1
       \equipment components]  \Chlorobenzene in the streamj x [ emission factor j x \Chlorobenzene service]
        One of the more complex methodologies may be used to obtain more accurate equipment
 leak emission estimates.   However, these methodologies require that some level of emission
*
 measurements be made for the facility's process equipment components. These methodologies
 are briefly described here, and the reader is referred to Fugitive Emission Sources of Organic
 Compounds-Additional Information on Emissions, Emission Reductions, and Costs for calculation
 details.3
                                          4-2

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                                     TABLE 4-1.
      AVERAGE EMISSION FACTORS FOR FUGITIVE EQUIPMENT
                               LEAK EMISSIONS


Equipment
m^m^mmmmmmmmmmm
Valves


Pump Seals

Compressor Seals
Pressure Relief Seals
Flanges
Open-Ended Lines
Sampling Connections


Service
— n^ m^^l
Gas
Light Liquid
Heavy Liquid
Light Liquid
Heavy Liquid
Gas/Vapor
Gas/Vapor
All
All
All

Emission
Factor
(kg/hr/source)
•""""^""^"•^"•"•TT
0.0056
0.0071
0.00023
0.0494
0.0214
- 0.228
0.104
0.00083
0.0017
0.0150

Emission
Factor
(Ib/hr/source)
0.0123
0.0157
0.00051
0.1089
0.0472
0.5027
0.2293
0.0018
0.0037
0.0331
=====
Emission
Factor
Quality
Rating*
^••••••••m
U


U

U
U
U
U
U
     'Based on engineering judgement
     Source:  Reference 2.
       The first methodology is referred to as the leak/no leak approach.  It is based on a
determination of the number of leaking and nonleaking components.  These values are then
multiplied by two separate sets of EPA-derived emission factors (for leaking and nonleaking).
The second methodology groups screening results of process equipment components into three
ranges: 0 - 1,000 ppmv; 1,000 - 10,000 ppmv; and greater than 10,000 ppmv. The number of
each component falling in  a particular range is then multiplied by the component-specific
emission  factor for that range.  The third methodology uses screening data in correlation
equations derived by EPA.   Finally, the fourth methodology gives each  facility  an option to
develop its own correlation equations, but requires more rigorous testing, bagging, and analysis
of equipment leaks to determine mass emission rates.3
                                       4-3

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        Although  no specific information on emissions controls used  by the  industry was
  identified, equipment components in chlorobenzene service typically have some type of control.
  Generally, control of fugitive emissions requires the use of seaUess or double mechanical seal
  pumps, an inspection and maintenance program, and routine replacement of leaking valves and
  fittings. Typical controls for equipment leaks are listed in Table 4-2.3  In addition, other leakless
  process equipment is available such as leakless valves and sealless pumps.

  4.2  MONOCHLOROBENZENE PRODUCTION

  4.2.1  Process Description

        In general, the most widely used process by which benzene is chlorinated to form MCB
 is by passing dry chlorine into benzene gas in the presence of a catalyst in me following reaction:
                             Catalyst
                          HC1
  Benzene     Chlorine
Monochlorobenzene  Hydrogen Chloride
       The catalyst most often used is ferric chloride (FeCl3); catalysts employed to a lesser
extent are anhydrous aluminum chloride, stannic chloride, molybdenum chloride, Fuller's earth,
and metallic iron or aluminum filings.4  Specific processes, including the continuous, batch, and
Raschig methods of benzene chlorination, are most often used in the production of MCB. A
purification process is then used to further separate the crude MCB from other chlorobenzene
forms and impurities.  Prior to the reaction for all of the above methods, benzene gas is dried
either by azeotropic distillation or with silica gel,  caustic soda, or alumina.  Chlorine gas is
prepared by scrubbing with concentrated sulfuric acid to remove moisture and impurities.5 The
chlorination then proceeds by one of the above-mentioned methods.
                                        4-4

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        The continuous process is most often used because it produces high yields containing up
 to 95 percent MOB and small amounts of DCB isomers. It is not possible by selecting catalyst
 conditions or by modifying process parameters to  prevent the formation of DCBs.  Basic
 operations that may be used in the continuous production of MCB are shown in Figure 4-L  The
 process begins with a series of small, externally cooled cast iron or steel vessels containing the
 catalyst (which may consist of Rashig rings of iron or iron wire). Chlorine is supplied into each
 vessel through suitably positioned inlets to maintain  a large benzene-to-chorine reaction at all
 points along the reaction stream.  The temperature is held between 20°C to 40°C (68°F to 104°F)
 to minimize the production of DCBs which form at higher temperatures. Dry benzene (Stream 1)
 and dried recycled benzene (Stream 2) are introduced into the reactor, which  produces an
 overhead gas  (Stream 3).  The gas stream (containing HC1, unreacted chlorine, inert gases from
 the chlorine feed, benzene, and other VOCs) is  sent to an organic absorber, where  benzene  and
 other VOCs are removed. The bottoms from the organic absorber (Stream 6) flow to  the HC1
 stripper for recovery of HC1.6 The overhead gas (Stream 5) is sent to HC1  absorption. Byproduct
 hydrogen chloride is then removed in the HC1 absorber where it is saturated by washing with a
 refrigerated solvent (e.g., o-dichlorobenzene) or low vapor pressure oil,  and then  recovered in
 wash towers as commercially usable hydrochloric acid.6-7

       Crude  reaction liquid product (Stream 4) enters the crude chlorobenzene distillation
 column which produces overheads (Stream 7) containing most of the chlorobenzenes, unreacted
 benzene, and  some HC1, and a bottom stream from  which catalyst and other byproducts  are
 separated (Stream 8) and processed  for reuse. The overheads (Stream 7) pass through an HC1
 stripper and into a benzene recovery column (Stream 9).  Part of the subsequent benzene-free
 stream (Stream 10) is returned to the "organic absorber while the remainder (Stream 11) enters
 the MCB distillation column. The overhead MCB distillation product (Stream 12) is then stored
 while the bottom  stream containing DCB and TCB isomers is processed.6  Although in most
 cases, isomer  separation processing is  conducted simultaneously with MCB production, it is
 discussed separately in subsequent sections of this document

       In the batch process, benzene is contained in a  deep, iron or mild  steel vessel lined with
lead cooling coils.  The catalyst,  usually  sublimed  FeCl3, is added in a benzene solution.

                                         4-6

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 Chlorine is fed into the bottom of the chlorinator through a lead covered pipe at a rate that
 maintains the temperature below 45°C (113°F) in order to minimize production of DCBs.5  The
 crude chlorobenzene stream and HC1 waste stream are collected and treated as in the purification
 and recovery processes described previously.

       Faith, Keyes, and  Clark's Industrial Chemicals describe a  higher temperature batch
 process where chlorine is bubbled into a cast iron or steel tank containing dry benzene with one
 percent of its own weight of iron filings. Temperature is maintained at 40°C to 60°C (104°F to
 140°F) until density studies indicate that  all benzene is chlorinated.  The temperature  is then
 raised to between 55°C and 60°C (131°F to 140°F)  for six hours until  the density raises to 1.280
 g/cm3 (79.91 Ib/ft3).  The same methods of chlorobenzene purification and HC1 recovery in batch
 form are  then employed.   At 100  percent chlorination, the products  are  80  percent
 monochlorobenzene, 15 percent p-dichlorobenzene, and  5 percent o-dichlorobenzene.7

       Another method of MCB production is the  vapor phase chlorination of benzene by the
 Raschig process. Chlorine produced by the catalytic oxidation of hydrogen chloride is introduced
 into a preheated mixture of benzene vapor, air and steam.  The mixture is then contacted at
 220°C to 260°C (428° to 500°F) with a mixed catalyst of copper oxide and oxides of Group in
 and VEI metals on  a silica gel.  To control the temperature, the catalyst is  packed in small
 diameter tubes. To reduce  DCB formation, only 10 percent of tlie benzene is reacted at a time.
 Purification and recovery proceed as indicated previously.5

       In 1989, three facilities  had the capacity to produce an annual total  of 168 million
 kilograms (371 million pounds).1-8 These three major producers of monochlorobenzene are listed
 in Table 4-3.  Plant-specific production processes from the producers of MCB were not available.
The facUities producing monochlorobenzene are subject to change as market conditions change,
facility ownership  changes, plants are closed, etc.   The reader should verify the existence of
particular facilities by consulting current listings and/or the plants themselves. The level of
chlorobenzene emissions from any given facility is a function of variables such as capacity,
throughput and control measures, and should be determined through  direct contact with plant
personnel.

                                          4-8

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                                       TABLE 4-3.
       CHEMICAL PRODUCERS OF MONOCHLOROBENZENE - 1989
Monsanto Company
Monsanto Industrial Chemicals Company
                                                Sauget,
                                                Illinois
80(176)
    PPG Industries, Inc.
    Chemicals Group
    Industrial Chemical Division
                                            Natrium,
                                            West Virginia
                                                                      20.4 (45)
    Standard Chlorine Chemical Company, Inc.
                                            Delaware City,
                                            Delaware
                                                                      68 (150)
    Total
   Source: References 1, 8.
                                                                     168.4 (371)
4.2.2  Emissions

       Figure 4-1 is labeled to show potential emission release points. The primary emissions
from the production of MCB result from the tailgas treatment vent (A), where inert gases
originally contained in the chlorine feed are vented. The vent stream also contains benzene and
chlorobenzenes. Other sources of chlorobenzene emissions include: benzene drying (B); heavy-
ends processing (C); benzene recovery (D); MCB distillation (E); emissions due to  storage
(F) and handling (G); volatilization of MCB from waste water (H); fugitive emissions during
solid waste handling (I); and fugitive emissions from valves, flanges, seals, etc. (J).6

       Emission factors for the production of monochlorobenzene are  given in Table 4-4. The
emission factors in Table 4-4  are only general estimates derived from site visit measurements.
No specific information was available on particular emission points  included in each of the
emission categories, on  the type of production processes used (batch or continuous),  or on
specific control technologies employed, if any.
                                        4-9

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                                  TABLE 4-4.
             EMISSION FACTORS FOR A HYPOTHETICAL
            MONOCHLOROBENZENE PRODUCTION PLANT*
Emission
Category
Process
Storage
Fugitive
TOTAL
kg MCB Emitted
PerMg
MCB Produced
2.06
0.45
0.69
3.20
Ib MCB Emitted
Per Ton
MCB Produced
mnmmmmmm^^mmmm
4.12
0.90
1.38
6.40
Emission
Factor
Quality
Rating
MBMMHMIB^^
E
E
E

  •1981 data.
  Source: Reference 9.
      Any given monochlorobenzene production plant may be different from this hypothetical
facility in configuration and level of control. The reader is encouraged to contact plant personnel
to confirm the existence of emitting operations and control technology at a particular facility prior
to estimating emissions.
                                  *
4.3  DICHLOROBENZENES PRODUCTION
      Mixtures of dichlorobenzenes can be produced  at facilities formulating MCB  by
chlorinating MCB or benzene at 150°C to 190°C (302° to 374°F) in the presence of ferric
chloride, as shown below.
      ran
                       FeCk
   moncchlorobenzene
o-dichlorobenzene
  4-10
p-dicitlorobenzene

-------
 4.3.1  Ortho- and Para-Dichlorobenzene

       The residue from distillation of crude chlorobenzene, consisting mainly of o- and p-DCB,
 is the principal source of these isomers. Figure 4-2 presents basic operations that may be used
 to produce o- and p-DCB and TCB. In a continuation of the production of MCB, o- and p-DCB
 can be separated by fractional distillation.  Isomer fractionation yields p-DCB (with traces of
 o-DCB and m-DCB) which enters the overhead (Stream 1) while the o-DCB enters the bottoms
 (Stream 2). The o-DCB bottoms (Stream 2) undergoes fractional distillation and produces an o-
 DCB overhead (Stream 3), which is  sent to storage, and bottoms (Stream 4), which is further
 processed to  yield TCBs.6

       The crude p-DCB with  other trace isomers (Stream 5) is purified by batch crystallization.
 Part of the purified p-DCB (Stream 6) is sent to liquid storage while the remainder (Stream 7)
 undergoes freezing, crushing, screening, and packing of p-DCB crystals. The mother liquor from
 crystallization (Stream 8) is sent to DCB solvent grade fractionalization where it is separated into
 solvent grade o-DCB (Stream 9)  and  p-DCB (Stream 10) and stored.6

       Currently, three facilities  have the capacity to produce both o- and p-dichlorobenzene.
 Annual capacity of o-dichlorobenzene is 36.7 million kilograms (80.9 million pounds).   The
 annual capacity of p-dichlorobenzene is 60 million kilograms (132 million pounds).  The three
 major producers of o- and p-dichlorobenzene are listed in Table 4-5.1-8  The major producers of
 dichlorobenzenes are subject to change as market conditions change, facility ownership changes,
plants are closed, etc. The reader should verify the existence of particular facilities by consulting
current listings and/or the plants  themselves.  The level of chlorobenzene emissions from any
given facility is a function of variables such as capacity, throughput and control measures, and
should be determined through direct contact with plant personnel.
                                         4-11

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                                    TABLE 4-5.
         CHEMICAL PRODUCERS OF o-DICHLOROBENZENE AND
                         p-DICHLOROBENZENE, 1989
Facility
— ^— .^^B^^..
Monsanto Company
Monsanto Industrial Chemicals Company
PPG Industries, Inc.
Chemicals Group
Industrial Chemical Division
.Standard Chlorine Chemical
Company, Inc.
Total
Location
Sauget,
Illinois
Natrium, West
Virginia
Delaware City,
Delaware

Capacity
Million kg/yr
(Million Ibs/yr)
o-DCB
4.5 (9.9)
9 (19.8)
22.7 (50)
36.7 (80.9)
p-DCB
11.3 (24.9)
13.6 (30)
34(75) .
59.6 (131.4)
  Source:  References 1, 8.
4.3.2  Meta-Dichlorobenzene


      The  isolation of m-dichlorobenzene from  mixed dichlorobenzene streams  is not
economical, since it usually occurs at a level of one (1) percent or less.  Meta-dichlorobenzene
is sold with other isomers as mixed chlorobenzenes.10


      It should be noted that discussions  in this chapter have principally  described the
manufacture of selected chlorobenzene isomers from non-chlorobenzene materials.  Numerous
manufacturers also purchase select chlorobenzene isomers from original manufacturers for

repackaging.  Other manufacturers purchase mixed chlorobenzenes and isolate selected isomers
for resale.10
                                     4-13

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 4.3.3  Emissions

        The level of chlorobenzene emissions from any given facility is a function of variables
 such as capacity, throughput and control measures, and should be determined through direct
 contacts with plant personnel. Emissions from the continuous process (Figure 4-2) are primarily
 from the batch p-DCB crystallization vent (A). An exhaust fan (B) releases sublimation losses
 from freezing, crushing, and the p-DCB crystal packaging hoods  to the atmosphere.  Some
 emissions are also  expected from  liquid product storage (C), handling (D), and the vacuum
 system (E) which services the vacuum stills.  Fugitive emissions may be expected from  certain
 valves, pumps, etc. (F).6 Data are not available to estimate emissions from the production of m-
 DCB. Emission factors for o- and p-DCBs are shown in Tables 4-6 and 4-7, respectively.  The
 emission factors are only general estimates derived from site visit measurements.  No specific
 information was  available on particular emission  points  included in each of the emission
 categories or on the type of production processes used (batch or continuous) or on only specific
 control technologies employed.

       Any actual o-DCB  and p-DCB production plant may vary in configuration and level of
 control from the hypothetical facilities.  The reader is encouraged to contact plant personnel to
 confirm the existence of emitting operations and control technology at a particular facility prior
 to estimating emissions therefrom.

 4.4 TRICHLOROBENZENES PRODUCTION

       The most  common  process by  which trichlorobenzenes are formed is the catalytic
cMorination of o- and p-DCB at 20°C to 30°C (68°F to 86°F) in the presence of ferric chloride.
The reaction is allowed to proceed until a density of 1.4 g/mL at 15°C (59°F) is obtained,
at which time the acid is neutralized and the products are fractionally distilled to yield 1,2,4- and
1,2,3-isomers.12
                                        4-14

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                              TABLE 4-6.
            EMISSION FACTORS FOR A HYPOTHETICAL
            o-DICHLOROBENZENE PRODUCTION PLANT3
      Emission
      Category
      ^mmmmm
       Process
kg o-DCB Emitted
    PerMg
 o-DCB Produced
     ••••
      2.32
Ib o-DCB Emitted
    Per Ton
o-DCB Produced
     m^mm
     4.64
  Emission
Factor Quality
   Rating"
    ••
     U
       Storage
      0.47
     0.94
                                        U
      Fugitive
      0.76
     1.52
                                                            U
      TOTAL
      3.55
                                           7.10
 *1980 data.
 bNot enough information available to assign a quality rating.

 Source: Reference 11.
                              TABLE 4-7.
           EMISSION FACTORS FOR A HYPOTHETICAL
           p-DICHLOROBENZENE PRODUCTION PLANT3
      Emission
      Category
      ••••••
       Process
  kg p-DCB Emitted
      Per Mg
  p-DCB Produced
       ••••
        5.81
   Ib p-DCB Emitted
       Per Ton
   p-DCB Produced
        •^••i
        11.62
    Emission
     Factor
    Quality
    Rating"
      ••n
      U
       Storage
       0.41
        0.82
                                                              U
       Fugitive
       1.02
        2.04
                                                             U
      TOTAL
       7.24
                                              14.48
'1980 data.
"Not enough information available to assign a quality rating.

Source:  Reference 11.
                                4-15

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                    a
                                     Fed3
                                     Fed3
                                                                   a
                                                          1A4-TCB
       Similarly, 1,3,5-TCB can be obtained by the chlorination of m-DCB.
                                       Fed,
                                                                       HC1
                1,3-DCB

       Most TCBs are produced at the same location as the lower chlorinated benzenes.  At these
facilities the TCBs are fractionally separated from DCBs.5  It is assumed that most TCBs are
produced by the batch method due to the low volume of domestic production.12

       Other trichlorobenzene production processes mentioned in the literature include:  (1) the
reaction of a,  p, or y-benzene hexachloride with alcoholic potash at 100°C (212°F) to  produce
all three TCB isomers; (2) the dehalogenation of cc-benzene hexachloride with pyridine to form
all three TCB isomers; and (3) the reaction of cc-benzene hexachloride with calcium hydroxide
to form primarily 1,2,4-TCB.6 Further process details are not available.  Contact should be made
with specific plants to determine manufacturing processes  used on site.  Currently, the Standard
Chlorine Chemical Company,  Incorporated,  of Delaware City, Delaware  is the only known
producer of trichlorobenzenes.8 The facility's  production capacity is unknown. The reader
should verify the existence of particular facilities by consulting current listings and/or the plants
themselves.  The level of chlorobenzene  emissions from any given facility is  a function of
                                        4-16

-------
variables such as capacity, throughput and control measures, and should be determined through
direct contacts with plant personnel.

       Trichlorobenzene emissions released during the continuous product process (Figure 4-2)
result from storage (Q and handling (D) of trichlorobenzene  products.  Fugitive emissions of
TCBs may also occur when leaks develop in valves, pump  seals, and  major equipment (F).
Secondary emissions from MCB production (Figure 4-1) are also possible from volatilization of
TCB from the wastewater stream (H) containing dissolved benzene and other VOC, and the
catalyst waste stream (I).6 No information was available concerning identification of specific
TCB isomers at the time this report was prepared.
                                        4-17

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-------
 4.5

 1.


 2.



 3.
4.
5.


6.



7.


8.


9.
10.
11.
 REFERENCES FOR SECTION 4.0

 7990 Directory of Chemical Producers,  United States of America, SRI International
 Menlo Park, CA, 1990.

 U.S. Environmental Protection Agency, Protocols for Generating Unit-Specific Emission
 Estimates for Equipment Leaks of VOC and VHAP, EPA-450/3-88-010, Office of Air
 Quality Planning and Standards, Research Triangle Park, NC, 1988.

 U.S.  Environmental  Protection  Agency,  Fugitive  Emission Sources  of Organic
 Compounds-Additional Information  on Emissions,  Emission  Reductions,  and Costs,
 EPA-450/3-82-010, Office of Air Quality Planning and Standards, Research Triangle Park
 NC, April 1982.

 Liepins, R. and F.  Nixon, Industrial Process Profiles for Environmental Use: Chapter
 6.  The Industrial Organic Chemicals Industry, EPA-600/2-77-023f, U.S. Environmental
 Protection  Agency, Industrial Environmental Research Laboratory,  Cincinnati  OH
 February 1977, pp. 6-55 to 6-56.                                           '     '

 Kirk-Othmer Encyclopedia of Chemical Technology, Volume 5, Third Edition, Wiley-
 Interscience Publication, New York, NY, 1980. pp. 797-808.

 U.S. Environmental Protection Agency, Organic Chemical Manufacturing, Volume 6-
 Selected Processes, EPA-450/3-80-028a, Office of Air Quality Planning and Standards
 Research Triangle Park, NC, December 1980.

 Lowenhiem, F.A. and M.K. Moran,  Faith,  Keyes, and Clark's Industrial Chemicals,
 Fourth Edition, John Wiley and Sons, New York, NY, 1975.

 SRI Chemical and Economics Handbook, "Chlorobenzene Production " Menlo Park CA
 1989.

 U.S. Environmental Protection Agency, Human Exposure to Atmospheric Concentrations
 of Selected Chemicals, Volume II: A Summary of Data on Chlorobenzenes, Office of Air
 Quality Planning and  Standards, Research Triangle Park, NC, PB83-265249, February
 1982. pp. 7-16.

 Opatick, Richard, Chlorobenzene Producers Association. Memorandum to Michael Ling,
 TRC Environmental Corporation, August 4, 1993.

 U.S. Environmental  Protection  Agency, An Exposure   and Risk  Assessment  for
Dichlorobenzenes, Final Draft, Office of Water Regulations  and Standards, Washington,
 DC, 1981, p. A-l.
                                       4-18

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12.    U.S. Environmental Protection Agency, Investigation of Selected Potential Environmental
      Contaminants: Halogenated Benzenes, EPA-560/2-77-004, Office of Toxic Substances
      Washington DC, July 1977.
                                      4-19

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                                     SECTION 5.0
               EMISSIONS FROM MAJOR USES OF CHLOROBENZENES

       Chlorobenzenes are used as a solvent and/or feedstock in the manufacture of many
 products, as discussed in Section 3.  Additionally, chlorobenzenes are used as a dye carrier in the
 textile industry and as an additive in functional fluids. This section discusses the emissions of
 chlorobenzenes from processes  that use chlorobenzenes as feedstocks in the manufacture of
 another product or as a solvent  Emissions of chlorobenzenes as residual components of a
 product containing chlorobenzenes are discussed  separately  in  Section  6.   Emissions of
 chlorobenzenes as byproducts of the manufacture of another product, or through combustion of
 fossil fuels or wood are discussed in Section 7.

 5.1    MANUFACTURE OF NTTROCHLOROBENZENES FROM MONOCHLOROBENZENE

       The largest consumption of monochlorobenzene in the United States is in the production
 of nitrochlorobenzenes.  In 1988, nitrochlorobenzenes production consumed 42 percent of all the
 monochlorobenzene produced in the United States.  Nitrochlorobenzene is used as a chemical
 intermediate in the manufacture of rubber chemicals,  antioxidants, and dyes and pigments. It is
 also used in the manufacture of pharmaceutical products.1

       Twenty-three percent of the nitrochlorobenzenes produced in 1983 were used in dye and
 pigment production.  Nitrochlorobenzenes are used  as starting materials and to  produce dye
 intermediates, including nitroaniline and phenylenediamine.2

       Nitrochlorobenzenes are also used in the manufacture of agricultural chemicals to produce
 intermediate forms  including p-chloroaniline and p-nitrophenol.  p-Nitrophenol is  necessary in
the manufacture of the organophosphate pesticides, parathion, and methylparathion.1 Reduction
of p-nitrophenol yields p-aminophenyl, which is further  processed to  make acetaminophen
 (analgesic/antipyretic).1-2
                                        5-1

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  5.1.1  Process Description

        Nitrochlorobenzenes are manufactured by the nitration of monochlorobenzene using a
  mixed acid solution of nitric acid and sulfuric acid at 40°C to 70°C (104°F to 158°F) for  12
  hours.  Input materials  to  produce 1 metric ton of combined  nitrochlorobenzenes include
  4536 kilograms (10,000 pounds) of MCB and 9570 kilograms (21,098 pounds) of combined 30
  to 35 percent nitric acid and 52 to 55 percent sulfuric acid.  The product mixture at the end  of
  12 hours is comprised of (34 percent) ortho- and (65 percent) para-nitrochlorobenzenes.3 This
  step is illustrated in the following reaction.
                            HNO,
             monochlorobenzene
l-chIoio-2-nitrobenzene
     NO,
l-chloro-4-nitrobenzene
       Table 5-1 lists producers of o- and p-nitrochlorobenzene in the United States. In 1989,
 66.2 million kilograms (146  million pounds) of nitroclilorobenzenes  were  produced and
 50 million kilograms (110 million pounds)  of monochlorobenzene were consumed for the
 production of nitrochlorobenzene.1  The manufacturers are subject to change as market conditions
 change, facility ownership changes, plants are closed, etc. The reader should verify the existence
 of particular facilities by consulting current listings and/or the plants themselves.

 5.1.2  Emissions
       The level of chlorobenzene emissions from any given facility is a function of variables
such as capacity, throughput and control measures, and should be determined through direct
contacts with plant personnel. Facilities manufacturing nitrochlorobenzene have a potential to
emit monochlorobenzene from process equipment vents, open process equipment,  equipment
leaks, storage tank vents, secondary sources, and transfer and handling operations. No specific
emissions data  are  currently  available  on  the  use  of  MCB  in  the  production  of
                                                                       d
                                          5-2

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                                     TABLE 5-1.
                     CHEMICAL PRODUCERS OF o- AND
                      p-NITROCHLOROBENZENES - 1989
Facility
E.I. duPont de Nemours & Company, Inc.
Chemicals and Pigments Department
Monsanto Company
Monsanto industrial Chemicals Company
TOTAL
Location
Deepwater, New Jersey
Sauget, Illinois

Capacity
Millions kg
(Millions Ibs)
27.5
(60.6)
38.7
(85.3)
66.2
(146)
   Source: Reference 4.
nitrochlorobenzenes.  The discussion in Section 4.1 on fugitive emissions should be referred to
for more detail.  The reader is advised to contact plant personnel to identify control technology
and emissions for a specific plant process.

5.2   MANUFACTURE OF DIPHENYL OXIDE FROM MONOCHLOROBENZENE

      Monochlorobenzene is used in the manufacture of diphenyl oxide. Diphenyl oxide (also
known as diphenyl ether) finds its major use in the manufacture of heat transfer fluids, such as
Therminol® VP-1, a product manufactured  by Monsanto Company, and Dowtherm®,  a product
manufactured by Dow Chemical.  Another use for diphenyl oxide is as a chemical intermediate
for brominated fire retardants.  The primary producers of fire retardants are Dow, Ethyl, and
Great Lakes Chemical Companies. Diphenyl oxide is. also used as an intermediate for specialty
surfactants.  Dowfax®, which is manufactured by Dow Chemical, is the leading surfactant
produced using the intermediate diphenyl oxide.  Diphenyl oxide is also used as a perfume in
soaps.1
                                      5-3

-------
 5.2.1   Process Description

        Diphenyl oxide is typically produced in a continuous flow tubular reaction  system.
 Chlorobenzene  is reacted  with aqueous  sodium  hydroxide (NaOH) and  recycled products
 (containing phenol and sodium phenoxide).  These reactants are heated to between 275°C and
 300°C  (527°F and 572°F) by passing through  a nickel-lined .heat exchanger.  The reaction
 temperature of 400°C (752°F) is achieved electrically and the reactants are allowed to flow
 through the system for 10 to 30 minutes. The reaction must be maintained at sufficient pressure
 [> 26.2 MPa (2586 atm)] to prevent vaporization, which would allow NaCl, NaOH, or phenoxide
 to be deposited on the tube walls causing hot spots and excessive corrosion.  The resulting two
 layers from the reaction are aqueous phenoxide and an oily layer consisting mainly of diphenyl
 oxide and unreacted chlorobenzene.   Diphenyl oxide is recovered by distillation  of this oily
 layer.3

       Dow Chemical, U.S.A. of Midland, Michigan is the only known  facility producing
 diphenyl oxide as reported in the SRI Chemical and Economics Handbook.1   This listing is
 subject to change as market conditions  change, facility ownership changes, plants are closed, etc.
 The reader should verify the existence of particular facilities by consulting current listings and/or
 the plants themselves.

 5.2.2 Emissions

      The level of chlorobenzenes emissions from any given facility is a function of variables
 such as capacity, throughput and control measures, and  should be determined  through direct
 contacts with  plant personnel.   Although quantitative estimates are unavailable,  only  small
 quantities  of MCB are believed to be emitted during the diphenyl oxide manufacturing process.
The reader is advised to contact plant personnel for information concerning emissions and control
technology employed for specific processes.
                                          5-4

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 5.3    MANUFACTURE OF PHENYLPHENOLS FROM MONOCHLOROBENZENE

        Monochlorobenzene is used in the manufacture of o-phenylphenol and p-phenylphenol.
 Ortho-phenylphenol  is  primarily  used  in hard  surface  disinfectants,  such  as  Lysol*.
 Para-phenylphenol is used in combination with formaldehyde to make a resin used in carbonless
 paper.  It is also used in resins found in marine varnishes.1

       In  1988, 20.4 million  kilograms  (45 million pounds)  of monochlorobenzene  were
 consumed during the manufacture of diphenyl oxide, o-, and p-phenylphenol.  Currently, Dow
 Chemical of Midland, Michigan is the only known producer of o- and p-phenylphenol.1  The
 manufacturers are subject to change as market conditions change, facility ownership changes,
 plants are closed, etc. The reader should verify the existence of particular facilities by consulting
 current listings  and/or the  plants  themselves.   Specific process information  used  in the
 manufacture of phenylphenols was not identified during the writing of this report.

       No emissions data are available on the use of MCB in the production of phenylphenols.
 The level of chlorobenzene emissions from any given facility is a function of variables such as
 capacity, throughput and control measures, and should be determined through direct contacts with
 plant personnel.  The reader is advised to contact plant personnel to identify control technology
 and emissions for a specific plant process.
5.4
MANUFACTURE OF 4,4'-DICHLORODff HENYLSULFONE FROM MONOCHLORO-
BENZENE
       Monochlorobenzene is used in the production of the sulfone-containing monomer, 4,4'-
dichlorodiphenylsulfone (4,4'-DCDPS), which is used in the manufacture of all polysulfone
engineering plastics.   Sulfone  polymers find major applications in the electrical/electronic
components, medical equipment and supplies, and food related industries.1
                                        5-5

-------
 5.4.1  Process Description

        Specific process information used in the manufacture of 4,4'-DCDPS was not identified
 during the writing of this report.   However, 4,4'-dichlorodiphenylsuIfone is  formed by  the
 following reactions:
                                      so3
    S03H
  6
                      monochlorob«nr8n«
                                                          wt
                                                 p-chlorob«inzon«sulfon« acid
                       S03H
                               SOCIj
                                                    so2c« •»• HCI + soj + a
               p-chtereb«nz«no»ulfon« acid   4-chlorob«nz«n«sulfone ehlorido
                                 S02CI
                 4-chlorob«nz*n««ulfon« chlorid*
              Cl + 2CI + SOj


4.4-d!e»itorodlph«nyl«ulfon«
       4,4»-Dichlorodiphenylsulfone is manufactured for captive use by Amoco Corporation of
Marietta, Ohio and ICI American Holdings Company of Fayetteville, North Carolina.  In 1988,
approximately 6.8 million kilograms (15 million pounds) of sulfone were produced.  During the
1988  production  year,  approximately 5.4  million  kilograms  (12  million  pounds)   of
monochlorobenzene were  consumed.1   The manufacturers  are  subject to change as market
conditions change, facility ownership changes, plants are closed, etc. The reader should verify
the existence of particular facilities by consulting current listings and/or the plants themselves.

5.4.2  Emissions

       No  emissions data are  available  on  the use of MCB  in the production of  4,4s-
dichlorodiphenylsulfone.    The level of chlorobenzene emissions from any given facility is a
                                           5-6

-------
 function of  variables such  as  capacity,  throughput and control measures, and  should  be
 determined through direct contacts with plant personnel. The reader is advised to contact plant
 personnel to  identify control  technology and emissions for a specific plant process.

 5.5    MANUFACTURE OF 3,4-DIOHLO^^

       An important compound derived from o-dichlorobenzene (o-DCB) is 3,4-dichloroaniline.
 In 1988, the manufacture of 3,4-dichloroaniline consumed 31 percent of all the o-dichlorobenzene
 produced in the United States. 3,4-Dichloroaniline is used as an intermediate in the production
 of an anilide pesticide (propanil), and two substituted urea pesticides (diuron and linuron).1
 Pesticides and production locations from the Farm Chemicals Handbook are listed in Table 5-2.5
 Dow Chemical also cited usage of 3,4-dichloroaniline as an intermediate for polyethers and as
 a cross-linkage agent in. epoxy tar products.6  A small volume of 3,4-dichloroaniline is used for
 the  production  of  3,4,4'-trichlorocarbanilide  (also known  as  TCC  and  triclocarbon).1
 3,4,4'-tricUorocarbanilide is used as a bacteriostat and antiseptic in soaps and other cleaning
 compositions.7

 5.5.1 Process Description
       Commercially, 3,4-dichloroaniline is prepared by the nitration of o-DCB followed by
reduction of the resulting 3,4-dichloronitrobenzene.  In many cases, the nitration operation
produces two immiscible layers.  For safety reasons and ease of operation, temperatures from
0°C to 120° C (32°F to 248°F) and atmospheric pressure are used. At higher temperatures,
competing oxidation reactions become important.  Reaction residence times for nitration range
from 1 to 60 minutes.3 The nitration reaction may be written as:
                                                         N02
                                 HN03
                                 H2S°4
o-dichlorobenzene
                                                 3,4-dichloronitrobenzene
                                        5-7

-------
                        TABLE 5-2.
         PESTICIDES USING 3,4-DICHLOROANILINE
                AS AN INTERMEDIATE - 1989
Pesticide
Class
Anilide
Pesticide






Substituted
Urea
Pesticide

















Scientific Name
3,4-DichIoropropionanilide







3-[3,4-Dichlorophenyl]-
1,1-dimethylurea









3-[3,4-Dichlorophenyi]-l
methoxy-1-methylurea






Common/Registered
Brand Name
Propanil
Stamm® and
Stampede®
Cedar Propanil® 4
and Wham EZ®

Chem Rice®

Diuron
Crisuron®

Diumate®
Kannex® and
Krovar®


Direx® 4L


Linuron

.orox®


-inures®



Producers


Rohm and Hass Company

Cedar Chemical Corp.

Tifa Ltd.


Crystal Chemical Inter-
America
Drexel Chemical Company
E.I. du Pont de Nemours
& Company, Inc.
Agricultural Products
Department
Griffin Corporation
Agricultural Chemicals
Group

1.1. du Pont de Nemours
& Company, Inc.
Agricultural Products
Department
Griffin Corporation
Agricultural Chemicals
Group

Location(s)


Philadelphia, PA

Memphis, TN
Vicksburg, MS

Millington. NJ

Houston, TX

Memphis, TN

LaPorte, TX



Valdosta, GA




LaPort, TX

Valdosta, GA


Source: References.
                           5-8

-------
       The  reduction of 3,4-dichloronitrobenzene may  be achieved in two ways:   (1) by
 employing iron and HC1; and (2) by using hydrogen and a catalyst with some heating.  Other
 operating parameters could not be found at the writing of this report3 The reduction reaction
 may be written as:
                         NO,
                                    (1)  Fe, HC1
                                    (2) Hj,  Catalyst, Heat
                 3,4-dichloronitrobenzene
       Cl
3,4-dichloroaniIine
       The Deep Waters, New Jersey plant of the E.I. duPont de Nemours & Company, Inc. is
the only known producer of 3,4-dichloroaniline.4-8  Producers of 3,4-dichloroaniline and their
locations for 1989 are given in Table 5-3. Production estimates of 3,4-dichloroaniline are not
available;  however, in 1988,  the production of 3,4-dichloroaniline consumed 11.3  million
kilograms (25 million pounds) of o-DCB.1
                                        TABLE 5-3.
         CHEMICAL PRODUCERS OF 3,4-DICHLOROANILINE - 1989
Facility
E.L duPont de Nemours & Company, Inc.
Chemicals and Pigments Department
Location
Deep Water, New Jersey
    Source: Reference 4,8.
5.5.2  Emissions
      Table 5-4 lists general process, storage, and fugitive emission factors, with no specific
controls, for the production of 3,4-dichloroaniline;  The emission factors were derived from
various detections of o-DCB in industrial wastewater streams. The discussion in Section 4.1 on
                                        5-9

-------
                                     TABLE 5-4.
            EMISSION FACTORS FOR THE PRODUCTION OF
                            3,4-DICHLOROANILINEa
Emission
Category
Process
Storage
Fugitive
TOTAL
kg o-DCB emitted
perMg
o-DCB used
1.05
0.15
0.30
1.50
Ibs o-DCB emitted
per ton of
o-DCB used
2.10
030
0.60
3.0
Emission
Factor
Quality
Rating*
u
u
u

     •1980 data..
     'Not enough information available to assign a quality rating.
     Source: Reference 9.
fugitive emissions should be referred to for more detail.  The reader is encouraged to contact
plant personnel for information regarding actual emissions and control technologies employed at
specific locations.
5.6
USE OF PARA-DICHLOROBENZENE IN THE PRODUCTION OF POLYPHENYLENE
SULFIDE
       Para-dichlorobenzene is used in the production of polyphenylene sulfide: it is the single
largest product manufactured from p-DCB.  Polyphenylene is a commercial polymer known as
Ryton*, having many industrial applications.1 Characteristics of polyphenyl sulfide (PPS), also
named polythio-l,4-phenylene, include good thermal stability, retention of mechanical properties
at elevated temperatures, excellent chemical resistance, and an affinity for a variety of fillers.10
Polyphenylene  sulfide  is  used in electrical applications for .its insulating, dielectric, and
chemical/heat resistant properties.1  Polyphenylene sulfide may also be used to replace fabricated
steel parts in mechanical, appliance, and automotive equipment such as molded parts including
                                       5-10

-------
 nonlubricated bearings, seals, pistons, impellers, pump vanes and electronic components.  It can
 also be used as a coating to metals and ceramics as a protective and corrosion resistant medium,
 which is useful for equipment in the chemical and petroleum industries. When mixed with small
 amounts of polytetrafluoroethylene, the  mixture provides a non-stick surface in cookware  and
 other industrial applications, such as  Teflon®  and Silverstone.1-10

 5.6.1  Process Description

       Polyphenylene sulfide is formed by the following reaction of p-DCB and sodium sulfide
 in a polar solvent
                                 NaoS
                                          Polar
                                          Solvent
          p-dichlorobenzene
             -S-  -r  2NaCl
               •X
polyphenylene sulfide
       Steps involved in the manufacture  of PPS  shown in Figure 5-1 are as  follows:
 (1) preparation of sodium sulfide from aqueous caustic and aqueous sodium hydrosulfide in a
 polar solvent; (2) dehydration by distillation of the above feedstock; (3) polymer formation from
 the reaction of the  sodium sulfide stream and p-DCB at an elevated temperature  in a polar
 solvent; (4) polymer recovery; (5) removal of byproduct sodium chloride by washing, (6) drying
 and (7) packaging.  PPS produced by this process can be used in coating applications by slurry-
 coating procedures;  however, it is most often used as a feedstock in the production of molding-
 grade resins."

       Molding-grade resins are produced by a curing process in which the virgin polymer is
exposed to a small amount of air at a high temperature. At this point, a higher molecular weight
resin  is produced while lower molecular weight polymers are volatilized.   Residence time,
reaction temperature, and melt viscosity are important in the formation of various grades of PPS.
                                         5-11

-------
           NaSH
P-DiCHLOROBENZENE •
                                   NaOH
                              Na2S PREPARATION
                                DEHYDRATION
POLYMERIZATION
                             POLYMER RECOVERY
                             POLYMER WASHING
                              POLYMER DRYING
                                                        POLAR SOLVENT
                         H20
              PACKAGING  (VIRGIN POLYMER)/CURING (MOLDING RESIN)
                                                                              (1)
                                                                              (2)
                                                                              (3)
                                               (4)
                                                                             (5)
                                              (6)
                                              (7)
    Figure 5-1.  Process flow diagram of polyphenylene sulfide manufacture.11
                                       5-12

-------
 The cured polymer is cooled, combined with fillers' (such as glass fibers, if desired), pelletized,
 and then packaged.11

       Polyphenylene sulfide is produced by Phillips Petroleum Company in Borger, Texas. This
 manufacturing facility had production capacities of 5.4 million kilograms (12 million pounds) and
 7.3  million kilograms  (16 million pounds) in  1988  and  1989,  respectively.   In  1988,
 polyphenylene  sulfide  production  consumed 22 percent  of all  the p-DCB produced.1
 Consumption of PPS  has continued to grow since the early 1980s.  This listing is subject to
 change as market conditions change, facility ownership changes, plants are closed,  etc.  The
 reader should verify the existence of particular facilities by consulting current listings and/or the
 plants themselves.

 5.6.2  Emissions

       Facilities manufacturing polyphenylene sulfide have a potential to emit p-dichlorobenzene
 from process equipment vents, open process equipment,  equipment leaks, storage tank vents,
 transfer and handling operations,  and polymer washing  and  drying operations.  No specific
 emissions data are available for the production of polyphenylene sulfide. The discussion in
 Section 4.1  on fugitive emissions  should be  referred to for more detail.   The  level  of
 chlorobenzene emissions from any given facility is a function of variables such as  capacity,
 throughput, and control measures,  and should be determined through direct contacts with plant
 personnel. To determine actual emissions from particular processes, specific plants should be
 contacted.
5.7
USE  OF  CHLOROBENZENES   IN  THE   MANUFACTURE   OF  TOLUENE
DHSOCYANATE
       Ortho-dichlorobenzene and MCB are used in the manufacture of 2,4-toluene diisocyanate
(TDD. Toluene diisocyanates are industrial intermediates used in the production of polyurethane
foams, paints, varnishes, elastomers, and coatings.  Rigid polyurethane foams, accounting for
                                        5-13

-------
 about five percent of TDI demand, are used as insulation in refrigeration equipment12 Flexible
 polyurethane foams, used in furniture  cushioning, transportation (e.g., automotive seating),
 bedding, packaging, and carpet underlay, account for approximately 90 percent of the use of
 toluene diisocyanates.13  Little or no growth in production of TDI is expected for several reasons.
 Methyl diphenyl diisocyanate (MDI) is replacing TDI in many polyurethane foam applications.
 TDI can react violently with compounds containing an active hydrogen atom.13  In the TDI
 manufacturing process described below,  o-DCB is used as an inert process solvent.

 5.7.1   Process Description

       The manufacture of commercial  toluene diisocyanates  is based on the phosgenation of
primary amines.  Most  commercial TDI plants also produce  the intermediates dinitrotoluene
(DNT), toluene diamine  (TDA) and phosgene.14
       TDI is produced by the following chemical reactions:
                          talum
                                                 2.4-£iritroinJucn
-------
        Figure  5-2  illustrates the basic  operations that may be  used  in toluene diisocyanate
 production.  The first step in the manufacture of TDI is the nitration of toluene (Step  1).
 Nitration grade toluene is reacted with nitric acid to form DMT, as shown in Reaction 1. The
 reaction takes place at 65°C to 80°C (149°F to 176°F) in a well-agitated reactor equipped with
 cooling coils using sulfuric acid (60 to 70 .percent) as the catalyzing agent.15  The spent sulfuric
 acid is separated from the DNT reaction mixture, concentrated in a direct contact evaporator, and
 recycled to the nitration reactor (Step 2).14

        The DNT is washed in a wash tank (Step 3) and then reacted with hydrogen in catalytic
 reduction reactors (Step 4), using precious metal, nickel, or carbon catalysts, to form crude TDA
 (Reaction 2).  The hydrogenation of DNT normally occurs in an inert diluent (e.g., an  alcohol)
 to avoid explosion hazards and to control the heat resulting from the exothermic process.  The
 crude TDA is purified by filtration and distillation (Step 5).14-15

       TDA   is  reacted  with  phosgene  in   a  solvent,  usually  o-dichlorobenzene   or
 monochlorobenzene, to form crude TDI and hydrogen chloride (HC1), as shown in Reaction 3
 (Step 6).  Phosgene is condensed out of the HC1 byproduct and recycled to the reactor.  The
 overhead HC1 stream from the condenser may contain trace amounts of phosgene and is therefore
 sent to the phosgene absorber.  Crude TDI is sent to a distillation column for the removal  of
 residual phosgene (Step 7). After a series of distillation and condensation steps, the phosgene
 (from the crude TDI) is recycled to the phosgenation reactor.  The phosgene overhead (Step 7)
 from this distillation column and the HC1 and trace-phosgene stream from the reactor condenser
 are combined and sent to a column that absorbs phosgene with the o-DCB solvent.  The solvent
 is then stripped of phosgene in a distillation column and recycled to the absorber.

       The crude TDI still contains some of the chlorobenzenes solvent in which it was reacted.
This mixture (TDI and solvent) is transferred to a vacuum distillation column where the solvent
is recovered and recycled (Step 8).  The remaining crude TDI is vaporized  by vacuum flash
distillation to separate TDI from any polymeric isocyanates that may have formed (Step 9). The
TDI is then condensed  and sent to a vacuum  distillation column from  which purified TDI is
                                         5-15

-------
                                                         "5

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                                                         o
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                                                         «
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                                                        fa
5-16

-------
 removed (Step 10).  The purified TDI stream undergoes a final condensation step before being
 transferred to product storage (Step II).14-15

       Toluene diisocyanate is currently produced by five companies at six facilities in three
 States.  These facilities and their 1989 production capacities are listed in Table 5-5. This listing
 is subject to change as market conditions change, facility ownership changes, plants are closed,
 etc. The reader should verify the existence of particular facilities by consulting current listings
 and/or the plants themselves.

 5.7.2  Emissions

       Potential o-DCB emissions may occur at the residue separation vacuum jet vent (A) and
 the vacuum jet vents (B) associated with solvent recovery distillation, TDI flash distillation, and
 TDI purification distillation.14  It is estimated that only a  small fraction of o-DCB utilized is
 released into the atmosphere.16  However, no emission factors could be found nor developed for
 this process.  The  level of chlorobenzenes emissions from any given facility is a function of
 variables such as capacity, throughput and control measures, and should be determined through
 direct contacts with plant personnel.
  •*
 5.8    USE OF CHLOROBENZENES IN THE PRODUCTION OF DYES AND PIGMENTS

       The uses of chlorobenzenes in  the dye  and pigment industry are  two-fold:  (1) to
 synthesize other intermediates which are subsequently utilized in the formation of specific dyes
 and pigments; and (2) as inert process solvents in dye and pigment manufacturing.  The use of
chlorobenzenes in each of these applications is described here. The Ecological and Toxicological
Association of Dyestuffs Manufacturing Industry indicated in 1985 that the process information
mentioned below is outdated; however, no new information was  available.17
                                        5-17

-------
                                     TABLE 5-5.
         TOLUENE DHSOCYANATE PRODUCTION LOCATIONS AND
                                    CAPACITIES
               Producers
         Location
 Capacity
Millions of
kilograms
(Millions of
 pounds)
      BASF Corporation
     Geismar, Louisiana
    73
                                                                     (161)
      Dow Chemical
       Freeport, Texas
                                                                      63

                                                                     (139)
      ICI Americas
     Geismar, Louisiana
                                                                      32
                                                                      (71)
      Mobay Chemical Corporation
New Martinsville, West Virginia
   45

   (99)
      Mobay Chemical Corporation
      Baytown, Texas
   61

  (134)
      Olin Chemicals Corporation
   Lake Charles, Louisiana
                                                                     (194)
    Source: Reference 4.
5.8.1  Use of Chlorobenzenes in the Synthesis of Intermediates


      The chlorobenzene group is one of many classes of compounds used to synthesize

intermediates in the dye and pigment industry. Chlorobenzenes are normally purchased outside
                                    5-18

-------
 of the industry, converted into more complex intermediates and ultimately into dyes and
 pigments.  Some more complex intermediates may be dyes themselves, making the distinction
 between them and dyes and pigments somewhat arbitrary.

 Process Description - -

        In the dye and pigment industry, reactions for the production of intermediate dyes are
 generally carried out in kettles made from cast iron; stainless steel; or steel lined with rubber,
 glass (enamel), brick, or carbon blocks. The kettles have capacities of 2,200 to 44,000 liters (581
 to  11,625 gallons) and are equipped with mechanical agitators, thermometers or temperature
 recorders, condensers, pH probes, etc.^ depending  on the nature of operation.  Jackets or coils
 heat by circulation  of high-boiling fluids (hot oil, Dowtherm®), steam or hot water.  The kettles
 may be cooled with chilled brine. Unjacketed kettles are often used for aqueous reactions where
 heating is effected  by direct introduction of steam and cooling is effected by addition of ice or
 by the use of heat exchangers.18

       Products are  transferred from one piece of equipment to  another by gravity flow,
 pumping, or by blowing with air or inert gas. Solids are separated by centrifuges, filter boxes,
 continuous belt filters, or either plate-and-frame or recessed plate filter presses.

       When possible, intermediates are taken for subsequent manufacture without drying. When
 drying is required, air or vacuum ovens, rotary dryers, or spray dryers are used.  Drum dryers
 (flakers) may also be used, although less commonly.  Dyestuffs which require wet grinding,
.especially disperse dryers, are often spray dried with solid diluents to achieve standardization.
18
       Because the dye industries' use of small amounts of numerous intermediates has made
continuous processes impractical,  batch processes remain the rule.   However,  progress  in
computer and electronic technologies has led to growing use of automatic process control.18
                                         5-19

-------
 Emissions - -

        Possible sources of chlorobenzenes emissions from the synthesis of intermediates include
 kettles, separation processes, equipment leaks, drying processes,  and  transfer and handling
 operations.   No emissions  data are available  for the synthesis of intermediates using
 chlorobenzenes.  The discussion in Section 4.1 on fugitive emissions should be referred to for
 more detail. To  determine actual emissions from particular processes, specific plants should be
 contacted.

 5.8.2   Use of Chlorobenzenes as Process Solvent

        Chlorobenzenes are-used as inert process solvents in the production of a number of dyes
 and pigments. In Table  5-6, dyes and pigments which use specific chlorinated benzenes as
 solvents are categorized into dye and pigment classes according to the nature of their chemical
 structure.  Table 5-7 presents common names and manufacturers for those generic dyes  and
 pigments shown in Table 5-6.  Individual dyes and pigments within a class are produced by the
 same processes described here.

 Process Description Using Monochlorobenzene - -

       Monochlorobenzene is used as a process solvent in the manufacture of three indigoid dyes
 and pigments. All the pigments and dyes are thioihdigoid colors. Due to the corrosive nature
 of  the  reactants  involved in  these  processes, glass-lined vessels  and  efficient stirring  are
required.20

       The manufacture of the thioindigoid colors involves two process steps, one of which is
a diazotization. Temperature conditions range from 0° to 70°C (32° to 158°F).20  Because low
temperatures are  required, ice is used in substantial quantities.   Information regarding these
processes is somewhat limited.
                                          5-20

-------
                                  TABLE 5-6.
                    DYES AND PIGMENTS UTILIZING
                      CHLOROBENZENE SOLVENTS
Solvent
Monochlorobenzene



o-Dichlorobenzene




1 ,2,4-Trichlorobenzene
Dye or Pigment
Class
Thioindigoid
Thioindigoid
Thioindigoid

Oxazine
Oxazine
Pyranthrone
Anthraquinone
(oxazine)

Benzanthrone
Color Index
(C.I.)
73312
73360
73385

51300
51319
69700
67000

59825
Generic Dye or
Pigment Name
•"^•^•^—B— H^^^
Pigment Red 88
Vat Red 1,
Pigment Red 181,
D+C Red 30
Vat Violet 2

Direct Blue 106
Pigment Violet 23
Vat Orange 9
Vat Red 10

Vat Green 1
    Source: Reference 19.
Process Description Using ortho-Dichlorobenzene


      Ortho-dichlorobenzene is used as a process solvent in the production of two oxazine
pigments, one pyranthrone dye, and one anthraquinone dye. In addition, these dyes may be used
to produce other related dyes and pigments by halogenation.


      The manufacture of the oxazine pigments involves the condensation of substituted aniline
compounds with a substituted phenolic compound (or a phenol ether), followed by an oxidative
                                     5-21

-------


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                                    S2 2
                                    O 4>
                                    U O
         -™ -*M <^^
         o o o
                             5*8
                             u. S
         S2 55  i2
         4) S  4)
         U u  <->
       = 333
       •O -O -o 13


&as,i.§,ii
                             « -s e.'S •=•=-=•=
                             aooToooSc
                             gcQQioaaacQaaaa

                            CO«^  w-a  u^. M
5-23

-------
 reaction which forms the oxazine ring system.20  Stirred batch reactors with glass linings are
 required for most of the reactions involved in making these products. The oxazine pigment (C.I.
 51319) is produced by condensing chloranil with 3-amino-9-ethylcarbazole using sodium acetate
 as a catalyst  Ortho-dichlorobenzene is used as the process solvent in the reaction which requires
 7 hours at 60° to 115°C (140° to 239°F).  The condensation product is cyclized (refers to ring
 formation) to the pigment with benzenesutfonyl chloride at 180°C (356°F). The crude pigment
 is subsequently washed and filtered.19 Ortho-dichlorobenzene is also used as a process solvent
 in the  manufacture  of another oxazine pigment  (CI. 51300); however, no specific  process
 information was  available at the time this report was prepared.

       Pyranthrone dye (C.I. 59700) can be made from either  l-chloro-2-methylanthraquinone
 of pyrene as  the principal organic starting material.  Glass-lined, stirred reaction vessels are
 required due to the corrosive nature of the reactants.  Ortho-dichlorobenzene is used as a process
 solvent in this process. The dimerization of the l-chloro-2-methyl-anthraquinone takes place at
 150° to 160°C (302° to 320°F) in 6 hours, while cyclization to the dye requires an additional
 3 hours at the same temperature.20

       The anthraquinone dye which uses o-DCB as a process solvent is an. oxazole compound
 (CI. 67000) and is made from 2-amino-3-hydroxyanthraquinone. Batch-type reactions made of
 iron and with  good stirrers are typically used. In addition, the reactor must have a cooling coil
 to remove  heat generated  by  the  moderately  exothermic first  reaction  between  the
 aminoanthraquinone and the acid chloride.  The cyclization of the resulting amide to the desired
 oxazole is carried out in o-DCB at 140°C (284°F) in 5 hours.20

 Description of Process Using Trichlorobenzenes - -

       Trichlorobenzene is used as a process solvent in the production of a benzanthrone dye,
commonly called  Vat Green 1 (C.I. 59825).  The manufacture of benzanthrone dyes depends on
the modification of the primary intermediate, benzanthrone.  In order to make Vat Green 1, three
process steps are required. The alkali treatment of benzanthrone to make dibenzanthronyl takes
                                         5-24

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 place at 112°C (234°F) for 1 to 4 hours.  The dibenzanthronyl is then oxidized to the diketo-
 compound  at 25°  to  30°C (77°  to 86°F) for 4 hours.  The methylation of the dihydroxy-
 compound is achieved by reducing the diketo-compound with boiling sodium bisulfite at 210°C
 (410°F) for 4 hours.20

        Table 5-8 lists dye and pigment manufacturers from Ward's Business Directory which
 may utilize chlorobenzenes in certain processes.21  The list of manufacturers is subject to change
 as market conditions  change, facility ownership  changes, plants are closed, etc.  The reader
 should verify the existence of particular facilities by consulting current listings and/or the plants
 themselves.

 Emissions

        Emission factors for  the  use^of o-DCB in  dye synthesis appear in Table 5-9.   The
 emission factors are only general estimates.  No  information was found on specific emission
 points included  in each emission category, the type of production processes used, or specific
 control technologies  employed,  if any.    Emission  factors  for  monochlorobenzene  and
 trichlorobenzenes were not available. The discussion in Section 4.1 on fugitive emissions should
 be referred to for more detail. Any given dye synthesis plant may vary in configuration and level
 of control from this hypothetical facility. The level of chlorobenzene emissions from any given
 facility is a function of variables such as capacity, throughput, and control measures, and should
 be determined through direct  contacts with plant personnel.  Literature information does not
 distinguish between emissions resulting from  the synthesis of intermediates or process  solvent
 usage.  Information  regarding the nature-and quantities of air emissions of other chlorobenzenes
produced during dye and pigment manufacture was not available. The reader is advised to seek
emissions data through contact with specific plant personnel.
                                         5-25

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                   TABLE 5-8.
DYE AND PIGMENT MANUFACTURING COMPANIES
State
Alabama

California


Faculties

McWane Inc.
Empire Coke-By-Products
Tuscaloosa, Alabama


Davis Colors
Rockwood Industries Inc.
Los Angeles, California
LM Scofield Company
Los Angeles, California
Hurst Graphics Inc.
Los Angeles, California

Connecticut

Crompton & Knowles Corporation
Stamford, Connecticut
Carey Industries Inc.
Danbury, Connecticut
Florida

Georgia »


Illinois



Indiana

Louisiana
Maryland

Southern Mill Creek Products Company, Inc.
Tampa, Florida

t
ABC Compounding. Company Inc.
Morrow, Georgia
Kemira Inc.
Savannah, Georgia
Colloids Inc.
Lyndal Division
Dalton. Georgia
New Riverside Ochre Co., Inc.
Cartersville, Georgia

Apollo Colors Inc.
Northbrook, Illinois
Chroma Corporation
St. McHenry, Illinois
Industrial Color Corporation Inc.
Joliet, Illinois
Chi-Vit Corporation
Downers Grove, Illinois
Color Communications Inc.
Chicago, Illinois


Western Tar Products Corporation
Terre Haute, Indiana
Omnitech International Inc.
Thibodoux, Louisiana -



Mineral Pigments Corporation
Rockwood Industries Inc.
Beltsville, Maryland
Mobay Corporation
Pemco Products
Baltimore, Maryland
                    (continued)
                     5-26

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                        TABLE 5-8.
DYE AND PIGMENT MANTJFACTORING COMPANIES (continued)
ll ' ' " "^^^^~^^^^^™
IjState
1
Massachusetts

Minnesota

^Mississippi

Missouri
	 : 	 _
[New Jersey








	 	 Facilities
^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^BHB^^^^BI^^^MBBBBi
SCM Chemicals Inc.
Baltimore, Maryland
	 — 1
1 	 ' 	

Roma Color Inc.
Fall River, Massachusetts

GNB Inc.
Metal Division
St. Paul, Minnesota


Spectrum Colors
Minneapolis, Minnesota

First Chemical Corporation
First Mississippi Corporation
Pascagoula. Mississippi

Wamer-Jekinson Company
St. Louis, Missouri
First Mississippi Corporation
Jackson, Mississippi



Buffalo Color Corporation
Parsippany, New Jersey
Dye Color Pope Inc.
Clifton, New Jersey
H Kohnstamm & Company Inc.
South Plainfield, New Jersey
International Dyestuffs Company
Clifton, New Jersey
Vfallinckrodt Inc.
Van Dyk & Co.
Belleville, New Jersey
Vfagruder Color Company Inc.
Elizabeth, New Jersey
'igment Dispersions Inc.
Edison, New Jersey
IBH Dispersions Inc.
Bound Brook, New Jersey
Colorco Inc.
Linden, New Jersey
H Kohnstamm & Company Inc.
Color Division
Indol Color Company Inc.
Magruder Color Inc.
Carteret, New Jersey
MA Hanna Company
PMS Consolidated Division
tfax Marx Color Company
Irvington, New Jersey
Pfister Chemicals Inc.
Ridgefield, New Jersey
PMS Consolidated
Somerset, New Jersey
lepeat-O-Type Manufacturing
Corporation
Wayne, New Jersey
                         (continued)
                          5-27

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                        TABLE 5-8.
DYE AND PIGMENT MANUFACTURING COMPANIES (continued)
state I Facilities
JRheox Inc.
NL Industries Inc.
Hightstown, New Jersey
[Whittaker Clark & Daniels
1 South Plainfield. New Jersey
New Yoik


North Carolina

Ohio


Pennsylvania



South Carolina

Tennessee

Standard Chlorine Chemical
Company
Kearny, New Jersey


EM Industries Inc.
Hawthorne. New York
Pennwalt Corporation
Lucidol Division
Buffalo, New York
Mearl Corporation
Ossining, New York
R & A Specialty Chemicals
Company Inc.
Brooklyn. New York

Sandoz Chemicals Corporation
Charlotte, North Carolina


Accurate Color Inc
Lodi, Ohio
Flint Ink Corporation
Ridgway Color Company
Cincinnati, Ohio
Americhem Inc.
Cuyahoga Falls, Ohio
Sun Chemical Corporation
Pigments Division
Cincinnati, Ohio

hidespec Chemical Corporation
Pittsburgh, Pennsylvania
Rutgers-Jenkinson Company
State College, Pennsylvania
Zinc Corporation of America
Monaco. Pennsylvania
Mobay Corporation
Dyes Pigments & Organic
Division
Pittsburgh, Pennsylvania
Siberline Manufacturing Company
Inc.
Tamaqua, Pennsylvania

ii
Pat-Chem Inc.
Greenville, South Carolina
Synalloy Corporation
Blackman Uhler Chemical
Division
Spartanburg, South Carolina
ii
Avecor Inc.
Vonore, Tennessee

                        (continued)
                         5-28

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                            TABLE 5-8.
  DYE AND PIGMENT MANUFACTURING COMPANIES (continued)
State
Texas
'


Virginia


Facilities

•MMMMHHMMHMMMMI
Allco Chemical Corporation (American Chrome & Chemical
Dallas, Texas ' ffnc.
1 Corpus Christe. Texas
Hitox Corporation of America
Corpus Christi, Texas
Valhi Inc.
Dallas, Texas
NL Industries Inc.
Valhi Inc.
Houston, Texas


tied Whitaker Company
Roanoke, Virginia
Hoover Color Corporation
Hiwassee, Virginia
Hoechst Celanese Corporation
Performance Products Division
Portsmouth. Virginia

Source: Reference 21.
                            TABLE 5-9.
     EMISSION FACTORS FOR o-DICHLOROBENZENE IN DYE
                          SYNTHESIS'1
Emission
Category
Process
Storage
Fugitive
TOTAL
kg o-DCB emitted
per Mg
o-DCB used
•MMMMHIM^HIMHHHMi
0.40
0.05
0.05
0.5
Ib o-DCB emitted
per ton
o-DCB used
MIWHMHMMMB
0.80
0.10
0.10
1.0
Emission
Factor
Quality
Rating5
•••••I^HMHB
u
u
u

'1980 data.
""Not enough information available to assign a quality rating.

Source: Reference 9.
                              5-29

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 5.9   USE OF MONOCHLOROBENZENE AND ORTHO-DICHLOROBENZENE AS DYE
       CARRIERS IN TEXTILE DYEING
       Monochlorofaenzene (MCB) and o-dichlorobenzene (o-DCB) are effective dye carriers in
 the coloring of textile products.18-22 Dye carriers or dyeing accelerants are used to promote dye
 migration and transfer to produce even and satisfactory dyeings.  They may be used on cellulose
 triacetate fibers, but are typically used on polyester.

       Carrier selection is governed primarily by the carrier's boiling point, which must be high
 enough to prevent evaporation or steam distillation of the carrier from occurring at the dyeing
 temperatures, and low enough to be removed from  the fabric under plant drying conditions.
 Since dye carriers have little or no solubility in water, emulsifiers are needed to disperse the
 carrier in the dye bath.  Many carriers are available  in the pre-emulsified form.  As a general
 rule, stronger carriers, including phenolic and chlorinated aromatic compounds, are used in open
 equipment, at a boil, while weaker carriers are used in high temperature dyeing.

       The Standard Industrial Classification (SIC)  codes for establishments engaged in the
 dyeing of fibers are listed below.

 «      Broadwoven fabric mills, wool - 2231
 •      Knitting mills - 225
       Finishers of broadwoven fabrics of man-made fibers and silk - 2262
 •      Finishers of textiles, not elsewhere classified - 2269
      In 1987, 106 wool, broadwoven fabric mills, 245 plants producing broadwoven fabrics
of man-made fibers and finishing silk, and 176 finishing plants for man-made fibers and silk were
in operation in the United States.23

      Knitting mills varied greatly in numbers depending on the type of product. In 1987, over
800 faculties were estimated to have produced knit outerwear (SIC 2253), while only 58 were
      *
                                        5-30

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 estimated to have produced knit underwear (SIC 2254).  The number of weft knit fabric mills
 (SIC 2257) was estimated at 304 in 1987.  SICs 2251 and 2252, which include women's hosiery
 (except socks and hosiery, not elsewhere classified), respectively, had a combined 514 facilities.23

       Ward's Business Directory lists 31 fabric finishing facilities (SIC 2262) in the United
 States with sales greater than $1,000,000.21  Ward's also lists 55 finishing facilities for SIC 2269,
 38 fabric mills for SIC 231, and 436 knitting mills for SIC 225.  These lists are provided in
 Appendix B, Tables B-l, B-2, B-3 and B-4, respectively.

       Potential emission sources of o-DCB in the  textile dyeing  industry  include process
 equipment vents, open process equipment, equipment leaks, drying operations, and transfer and
 handling operations.  The discussion in Section 4.1 on fugitive emissions should be referred to
 for more detail. No quantitative emissions data for the textile dyeing industry are available. The
 reader is encouraged to contact plant personnel to confirm the existence of emissions and control
 technology to estimate emissions for a specific source.

 5.10   USE OF 1,2,4-TRICHLOROBENZENE AS  A  DYE CARRIER  IN THE  TEXTILE
       DYEING INDUSTRY
  »

       Textile mill operations which  use* 1,2,4-TCB  include wool  scouring, woven fabric
 finishing (simple and complex processing with desizing), and knit fabric finishing. In most cases,
 1,2,4-TCB dye carrier is used only when specific (usually darker) hues are required in man-made
 fibers.24
       When used as a dye carrier, 1,2,4-TCB is combined with a disperse dye and a leveling
agent, and then applied to the material at 100°C (212°F) for several hours. Typically, the amount
of TCB contained in the dye carrier formulation ranges from 10 percent to 90 percent of the total
formulation or from less than 2 percent to 10 percent by weight, once added to the bath.  At this
point, excess carrier is removed by either alkaline scour at 70° to 80°C (158° to 176°F) with
sulfated fatty alcohol, or rinsing the material followed by heating to 190°C  (374°F) for one

                                        5-31

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 minute.24 General processes and equipment for use of dye carriers are described in Section 5.8
 of this report.

       A listing of the  plants involved in the finishing of textile products is included in
 Appendix B.  The Standard Industrial Classification (SIC) codes for these establishments are
 listed below.

 •      Finishers of broadwoven fabrics of man-made fibers and silk - 2262
 •      Finishers of textiles, not elsewhere classified - 2269

       Potential emission sources of 1,2,4-TCB in the textile dyeing industry include process
 equipment vents, open process equipment, equipment leaks, drying operations, and transfer and
 handling operations. The discussion in Section 4.1 on fugitive emissions should be referred to
 for more detail. No quantitative emissions data for the textile dyeing industry are available.  The
 reader is encouraged to contact plant personnel to confirm the existence of emissions and^ontrol
 technology to estimate emissions for a specific source.

 5.11   USE OF PARA-DICHLOROBENZENE AS A PESTICIDE

       Para-dichlorobenzene has historically been used in a variety  of agricultural applications
 including use in tobacco seed beds for blue mold control and in peach trees for borer control.5-8
 However, current federal manufacturing  use registrations  support only indoor use, including
 primarily moth control.8

       The pesticide Paracide® is produced  at PPG Industries, Inc. of Pittsburgh, Pennsylvania.
 In 1988, the consumption of p-DCB (para-dichlorobenzene)  as a  pesticide was 4.5 million
kilograms (10 million pounds).1  Para-dichlorobenzene is typically used  hi its solid  form at
nominally 100 percent purity.8  The manufacturers are subject to change as market conditions
change, facility ownership changes, plants are closed, etc. The reader should verify the existence
of particular facilities by consulting current  listings and/or the plants themselves. The  level of
                                         5-32

-------
 chlorobenzene emissions  from any given facility is a function of variables such as capacity,
 throughput and control measures, and should be determined through direct contacts with plant
 personnel.
5.12   USE OF  1,2,4-TRICHLOROBENZENE  IN  THE  MANUFACTURE  OF  THE
       HERBICIDE BANVEL*
       Trichlorobenzene is used in the formulation of the herbicide Banvel* The common name
of Banvel* is dimethylamine salt of dicamba (CAS number 2300-66-5).  Banvel* is used as a
herbicide to  control weeds in crops such as asparagus, com, grain sorghum, and sugarcane.
Banvel* is also used in noncropland areas such as rangeland and pastures to control brush and
vines.5

5.12.1 Process Descriptions
                                        j

      U,4-Trichlorobenzene is used to produce dicamba (Banvel*, 3,6-dichloro-o-anisic acid,
3,6-dichloro-2-methoxybenzoic acid) by what is known as the dicamba process.
         a
                                                             COOH
                     NaOI
CO?    Dimethyl
                   CH3OH
          Sulfate
                                                                    OCH<
     1,2,4-TCB
                          dicamba
                                     5-33

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 Li the process, TCB and sodium hydroxide are dissolved in methanolin the presence of carbon
 dioxide and dimethyl sulfate and heated to 190°C (374°F) for 4 hours in a bomb.  The resultant
 mixture is cooled, filtered, dried, and further processed to make Banvel*.24

        In 1988, the production of Banvel* consumed  6.4  to 7.3 million kilograms  (14 to
 16 million  pounds) of trichlorobenzene.1  In  1991,  Sandoz Crop Protection Corporation of
 Beaumont, Texas was the only facility to produce  Banvel®.1-5  Capacity and/or production
 estimates were not available from this facility. The manufacturer is subject to change as market
 conditions change, facility ownership changes, plants are closed,  etc. The reader  should verify
 the existence of particular facilities by consulting current listings and/or the plants themselves.
 Due to the limited number of production facilities, information was riot available for  the
f formulation process or specific application procedures of Banvel®.

 5.12.2 Emissions

        An estimated 33 percent of the total quantity of the TCB used by the pesticide industry
 was converted or consumed during the manufacturing process. Furthermore, based, on process
 descriptions, approximately one percent of the TCB used  was released into the environment, of
 which two-thirds was discharged to air.24

       In the  first step  of Banvel® manufacture, 90 percent of 1,2,4-TCB  is consumed in
 production of 2,5-dichlorophenyl.5 The remaining 10 percent is assumed to be released into  the
 environment, most of which is probably converted to other compounds by side reactions.  Less
 than 1 percent used for dicamba (Banvel*) production was released to the  air in the form of
 fugitive and handling emissions.2*
                                          5-34

-------
 5.13   USE OF ORTHO-DICHLOROBENZENE AS A SOLVENT IN PHARMACEUTICAL
        MANUFACTURING
        Ortho-dichlorobenzene is  used  as  a solvent in the manufacturing of pharmaceutical
 products by chemical synthesis.  Current consumption estimates of o-DCB in pharmaceutical
 preparations were not available.

 5.13.1  Process Description

        Synthetic Pharmaceuticals are normally manufactured in batch operations, many of which
 involve the use of solvents.25 Figure 5-3 presents basic operations that may be used in a batch
 synthesis process. To begin a production cycle, the reactor is washed with water and dried with
 a solvent  Air or nitrogen is usually used to purge the tank after it is cleaned.  Solid  reactants
 and solvent are then charged to the reactor (Step 1).  After the reaction is complete, remaining
 unreacted volatile compounds and solvents may be distilled off, typically using a water cooled
 condenser.  The pharmaceutical product is then transferred to  a  holding tank (Step 2)i  In  the
 holding tank, the product may be washed three to four times with water or solvent to remove any
 remaining reactants  and byproducts. The solvent used in washing is generally distilled  from  the
 reaction product (Step 3).  The crude product may then be dissolved in another solvent and
 transferred to a crystallizer for purification  (Step 4).  After crystallization, the solid material is
 separated from the  remaining solvent by centrifuging  (Step 5).  While  in the centrifuge,  the
 product cake may be washed several times with water or solvent.  Tray, rotary, or fluid-bed
 dryers are employed for final product finishing (Step 6)."

       The Standard Industrial Classification (SIC) code for pharmaceutical preparations is 2834.
There are approximately 732 pharmaceutical plants producing drugs in the United States and its
territories.  Fifty percent of the plants are small and have fewer than 20 employees.  Fifty-three
percent of the plants are located in 6 states:  13 percent in New York, 13 percent in California,
 12 percent in New Jersey, and 5 percent in Pennsylvania, Illinois and Texas.23 These states also
                                         5-35

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                      CD
                                                     £
                                                      e

                                                      c
                                                     CJ
                                                     u
                                                     i.

                                                     S5
                                                     •a
                                                     o

5-36

-------
 contain the largest plants in the industry.  Puerto Rico has had the largest increase in number of
 operational plants hi recent years.

 5.13.2  Emissions

        Each step of the manufacturing process of a pharmaceutical product may be a source of
 o-DCB emissions.  The magnitude of emissions varies widely within and among operations;
 therefore,  it is impossible to cite typical emission rates for various operations.  Figure 5-3
 identifies process vents (A) or  solvent waste streams (B) from which potential emissions are
 possible.

       The following is an approximate ranking of emission sources that has been established
 in order of decreasing emission significance.  The first four sources typically account for the
 majority of emissions from a plant25

 •      Dryers
 •      Reactors
 •      Distillation units
       Storage and transfer
       Filters
 •      Extractors
 •      Centrifuges
 •      Crystallizers

       Another potential emission source is equipment leaks.  The discussion in Section 4.1 on
fugitive emissions should be referred to for more detail.

       Condensers, scrubbers, and carbon adsorbers can be used to control emissions from all
of the above emission sources. Storage and transfer emissions can also be controlled by the use
                                          5-37

-------
 of vapor return lines, conservation vents, vent scrubbers, pressurized storage tanks, and floating
 roof storage tanks.

 5.14   MISCELLANEOUS USES OF CHLOROBENZENES

      " This section discusses miscellaneous production uses of chlorobenzenes for which no
 detailed process information was available.

 Use of Trichlorobenzenes - -

       l,2,4rTrichlorobenzene is  used in formulations of functional fluids such as dielectric
 liquids and transformer oils.   1,2,4-TCB is also used as a solvent for crystallization of high
 melting point products, in termite control, septic tank and drain cleaner preparations, and as a
 lubricant Further information on  these uses was not available at the time of report preparation.
 Emissions occur during production and use of secondary products.22

       1,3,5-Trichlorobenzene is used as a solvent for high temperature melting point products
in addition to uses as coolants in electrical  installations and glass tempering, heat transfer
mediums, lubricants, and synthetic transformer oils.  It is used in termite preparations and
                                                                          %
polyester dyeing. Emissions of 1,3,5-trichlorobenzene are expected during the production and
use of these products.18'24

       1,2,3-Trichlorobenzene is used as an organic intermediate and in synthetic transformer oil.
Emissions are expected from general laboratory usage and from its  use as a transformer oil.9
Historically, 1,2,3-trichlorobenzene was also used as a termite control agent but is not currently
used for that purpose.8
                                         5-38

-------
 5.15   REFERENCES FOR SECTION 5.0
 1.
 3.
5.

6.




7.

8.


9.




10.



11.


12.


13.
 SRI Chemical and Economics Handbook, "Chlorobenzene Production," Menlo Park CA
 1989.                                                                   '   '


 Nitrochlorobenzene  Chemical Product  Synopsis,   Mannsville Chemical Products
 Corporation, Asbury Park, NJ, September 1983.
                                                                            ft*

 Liepins, R. and F. Nixon, Industrial Process Profiles for Environmental Use:  Chapter
 6.  The Industrial Organic Chemicals Industry, EPA-600/2-77-023f, U.S. Environmental
 Protection Agency,  Industrial Environmental Research Laboratory, Cincinnati  OH
 February 1977.                                                          '


 7990 Directory of Chemical Producers, United States  of America,  SRI International
 Menlo Park, CA, 1990.


 Farm Chemicals Handbook, 1991, Meister Publishing Company, Willoughby, OH, 1991.


 U.S. Environmental Protection Agency, Investigation of Selected Potential Environmental
 Contaminants: Halogenated Benzenes, EPA-560/2-77-004, Office of  Toxic Substances
 Washington, DC, July 1977.


 The Merck Index, Tenth Edition, Merck and Company, Rahway, NJ,  1984.


 Opatick, Richard, Chlorobenzene Producers Association.  Memorandum to Michael Ling
 TRC Environmental Corporation, August 4,  1993.


 U.S.  Environmental Protection Agency,  An Exposure  and  Risk Assessment for
 Dichlorobenzenes, Final Draft, Office of Water Regulations and Standards, Washington
Boscato, J.F. et al., Synthesis of Polyphenylene  Sulfur,   Polymer Bulletin (Berlin)
4(7):357-359, 1981.


Kirk-Othmer Encyclopedia of Chemical Technology, Volume 18,  John Wiley and Sons
New York, NY, 1982.


Toluene Dissocyanate Chemical Products Synopsis, Mannsville Chemical Products Corp
Asbury Park, NJ, October 1990.


International Programme on Chemical Safety, Environmental Health Criteria 75- Toluene
Dnsocyanates, World Health Organization, Geneva, 1987.
                                       5-39

-------
 14.



 15.


 16.
 17.



 18.


 19.


 20.



 21.


 22.



 23.

 24.



25.
 U.S. Environmental Protection Agency, Organic Chemical Manufacturing, Volume 7:
 Selected Processes, Report 4: Toluene Diisocyanate, EPA-450/3-80-028b, Office of Air
 Quality Planning and Standards, Research Triangle Park, NC, December 1980.

 Hancock, E.G. (ed.), Toluene, the Xylenes and their Industrial Derivatives, Elsevier
 Scientific Publishing Company, New York, NY,  1982.

 Rosensteel, R.E.,  U.S.  Environmental  Protection Agency, Chemicals Manufacturing
 Section.  Memorandum  to T. Lahre, including review comments by D. Beck, U.S.
 Environmental Protection Agency,  Air Management  Technology Branch, Research
 Triangle Park, NC, November  16, 1984.

 Clarke, Eric A., Ecological and Toxicological Association of Dyestuffs Manufacturing
 Industry, Scarsdale, New York.  Letter to Tom  Lahre, U.S. Environmental Protection
 Agency, Office of Air Quality  Planning and Standards, Durham, NC, March 13, 1985.

 Kirk-Othmer Encyclopedia of Chemical Technology, Volume 8, Third Edition, John Wiley
 and Sons, New York, NY, 1979.

 Color Index International, Third Edition, The Society of Dyers and Colourists, London
 England. 1987.

 Steadman, T.R., et al. Industrial Process Profiles for Environmental Use: Chapter 7,
 OrganicDyes and Pigments Industry, EPA-60Q/2-77-023g, U.S. Environmental Protection
 Agency, Cincinnati, OH, February 1977.

 Gale Research Inc., Ward's Business Directory of U.S. Private and Public Companies-
 1991, Volume 4, Detroit, MI. 1991.

 Slimak, K. et al., Materials Balance for Chlorobenzenes, EPA-560/13-80-001,  U.S.
 Environmental Protection Agency, Office of Toxic Substances, Washington, DC January
 1980.                                                                       *

 1987 Census of Manufacturers, U.S. Department of Commerce, Bureau of Census.

 McNamara, P.W. et al.,  An Exposure and Risk Assessment for  12,4-Trichlorobenzene
 Final Draft, U.S.  Environmental Protection Agency, Office of Water Regulations and
 Standards, Washington, DC, June  1981.

 Control of Volatile Organic Emissions from Manufacture of Synthesized Pharmaceuticals
Products, EPA-450/2-78-029,  U.S. Environmental  Protection Agency, Office of Air
 Quality Planning and Standards, Research Triangle Park, NC, December 1978.
                                        5-40

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                                    SECTION 6.0
   EMISSIONS FROM THE USE OF MATERIALS CONTAINING CHLOROBENZENES

      Chlorobenzenes are an ingredient in the manufacture of a number of products and materials.
 This section discusses air emissions from these products containing chlorobenzenes.  Potential
 emissions sources are  identified and available  emission factors are presented where available.
 The reader is advised to contact the specific sources in question to verify the nature of the
 process, production volume, and control techniques used before applying any of the emission
 factors presented in this section.

 6.1   USE OF PARA-DICHLOROBENZENE IN MOTH CONTROL

      Para-dichlorobenzene is used in consumer, commercial,  and industrial sectors for moth
 control. Cakes, blocks, and balls formulated by p-DCB contain  greater than 99 percent p-DCB.1
 In 1988, ten percent of p-DCB production in the United States, equalling 4.5 million kilograms
 (10 million  pounds),  was consumed  as  a moth control substance.2   Information on the
 manufacture of these products was not available at the time of  report preparation.

     Commercial applications of moth control products include preservation of glycerin treated
 dried  flowers  during storage  and handling and moth proofing of textiles during production.1
 Para-dichlorobenzene is applied to the textiles during the dyeing operation and may be fixed in
 the fibers by chemical reactions with protein.3  It may also be combined and sprayed with a
 volatile solvent onto fabric.

     A study performed in 1987 tested fourteen combinations of several variables affecting the
rate of p-DCB emissions from crystal  moth control cakes.4   These  tests were conducted in
environmental test chambers with temperature,  humidity, and air exchange rate controls. The
measured emission rate was compared with a model emission rate equation and found to be
within ten percent in all cases. The emission rate equation is presented below.
                                        6-1

-------
                                    E - (Q x (F/A)
 where:
      E - emission rate (pg/cm2-hr)
      C SB concentration of p-DCB (ug/cm3)
      F = flow rate through chamber (106 cm3/hr)
      A » area of sample (cm2)

      All of the p-DCB used in moth control products and applications is expected to be emitted
 to the atmosphere by sublimation during production or use.1  In general, the use of moth control
 agents are too widespread to categorize. Manufacturers of moth control agents containing p-DCB
 were not identifiable due to limited information.

 6.2   USE OF PARA-DICHLOROBENZENE AS A SPACE DEODORANT

      Sixteen percent of p-DCB produced in the United States has a non-intermediate dispersive
 use in space, toilet bowl, and garbage deodorants.  Due to its volatility, density, pleasant odor,
 and  solid nature  at room  temperature,  it is used alone or in combination  with  disinfectant
 substances to produce deodorants in a variety of continuous evaporation forms, most commonly
 solid air deodorizers and toilet blocks.

 6.2.1 Process Description

      Para-dichlorobenzene-derived deodorant products contain up to 100 percent p-DCB with
 a perfume added in some cases.  Limited information was available detailing the processes by
 which the deodorant types are manufactured. However, most solid block deodorants are formed
by combining the active ingredients such as p-DCB with a carrier substance.  The most common
carrier for all types of deodorants is water; however, other carriers such as process oils, solvents,
and various petroleum products are also employed depending on the form of the deodorant. In
solid and semisolid products, active ingredients are incorporated into sublimable water based gels,
                                         6-2

-------
 waxy solids, or powder form.5  The process by which active substances are incorporated into
 toilet blocks is assumed to be similar in nature.

      In 1988, 16  percent of p-DCB production in the United States, equalling 6.8 million
 kilograms (15 million pounds), was  consumed in the manufacture  of space deodorants.2
 Information  concerning specific manufacturers  was not available.  Users of p-DCB-based
 deodorant products include the industrial, commercial, and consumer sectors.

 6.2.2  Emissions

      It is estimated that all p-DCB incorporated into solid space and garbage deodorants will
 enter the atmosphere by sublimation during production or use. It is estimated that approximately
 90 percent of the p-DCB used for this purpose is released to the air, the remaining 10 percent
 is released to either land or water, depending upon whether it is used as a garbage deodorant or
 toilet deodorant, respectively.1                      .

 6.3   USE OF CHLOROBENZENES AS SOLVENTS IN ORGANIC SOLVENT CLEANING
      OPERATIONS
      Surface  cleaning or degreasing includes the solvent cleaning  or conditioning of metal
surfaces and parts, fabricated plastics, electronic and electrical components, and other nonporous
substrates. These cleaning processes are designed to remove foreign materials such as grease,
oils, waxes, carbon deposits, and moisture, usually in preparation for further treatment such as
painting, electroplating, galvanizing, anodizing, or applying conversion coatings.

      Chlorobenzenes are employed as cleaning  and  degreasing agents in solvent cleaning
operations to remove water-insoluble soils from  metal, plastic, fiberglass  or other  surfaces.
Ortho-DCB is contained in automobile engine cleaners; carburetor cleaners; in formulations to
remove paints, inks,  varnishes, lacquers/resins, gums,  waxes, heavy greases, acetylcellulose,
sulfur and organic sulfur compounds, and tarry substances in stills and processing equipment;

                                         6-3

-------
 shoe polish; metal polish; rust preventatives; and other cleaning/polishing formulations.1  1,2,4-
 Trichlorobenzene  is used in degreasing formulations for electronic wafer  stripping in  the
 electronic components industry and engine cleaning.6

      Data on the current use of chlorobenzenes in solvent cleaning operations are scarce.7 This
 section describes  general  processes, emissions  sources, and  available emissions data from
 degreasing operations.

 6.3.1  Process Description

      The three most commonly used types of organic solvent cleaners,are open top vapor
 cleaners  (OTVCs),  in-line cleaners,  and  cold cleaners.   OTVCs  are  primarily  used in
 metalworking operations and other manufacturing operations.* The vapor cleaning process is one
 in which solvent vapors rise to the level of the condensing coils and form a controlled vapor zone
 that prevents vapors from escaping the tank. Parts are immersed into  this zone where solvent
 vapors condense and dissolve foreign materials on the parts.7

      In-line cleaners (also called conveyorized cleaners) employ a continuous feed of soiled parts
 into the cleaning unit The majority of in-line cleaners operate in the vapor phase, however, they
 may also operate hi the non-vapor phase.  In-line cleaners are typically used in large-scale
 operations and are  normally enclosed except for parts inlet and exit openings.8  With these
 exceptions, the cleaning techniques are the same as those used in vapor or cold cleaning.

      Cold cleaning is a batch process operation  in  which  solvents are applied at room
temperature  or  slightly above room temperature, but always below the solvent's boiling point.
The mechanical or industrial parts or tools to be cleaned are placed in  a basket inside the cold
cleaner and immersed in the solvent  Parts too large for immersion may be sprayed or brushed.
The solvent tank is often agitated to enhance its cleaning action.  After cleaning, the pans are
removed from the tank and allowed to dry.
                                          6-4

-------
      Cold cleaners are usually the simplest and least expensive to operate of the three types of
 solvent cleaners.  The two basic types of cold  cleaners are maintenance  cold cleaners and
 manufacturing cold cleaners. The primary cold cleaning application is cleaning of tools or metal
 parts at service and automotive repair stations and manufacturing facilities. Cold cleaners may
 incorporate covers and freeboards to limit the  evaporative loss of solvents.  Freeboard is the
 distance between the solvent level and the top edge of the unit.*

      No further information could be gathered  on the actual quantities of chlorobenzenes used
 or  specific  processes or equipment which are employed for the  uses  of chlorobenzenes as
 cleaning solvents.

 6.3.2 Emissions

      Types of emissions produced by cold cleaning include those generated by bath evaporation
 to surrounding air, solvent carry-out of cleaned  parts, agitation, waste solvent evaporation, and
 spray evaporation.  Emissions associated with  conveyorized degreasers result from the same
 processes but are reduced because of the nearly complete enclosure of the conveyorized system.
 Some emissions are also expected from evaporation of blended cleaning solvents during mixing
 and handling.10

      Uncontrolled emissions from degreasers  can  be approximated by  material balance by
 assuming that the quantity of makeup solvent is equal to the amount of solvent evaporated from
 the process over the long term.  To estimate emissions after controls by material balance,  the
quantity of solvent collected or destroyed in control devices, and not recycled to the process,
must be subtracted from the quantity of makeup solvent.

     Although chlorobenzenes are expected to contribute to degreaser emissions, it should be
noted that  significant use of chlorobenzenes as  primary degreasing  solvents  has  not been
documented. Chlorobenzenes, by themselves, are not used as solvents, but probably occur only
in solvent mixtures:  Moreover, the quantities of chlorobenzenes used in solvent mixtures are not
                                          6-5

-------
likely  to  be very large."  The reader  is encouraged to contact local plant personnel for
information on specific processes, solvent formulations emissions, and control technologies.

6.4  USE OF TRICHLOROBENZENES IN WOOD PRESERVATIVES

     Trichlorobenzene is  used as  a "soil treatment to repel or poison termites  around the
foundation of buildings.12 The trichlorobenzene products are applied on surfaces or injected into
standing wood buildings.*  The technical product of trichlorobenzene is a mixture of the
1,2,3-trichlorobenzene and  1,2,4-trichlorobenzene isomer.12  No information was available on the
formulation process or application practices.

     The formulations and users of wood preservatives and products containing trichlorobenzene
could not be identified from the literature.  Approximately one percent of 1,2,4-TCB is estimated
to be emitted to the atmosphere during application and handling, with the balance remaining in
the wood.'  Emissions factors for 1,2,3-TCB have not been reported.
                                         6-6

-------
 6.5   REFERENCES FOR SECTION 6.0

 1.    U.S.  Environmental  Protection  Agency,  An Exposure  and Risk  Assessment for
      Dichlorobenzenes, Final Draft, Office of Water Regulations and Standards, Washington
      DC, 1981. p. A-l.                                                             '


 2.    SRI Chemical and Economics Handbook, "Chlorobenzene,"  Menlo Park, CA  October
      1989.                                                                 '


 3.    Kirk-Othmer Encyclopedia of Chemical Technology, Volume 13, John Wiley and Sons, New
      York, NY, 1981.


 4.    Nelms,  L. M. et al., Determination of Emission Rates and Concentration Levels of p-
      Dichlorobenzene from Moth Repellant, EPA-600/D-87/165, Research Triangle Park, NC
      May 1987.


 5.    Kirk-Othmer Encyclopedia of Chemical Technology, Volume 16, John Wiley and Sons  New
      York, NY, 1982. pp. 297-306.


 6.    McNamara,  P.W., et al., An Exposure and Risk Assessment for 12,4-Trichlorobenzene,
      Final Draft, U.S. Environmental  Protection  Agency, Office of Water Regulations and
      Standards, Washington, DC, June 1981.


7.    Grume,  R.V. and M.B. Turner, Air Pollution Engineering Manual, "Organic  Solvent
      Cleaning (Degreasing)," Air & Waste Management Association, Van Nostrand Reinhold,
      New York, NY, 1992.


8.    U.S. Environmental Protection Agency, Alternative  Control Technology Document  -
      Halogenated Solvent Cleaners, EPA-450/3-89-030, Office of  Air Quality Planning and
      Standards, Research Triangle Park, NC, August 1989.

9.    U.S.  Environmental  Protection Agency,  Organic  Solvent  Cleaners - Background
     Information of Proposed Standards, EPA-450/2-78-045a, 1979.

 10.    U.S. Environmental Protection Agency, Guidelines  for Control of Trichloroethylene,
     Perchloroethylene, 1,1,1-Trichloroethane, Methylene Chloride,  and Trichlorofluoroethane
     from Existing Organic  Cleaners,   Working Group Draft,  Office of  Air Quality and
     Planning Standards, Research Triangle Park, NC, July 1981.

11.   Rosensteel, R.E., U.S. Environmental Protection Agency, Chemicals Manufacturing Section.
     Memorandum to T. Lahre, including review comments by D. Beck, U.S. Environmental
     Protection Agency, Air Management Technology Branch, Research Triangle Park NC
     November 16, 1984.
                                        6-7

-------
12.   Ulbnann's Encyclopedia of Industrial Chemistry, Fifth Edition, Volume  AM, "Insect
     Control," VCH Publishers, New York, NY, 1989.
                                        6-8

-------
                                    SECTION 7.0
                            BYPRODUCT EMISSIONS -
    PROCESSES UNRELATED TO PRODUCTION OR USE OF CHLOROBENZENES
      Chlorobenzenes and many other pollutants can be emitted to the atmosphere as the result
 of  product manufacturing or from the burning of fossil fuels.   Processes  that release
 Chlorobenzenes as a byproduct are described in  this section.  These processes include waste
 treatment processes, waste oil combustion, and chlorinated solvent production.

 7.1   VOLATILIZATION OF  CHLOROBENZENES FROM WASTEWATER TREATMENT
      OPERATIONS

      Chlorobenzenes may be  emitted when wastes containing  Chlorobenzenes are present in
 surface impoundments for treatment and storage of wastewater or in open treatment and storage
 tanks. Treatment and storage facilities may be located at the site of generation of the waste, or
 at a separate commercial waste treatment plant  In addition, publicly owned treatment works
 (POTWs)  may  emit Chlorobenzenes if they receive  wastewater from  plants producing
 Chlorobenzenes either as a main product or as a byproduct, or from plants using Chlorobenzenes
 as an  intermediate.  For example, at one 42 million gallon per day (MOD) POTW, 93, 61 and
 100 percent, of the influent contributions of 1,2,4-TCB, m-DCB,  and p-DCB, respectively, were
 found to have originated as  byproducts of  industrial processes.   Moreover,  at this plant,
 approximately 54 percent of the volatile organics (including MCB) were attributed to industrial
 origins.1
     A typical secondary treatment facility sequence utilized by many existing wastewater
treatment facilities consists of screening, grit removal, primary clarification, use of conventional
activated sludge with aeration, and chlorination. Due to the volatile nature of Chlorobenzenes,
air emissions are expected mainly from clarification and aeration processes.  Measurements of
the concentrations of Chlorobenzenes in the effluent of the 42 MGD  POTW discussed above
suggest that the  overall  treatment process  removes 40  to  90  percent of the incoming
Chlorobenzenes, primarily during activated sludge aeration.  Partitioning of 1,2,4-TCB, m-DCB,

                                       7-1

-------
 and p-DCB to the primary clarifier sludge and activated sludge indicates that some fraction of
 these pollutants may accumulate onto settleable or floatable solids. However, the remainder is
 expected to be removed by either air stripping or by biodegradation.1 Air stripping would result
 in air emissions of chlorobenzenes.

      A study conducted at two Chicago-area wastewater treatment facilities estimated  that
 approximately 95 percent of the chlorobenzenes in the influent waters biodegraded in activated
 sludge systems while only 2 percent volatilized. However, if all of the influent chlorobenzenes
 at the two facilities were to volatilize,  it would account for 7 kilograms (15.4 pounds) per year.2
 Another study conducted in California on  statewide municipal wastewater treatment plants
 identified chlorobenzenes as one category of 16 VOC compounds being emitted.3 The study did
 not elaborate on the amount of chlorobenzenes emitted because the compounds had been detected
 in fewer than 25 percent of the plants. No other information was available on emissions from
 this  study."
      Testing of the aeration basins at a small municipal treatment plant (handling 40 percent
industrial and 60 percent municipal sewage) resulted in the measurement of emissions of o-DCB
and m-DCB ranging from levels of 148  to  478 grams/hour  and  155 to 609 grams/hour,
respectively.4 Monochlorobenzene was measured only at trace quantities. No data were collected
for other chlorobenzenes.  Too little data are available to extrapolate these test results to other
wastewater treatment plants.

      A study developed for emissions modeling from a typical POTW facility identified that
chlorobenzenes were present The emission factors from the model POTW plant are presented
in Table 7-1, and represent emissions from the POTW overall.  [Further information was not
available due to  the inability to locate  the document from which the emission factors were
presented.  The following reference is likely to have information on the emission factors located
in the table:  White, T.S.  Volatile Organic Compound Emissions From Hazardous Waste
Treatment Facilities at Downstream POTW (Final Report).  Radian Corporation.  Prepared
under EPA Contract No. 68-02-4378. U.S. Environmental Protection Agency, Research Triangle
Park, NC, 1987.]

                                         7-2

-------
                                 TABLE 71
         EMISSION FACTORS FOR WASTEWATER TREATMENT
                               OPERATIONS
                                 Emission Factor"

                                 ••«•••••••»
                     0.39 Mg/Mg p-DCB in influent
                     (780 Ib/ton p-DCB in influent)

                     0.41 Mg/Mg o-DCB in influent
                     (820 Ib/ton o-DCB in influent)

                     0.50 Mg/Mg m-DCB in influent
                     (1000 Ib/ton m-DCB in influent)

                     0.52 Mg/Mg chlorobenzenes in influent
                     (1040 Ib/ton chlorobenzenes in influent)
                                                              Emission
                                                               Factor
                                                               Quality
                                                               Rating
    Source: Reference 5.
            T

                                  '"tal-."™-
                                                      average POTW
                                                                were nct
                                                         if such wastes are
7.2  HAZARDOUS AND SOLID WASTE INCINERATION
     fron, „«„„. ta addition
o ga,uc compos (including chloroben2enes)
 iz:    combustion of
                                     carbon
                                 to

                                 7-3

-------
      Several methods are used to incinerate municipal waste.  These include mass burn excess
 air  combustion, starved  air  or  modular  combustion, and  refuse-derived fuel combustion.
 Approximately 70 percent of the total municipal solid waste is incinerated in mass burn units.
 More information on the methods of municipal waste combustion can be found in the document,
 Characterization of the Municipal Waste Combustion Industry.6  Similarly, hazardous waste can
 be incinerated by several methods including thermal, catalytic and regenerative incineration.

      Several chlorobenzenes emission factors have been  identified  for municipal  waste
 combustion and are presented in Table 7-2.  The emission factors include all isomers  of
 chlorobenzenes.  These emission  factors were derived from tests on five facilities which were
 using electrostatic precipitators (ESPs) or dry alkaline scrubbers in combination with fabric filters
 as control devices.  The emission factors were determined by calculating the average emission
 rate for all facilities of a given type.7  Therefore, the emission factors are given a rating of "D".

      Open-air burning presents  a particularly unique source of  atmospheric  emissions of
 pollutants.  This method  of solid waste incineration  allows  for exposure to many variables
 including wind, ambient temperatures, and other environmental parameters such as rain and
 humidity, degree of compactness of the refuse, and composition and  moisture of the refuse.  In
 general,  lower temperatures are  achieved  in open-air burning than in closed combustion.
 Therefore, this allows for increased emissions of particulate matter, carbon monoxide, and volatile
 organic compounds (including chlorobenzenes) with decreased emissions of nitrogen  oxides.
 Other important regulating factors for open-air burning are fuel loading  (how  much refuse
 material is burned per unit of land area) and arrangement of the refuse (in rows, piles, or spread
 out).9 Emission factors for chlorobenzenes have not been identified.

7.3   BURNING OF WASTE OIL
     Monochlorobenzene and  o-dichlorobenzene have been  identified as  contaminants  of
potential concern in waste crankcase oils used as fuel. Approximately 1.2 billion gallons of used
automotive and industrial oils are generated annually, of which 35 percent is coUected and used
as fuel.10 Studies of waste oil composition show that waste industrial oils are contaminated with
                                          7-4

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 chlorinated solvents.  It has also been suggested that chlorinated hydrocarbons in the oils are
 formed chemically during oil use or may result from contamination by solvents in holding tanks.
 Observed concentration ranges for MCB and o-DCB in waste oils are 4 to 500 pg/1 and 60 to
 160 ug/1, respectively.10

      Locations of boilers which use waste oils for fuel have not been identified hi the literature.
 It is uncertain how much MCB and o-DCB are released into the atmosphere during the burning
 of waste oil as fuel.  Emissions are related to initial concentrations  of chlorobenzenes in the
 waste oil as well as  boiler operating parameters and control devices.  No information  was
 available concerning actual emission rates.
7.4   HEXACHLOROBENZENE  GENERATION DURING  CHLORINATED  SOLVENT
      PRODUCTION
      Approximately 60 percent of the total national HCB waste load is attributable to chlorinated
solvent production, primarily from the production of carbon tetrachloride, trichloroethylene, and
perchloroethylene. Of these, perchloroethylene production is expected to produce the greatest
quantity. The production of several other chlorinated solvents, such as ethylene dichloride and
1,1,1-trichloroethane, also has the potential to produce HCB at trace levels."

7.4.1 Process Description

      During the production of carbon tetrachloride, trichloroethylene, and perchloroethylene,
HCB is  formed as a  reaction byproduct from chlorination,  oxychlorination,  and  cracking
operations. Flow diagrams illustrating the main processes from producing carbon tetrachloride,
trichloroethylene, and perchloroethylene are presented in Figures 7-1,7-2, and 7-3, respectively.
Potential HCB-containing waste streams are indicated in these figures.  Hexachlorobenzene is
usually found as a residue in the heavy ends of still bottoms during distillation of the purification
process.  The heavy, tarry residue also contains other chlorinated hydrocarbons in addition  to
                                         7-6

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7-7

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 HCB.  Generally, these wastes are removed and stored in containers prior to their ultimate
 disposal by incineration."

      The HCB levels in production wastes vary greatly by chemical  and  by plant.  This
 variability in the HCB concentration is related to the processes and feedstock materials used.
 Wastes generated by trichloroethylene production appear to contain the lowest levels of HCB.
 In general, it is difficult to quantify a typical HCB concentration in the process wastes."

      Currently, known producers of carbon tetrachloride, trichloroethylene, and perchloroethylene
 and their methods of production are shown in Tables 7-3, 7-4, and 7-5, respectively.  Most of
 the listed facilities reported HCB-containing wastes on their Resource Conservation and Recovery
 Act (RCRA) Part A applications on file with  the EPA and state hazardous waste agencies.11

                                      TABLE 7-3.
      CHEMICAL PRODUCERS OF TRICHLOROETHYLENE - 1989
Company
Location
••••••••••••MMMMI
Dow Chemical U.S.A.
Freeport, Texas
PPG Industries, Inc.
Lake Charles, Louisiana
Capacity
Millions kg/yr
(Millions Ibs/yr)
^mmimn^mammmm
54.4 (120)
90.7 (200)
Method of Production
^^^^^^^^^^^^^^^^^^BHI^^^HMMI^^HHI^^H^IHHMI^^^^^HI
Chlorination of ethylene dichloride
Oxychlorination of ethylene dichloride
Source: Reference 12.
7.4.2 Emissions

     The HCB generated by the production of the chlorinated solvents occurs as bottoms from
distillation processes.  When the HCB-containing waste is removed from the distillation unit, the
HCB portion is essentially solid.  Considering its physical state and the low vapor pressure of
HCB at ambient temperatures (i.e., 20°C or 68°F), the potential for fugitive HCB volatilization
                                       7-10

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                                         TABLE 7-4.
       CHEMICAL PRODUCERS OF  CARBON TETRACHLORIDE  -
                                             1989
               Company
                Location
     Akzo Chemicals Inc.
      Akzo America Inc.
      Chemical Division
      Le Moyne, Alabama
   Capacity
 Millions kg/yr
(Millions Ibs/yr)
   118 (260)
                                                                Method of Production
 Not available
     Dow Chemical U.S.A.
      Pittsburg, California
      Plaquemine, Louisiana
   36.3 (80)
   56.7 (125)
 Methane chlorination and chlorinolysis
 of mixed hydrocarbons with
 perchloroethylene co-product

 Chlorinolysis of mixed hydrocarbons
 with perchloroethylene co-product
     Hanlin Group, Inc.
      LCP Chemicals Division
      Moundsville, West Virginia
    3.6 (8)
Not available
     Occidental Petroleum Corporation
      Occidental Chemical Corp.,
      subsidiary
      Electrochemical & Specialty
      Products Group
      Electrochemicals Division
      Belle, West Virginia
   negligible
Not available
    Vulcan Materials Company
      Vulcan Chemicals Division
      Geismar, Louisiana

      Wichita, Kansas
   40.8 (90)
   272 (60)
Chlorinolysis of mixed hydrocarbons
with perchloroethylene co-product
Methyl chloride chlorination and
methane chlorination, chlorinolysis of
mixed hydrocarbons with
perchloroethylene co-product
   Source: Reference 12.


during  waste  generation  and  waste  handling  operations is minimal.   Actual tests  at a

perchloroethylene plant have indicated that HCB waste handling operations are not a source of
                                            7-11

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                                         TABLE 7-5.
       CHEMICAL PRODUCERS OF PERCHLOROETHYLENE - 1989
                Company
                 Location
       Dow Chemical U.S.A.
        Pittsburg, California

        Plaquemine, Louisiana
      Occidental Petroleum Corporation
        Occidental Chemical Corp.,
        subsidiary
        Electrochemical & Specialty
        Products Group
        Electrochemicals Division
        Deer Park, Texas
      PPG Industries, Inc.
       Chemicals Group
       Lake Charles, Louisiana
   Capacity
 Millions kg/yr
(Millions Ibs/yr)
   22.7 (50)

   40.8 (90)
  81.6 (180)
  90.7 (200)
                                                            Method of Production
 Chlorinolysis of mixed hydrocarbons producing
 carbon tetrachloride as a co-product

 Chlorinolysis of mixed hydrocarbons producing
 carbon tetrachloride as a co-product
Not available
Chlorination of ethylene dichloride
      Vulcan Materials Company
       Vulcan Chemicals Division
       Geismar, Louisiana

       Wichita, Kansas
   68 (150)
  22.7 (50)
Chlorinolysis of mixed hydrocarbons producing
carbon tetrachloride as a co-product

Chlorinolysis of mixed hydrocarbons producing
carbon terrachloride as a co-product
     Source: Reference 12.
                                        «


HCB air emissions. In these tests, neither uncontrolled air emissions associated with handling

HCB-containing waste nor air emissions from waste storage tanks were found to contain HCB.11


      In the past, waste storage piles at plants indirectly generating HCB may have released

fugitive HCB emission due to slow evaporative losses.   However, the recent advent  of the

management and control of hazardous wastes under the Resource Conservation and Recovery Act

(RCRA),  has  greatly reduced  the use  of waste storage piles because of the stringent site

contaminant and monitoring requirements in place for open piles.  Most HCB waste generators

currently store their wastes  in containers prior to final disposal in incinerators or landfills.11
                                           7-12

-------
     The majority of chlorinated solvent plants known to generate HCB wastes use incineration
as a means of ultimate disposal, while a few  utilize  offsite landfill facilities.  The offsite
incinerator must meet the same RCRA requirements to be allowed to burn HCB. The ultimate
HCB emission point from incinerating these wastes will not necessarily be the incinerator stack,
but wiU probably be the stack on the caustic wet scrubber  used to control hydrochloric acid
emissions from the incinerator.11
                                        7-13

-------

-------
7.5   REFERENCES FOR SECTION 7.0
 1.    U.S. Environmental Protection Agency, Fate of Priority Toxic Pollutants in POTWs - 30-
      Day Study, EPA-440/1-82-302, Effluent Guidelines Division, August 1982, pp. 1-65.

 2.    Rittman, B.E. and  N.  Eun, "Estimating Volatile Organic Compound Emissions from
      Publicly Owned Treatment Works," Journal of the Water Pollution Control Federation,
      59(7):670-678, July 1987.

 3.    Corsi, Richard L, "Emissions of Volatile and Potentially Toxic Organic Compounds from
      Municipal Wastewater Treatment Plants," Presented at the SO* Annual Meeting of APCA
      New York, NY, June 21-26, 1987.

 4.    Pellizzari, E.D,  Volatile Organics in Aeration  Gases of Municipal  Treatment Plants:
      Project Summary, EPA-600/52-82-056, U.S. Environmental Protection Agency, Office of
      Research and Development, Municipal Environmental Research Laboratory, Cincinnati, OH
      August 1982.

 5.    White, T.S., Volatile Organic Compounds Emissions From Hazardous Waste Treatment
      Facilities at Downstream POTW (Final Report). Radian Corporation. Prepared under EPA
      contract No. 68-02-4378. U.S. Environmental Protection Agency, Research Triangle Park
      NC, 1987.

 6.    Radian  Corporation, Characterization of the Municipal Waste Combustion Industry,
      Appendix A, Research Triangle Park, NC, October 1986.

 7.    U.S. Environmental Protection Agency, Municipal Waste Combustion Study: Assessment
      of Health Risks Associated with Municipal Waste Combustion Emissions, EPA/530-SW-87-
      021g, Standards and Air Strategies Division, Research Triangle Park, NC, 1987.

 8.    U.S.  Environmental Protection  Agency, Emission  Data Base for  Municipal  Waste
      Combustors, EPA/530-SW-87-021b, Standards and  Air Strategies Division  Research
      Triangle Park, NC, 1987.

9.    Gerstle, R.W., and D.A. Kemnitz, "Atmospheric Emissions from Open Burning," Journal
      of the Air Pollution Control Association, 12:324-327, May 1967.

 10.   Liquid Fuel Sample Analysis, Eureka Laboratories, Inc., Sacramento, CA, November 10,
      1984.

 11.    Brooks, G.W. and G.E.  Hunt, Source Assessment for Hexachlorobenzene,  Final Report,
     U.S. Environmental Protection Agency, Pollutant Assessment Branch, Research Triangle
     Park, NC, 1984.
                                        7-14

-------
12.   1990 Directory of Chemical Producers, United States of America, SRI International, Menlo
     Park, CA, 1990.
                                       7-15

-------
                                    SECTION 8.0
           AMBIENT AIR AND STATIONARY SOURCE TEST PROCEDURES

       Chlorobenzene emissions  can be measured from ambient air and stationary sources
 utilizing the test methods presented below.   If applied to stack sampling, the  ambient air
 monitoring methods may require adaptation or modification.  If ambient air methodology is
 applied to  stationary source testing, appropriate precautions must be taken to ensure that the
 capacity of the methodology is not exceeded so that results  will be quantitative.  Ambient
 methods which require  the  use  of  sorbents  are  susceptible to sorbent  saturation if  high
 concentration levels exist If this happens, breakthrough will occur, and quantitative analysis is
 not possible.
       EPA ^mf111011 TO"1: Determination of Volatile Organic Compounds in Ambient Air Using
       Tenax® Adsorption and Gas Chromatography/Mass Spectrometry (GC/MS)
       EPA Method TO-14: Determination of Volatile Organic Compounds (VOCs) in Ambient
       Air  Using SUMMA® Passivated Canister Sampling and Gas Chromatographic (GC)
       Analysis
       EPA Method 0030: Volatile Organic Sampling Train (VOST) with EPA Method 5040:
       Analysis of Sorbent Cartridges from VOST
       EPA Method 0010:  Modified Method 5 Sampling Train with EPA Method 8270: Gas
       Chromatography/Mass Spectrometry  for Semi-volatile  Organics:  Capillary Column
       Technique
The following subsections briefly describe the recommended sampling and analytical methods
for determining chlorobenzene emissions.

8.1   EPA METHOD TO-11
      Ambient air concentrations of chlorobenzene can be measured using EPA Method TO-1
from the Compendium of Methods for the Determination of Toxic Organic Compounds in
Ambient Air. This method is used to collect and determine volatile nonpolar organics (aromatic
hydrocarbons, chlorinated hydrocarbons) that can be captured on Tenax® and determined by
                               .        8-1

-------
 thermal desorption techniques. The compounds determined by this method have boiling points
 in the range of 80°C to 200°C (180°F to 390°F).   Figure 8-1 presents  a schematic of the
 sampling system and Figure 8-2 presents a schematic of typical Tenax® cartridge designs.

       Ambient air is drawn through the  cartridge  which contains approximately 1-2 grams
 (0.035 to 0.07 ounces) of Tenax®.  Chlorobenzene is trapped oh the Tenax® cartridge which is
 then  capped  and  sent   to  the  laboratory  for  analysis  utilizing  purge-and-trap   gas
 chromatography/mass spectrometry  (GC/MS) according  to the procedures specified in EPA
 Method 5040 (see Section 8.4). The recommended GC column is a 50 meter capillary, type SE-
 30 with an internal diameter of 0.3 mm.

       The exact run time, flow rate and volume sampled varies from source to source depending
 on the expected concentrations and the required detection limit. Typically,  10 to 20 L (0.35 to
 0.7 ft3)  of ambient air are sampled. Analysis should be  conducted within  14 days of sample
 collection.

 8.2    EPA METHOD TO-141
       Ambient air concentrations of chlorobenzene can also be measured using EPA Method
TO-14 from the Compendium of Methods for the Determination of Toxic Organic Compounds
in Ambient Air.  This method is based on collection of a whole air sample in SUMMA®
passivatcd stainless steel canisters and is used to determine semi-volatile and volatile organic
compounds.  The compounds are separated by gas chromatography and measured by mass-
selective detector or multidetector techniques such as FID, electron capture detection (ECD), and
photoionization detection (PID).  The recommended column for Method TO-14 is an HP OV-1
capillary with 0.32mm I.D. x 0.88 pm cross-linked methyl  silicone  coating or equivalent.
Samples should be analyzed within 14 days of collection.

       This method is applicable to specific semi-volatiles and volatile organic compounds that
have been tested and determined to be stable when stored in pressurized and subatmospheric
pressure canisters.  Chlorobenzene can be successfully measured  at the parts per billion by
                                         8-2

-------
Vent
                     Rotometer
                                 Needle
                                 Vaive
Coupling to
Connect Tenax
Cartridge
                Figure 8-1.  EPA Method TO-1 sampling system.1
                                      8-3

-------
                                   .Tenox
                                    ~1.5 Grams (6 cm  Bed Depth)



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                        Glass Wood Plugs
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                                 (13.5 mm  OD x
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                          Gloss Wool
                          Rugs
                          (0.5 cm  Long)
                                 1/8"  End Cap-
                                                            TiTT
     Swagelok
     Fitting
. Tenax
 ~1.5 Grams (7 cm Bed Depth)
, Metal Cartridge
 (12.7 mm  OD x
 100 mm LOna)
           Figure 8-2.  Tenax® cartridge design.1
                              8-4

-------
 volume (ppbv) level using this method.  Figure 8-3 presents a diagram of the canister sampling
 system.

 8.3    EPA METHOD 00302

       The volatile organic sampling train (VOST) from SW-846, (third edition) is designed for
 the collection of volatile organic compounds from the  stack gas effluents  of hazardous waste
 incinerators. The VOST method was designed to collect volatile organics with boiling points in
 the range of 30°C to 100°C (86°F to 212°F). Many compounds with boiling points above 100°C
 (212°F) may also be effectively collected using this method. Chlorobenzene concentrations can
 be measured using this method. Figure 8-4 presents a schematic of the principle components of
 the VOST.                                     -

       In most cases, 20 L (0.7 ft3) of effluent stack gas are sampled at an approximate flow rate
 of 1 L/minute (0.035 ftVmin) using a glass-lined heated probe. The gas stream is cooled to 20°C
 (68°F) by passage through a water-cooled condenser and the volatile organics are collected on
 a pair of sorbent resin traps.  Liquid condensate is collected in the impinger located between the
 two resin traps.  The first resin trap contains about  1.6 g (0.06 ounce) Tenax® and the second
 trap 'contains about 1 g (0.04 ounce) each of Tenax® and petroleum-based charcoal.

       The  Tenax® cartridges are  then thermally  desorbed and analyzed by purge-and-trap
 GC/MS along with the condensate catch as specified in EPA Method 5040.  Analysis should be
 conducted within 14 days of sample collection.

 8.4    EPA METHOD 50402
       The contents of the sorbent cartridges (collected via EPA Method 0030) are spiked with
an internal standard and thermally desorbed for 10 minutes at 80°C (176°F) with organic-free
nitrogen or helium gas (at a flow rate of 40 mL/min (2.4 in'/min)), bubbled through 5 mL
(0.3 in3) of organic-free water, and trapped on an analytical adsorbent trap. After the 10 minute
desorption, the analytical adsorbent trap is rapidly heated to 180°C (356°), with the carrier gas

                                         8-5

-------
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                                                 8-6

-------
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                                  8-7

-------
 flow reversed so that the effluent flow from the analytical trap is directed into the GC/MS.  The
 volatile organics are separated by temperature-programmed gas chromatography and detected by
 low resolution mass spectrbmetry.  The concentrations of the volatile organics are calculated
 using the internal standard technique.

       EPA Methods 5030 and 8240 may be referenced for specific requirements for the thermal
 desorption unit, purge-and-trap unit, and GC/MS system.

       A diagram of the analytical system is presented in Rgure  8-5.  The Tenax® cartridges
 should be analyzed  within 14 days of collection.  The desired detection limit of this method is
 0.1 ng/L (20 ng per Tenax® cartridge).

 8.5    EPA METHOD 00102

       EPA Method 0010  (Modified  Method 5 Sampling  Train) is used to determine the
 destruction and removal- efficiency of semi-volatile principal organic  hazardous constituents
 (POHCs) from incineration systems. This method may be used for determining chlorobenzene
 emissions.

       Gaseous and particulate pollutants are withdrawn isokinetically from an emission source
 and collected  in a multicomponent sampling  train.  Figure 8-6 presents a schematic of the
 sampling system.  Principal components of the train include a high-efficiency glass- or quartz-
 fiber  filter and a packed bed of porous polymeric adsorbent resin (typically XAD-2® or
polyurethane foam for PCBs).  The filter is used to collect organic-laden particulate materials and
the porous polymeric resin to adsorb semi-volatile organic species (compounds with a boiling
point  above 100°C (212°F)).  Comprehensive chemical analyses, using a variety of applicable
analytical methodologies, are conducted to determine the identity and concentration of the organic
materials.
                                         8-8

-------
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         8-10

-------
8.6    EPA METHOD 82702

       EPA Method 8270 is  used to  determine the concentration of semi-volatile organic
compounds in extracts prepared from all types of solid waste matrices, soils, and ground water.
It is also applicable to an extract from sorbent media in conjunction with Method 0010. Direct
injection of a sample may be used in limited applications.

       Method 8270 can be used to quantify most neutral, acidic, and basic organic compounds
that are soluble in methylene chloride and capable of being eluted without derivatization as sharp
peaks from a  gas chromatographic fused-silica 'capillary column coated with a slightly polar
silicone.  Chlorobenzenes are within the boiling  point range and may be determined using this
methodology.

       The practical quantisation limit for Method 8270 is approximately 50 ug/mL of extract
The entire sorbent module with filter is  typically extracted and concentrated to 1 mL (0.03 in3)
[a final volume of 5 mL (0.3 in3) is used to avoid loss of volatile compounds], and this final
extract volume represents the entire volume of gas sampled.
                                         8-11

-------

-------
8.7
1.
2.
         JCES FOR SECTION 8.0

U.S. Environmental Protection Agency, Compendium of Methods for the Determination
of Toxic Organic Compounds in Ambient Air, EPA/600/4-89/017, Atmospheric Research
and Exposure Assessment Laboratory, Research Triangle Park, NC, June 1988.

U.S. Environmental Protection Agency, Test Methods for Evaluating Solid Waste, Third
Edition, Report No, SW-846, Office of Solid Waste  and Emergency Response,
Washington, DC, November 1986.
                                      8-12

-------

-------
                      APPENDIX A




POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES EMISSIONS
                          A-l

-------

-------
                   TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
                  EMISSIONS
SIC Code
Source Description
1,2,3-TCB (87-61-6)
3679
5093
Electronic components, nee
Scrap and waste materials
o-DCB (95-50-1)
0711
0721
1382
1400
1475
1499
2044
2082
2262
2269
2491
2611
2621
2791
2800
2812
2813
2816
2819
Soil preparation services
Crop planting and protecting
Oil and gas exploration services
Mining and quarrying of nonmetallic minerals
Phosphate rock
Asbestos milling
Rice milling
Beer production
Finishing plants, manmade
Finishing plants, nee
Wood preserving
Pulp mills
Paper mills
Typesetting (lead remelting)
Floating roof tanks
Alkalies and chlorine
Industrial gases
Inorganic pigments
Industrial inorganic chemicals, nee
(continued)
A-2

-------
                    TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
               EMISSIONS (continued)
SIC Code
2821
2822
2833
2834
2841
2842
2844 ,
2851
2861
2865
2869
2873
2874
2879
2899
2911
3111
3241
3255
3275
3299
3312
3354
Source Description
Plastics materials and resins
Synthetic rubber
Medicinals and botanicals
Pharmaceutical preparations
Soap and other detergents
Polishes and sanitation goods
Toilet preparations
Paints and allied products
Gum and wood chemicals
Cyclic crudes and intermediates
Industrial organic chemicals, nee
Nitrogenous fertilizers
Normal superphosphate
Agricultural chemicals, nee
Chemical preparations, nee
Petroleum refining
Leather tanning and finishing
Cement mfg.: Wet process
Castable refractory
Gypsum mfg
Nonmetallic mineral products, nee
By-product coke manufacturing
Aluminum extruded products
                    (continued)
                      A-3

-------
                    TABLE A*l.
POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
               EMISSIONS (continued)
SIC Code
3400
3431
3449
3471
3544
3571
3572
3575
3577
3671
3674
3679
3695
3699
3812
3861
3900
3949
4011
4013
4491
4741
Source Description
General processes
Porcelain enamel/ceramic glaze spraying booth
Miscellaneous metal work
Plating and polishing
Special dies, tools, jigs & fixtures
Electronic computers
Computer storage devices
Computer terminals
Computer peripheral equipment, nee
Electron tubes
Semiconductors and related devices
Electronic components, nee
Magnetic and optical recording media
Electrical equipment & supplies, nee
Search and navigation equipment
Photographic equipment and supplies
Miscellaneous industrial processes
Sporting and athletic goods, nee
Railroads, line-haul operating
Switching and terminal services
Bulk materials elevators
Rental of railroad cars
                    (continued)
                       A-4

-------
                    TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
               EMISSIONS (continued)
SIC Code
4953
5085
5541
7342
Source Description
Refuse systems
Drum cleaning/reclamation
Gasoline service stations
Disinfecting & pest control services
p-DCB (106-46-7)
0711
0721
1400
1475
1499
2044
2082
2261
2392
2491
2791
2800
2812
2816
2819
2821
2822
2834
Soil preparation services
Crop planting and protecting
Mining and quarrying of nonmetallic minerals
Phosphate rock
Asbestos milling
Rice milling
Beer production
Finishing plants, cotton
House furnishings, nee
Wood preserving
Typesetting (lead remelting)
Floating roof tanks
Alkalies and chlorine
Inorganic pigment
Industrial inorganic chemicals, nee
Plastics materials and resins
Synthetic rubber
Pharmaceutical preparations
(continued)
A-5

-------
                    TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
               EMISSIONS (continued)
SIC Code
2841
2842
2843
2861
2865
2869
2873"
2874
2879
2992
3241
3251
3253
3255
3275
3291
3312
3400
3431
3471
3674
3900
3991
Source Description
Soap and other detergents
Polishes and sanitation goods
Surface active agents
Gum and wood chemicals
Cyclic crudes and intermediates
Industrial organic chemicals, nee
Nitrogenous fertilizers
Normal superphosphate
Agricultural chemicals, nee
Lubricating oils and greases
Cement mfg.: Wet process
Brick and structural clay tile
Ceramic wall and floor tile
Castable refractory
Gypsum mfg
Abrasive products
By-product coke manufacturing
General processes
Porcelain enamel/ceramic glaze spraying
Electroplating operations
Semiconductors and related devices
Miscellaneous industrial processes
Brooms and brushes
(continued)
A-6

-------
                                 TABLE A-l.
    POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
                          EMISSIONS (continued)
  SIC Code
  ••Mi
 4491
 Bulk materials elevators
                         Source Description
 4952
 Sewerage systems
 4953
 Refuse systems
 5085
 Drum cleaning/reclamation
 7342
 Disinfecting & pest control services
                               MCB   (108-90-7)
 1311
 Crude petroleum and natural gas
 1321
 Natural gas liquids
 1382
 Oil and gas exploration services
 1400
 Mining and quarry of nonmetallic minerals
 1475
Phosphate rock
 1499
Asbestos milling
2044
Rice milling
2082
Beer production
2200
Knit fabric scouring with chlorinated solvent
2262
Finishing plants, manmade
2269
Finishing plants, nee
2295
Coated fabrics, not rubberized
2395
Pleating and stitching
2672
Paper coated and laminated, nee
2791
Typesetting (lead remelting)
2800
Floating roof tanks
2812
Alkalies and chlorine
                                 (continued)
                                    A-7

-------
                    TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
               EMISSIONS (continued)
SIC Code
2813
2816
2819
2821
2822
2833
2834
2842
2851
2861
2865
2869
2873
2874
2879
2891
2899
2911
2951
2992
3053
3069
3142
Source Description
Industrial gases
Inorganic pigments
Industrial inorganic chemicals, nee
Plastics materials and resins
Synthetic rubber
Medicinals and botanicals
Pharmaceutical preparations
Polishes and sanitation goods
Paints and allied products
Gum and wood chemicals
Cyclic crudes and intermediates
Industrial organic chemicals, nee
Nitrogenous fertilizers
Normal superphosphate
Agricultural chemicals, nee
Adhesives and sealants
Chemical preparations, nee
Petroleum refining
Asphalt paving mixtures and blocks
Lubricating oils and greases
Gaskets, packing and sealing devices
Fabricated rubber products, nee
House slippers '
(continued)
A-8

-------
                     TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
                EMISSIONS (continued)
SIC Code
3241
3255
3275
3292
3295
3312
3364
3366
3400
3431
3471"
3555
3674
3679
3699
3711
3714
3728
3812
3861
3900
3999
4011
Source Description
Cement, hydraulic
Castable refractory
Gypsum mfg.
Asbestos products
Minerals, ground or treated
By-product coke manufacturing
Nonferrous die-casting exc. aluminum
Copper foundries
General processes
Porcelain enamel/ceramic glaze spraying
Electroplating operations ,
Fruiting trades machinery
Semiconductors and related devices
Electronic components, nee
Electrical equipment & supplies, nee
Motor vehicles and car bodies
Motor vehicle parts and accessories
Aircraft parts and equipment, nee
Search and navigation equipment
Photographic equipment and supplies
Miscellaneous industrial processes
Manufacturing industries, nee
Railroads, line-haul operating
                     (continued)
                       A-9

-------
                                 TABLE A-l.
   POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
   	    EMISSIONS (continued)
  SIC Code
 4013
                         Source Description
 Switching and terminal services
 4226
 Special warehousing and storage, nee
 4491
 Bulk materials elevators
 4741
 Rental of railroad cars
 4952
 Sewerage systems
 4953
 Refuse systems
 5085
 Drum cleaning/reclamation
5171
Petroleum bulk stations & terminals
5541
Gasoline retail operations - Stage I
7389
Business services, nee
9511
Air, water, & solid waste management
                               HCB  (118-74-1)
0721
Crop planting and protecting
2812
Alkalies and chlorine
2813
Industrial gases
2819
Industrial inorganic chemicals, nee
2821
Plastics materials and resins
2865
Cyclic crudes and intermediates
2869
Industrial organic chemicals, nee
2879
Agricultural chemicals, nee
2892
Explosives
2951
Asphalt paving mixtures and blocks
3822
Environmental controls
                                 (continued)
                                   A-10

-------
                               TABLE A-l.

   POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES

                        EMISSIONS (continued)
 SIC Code
 tmm

4952        Sewerage systems
Source Description
            Refuse systems
                           1,2,4-TCB  (120-82-1)
            Broadwoven fabric mills, cotton
            Broadwoven fabric mills, manmade
            Broadwoven fabric mills, wool
            Knit outerwear mills
            Knit underwear mills
            Weft knit fabric mills
            Lace & warp knit fabric mills
            Finishing plants, cotton
            Finishing plants, manmade
            Finishing plants, nee
            Carpets and rugs
            Wood preserving
            Alkalies and chlorine
            Inorganic pigments
            Industrial inorganic chemicals, nee
            Soap and other detergents
            Polishes and sanitation goods
            Surface active agents
           Gum and wood chemicals
           Cyclic crudes and intermediates
                              =====

                               (continued)
                                 A-ll

-------
                    TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
               EMISSIONS (continued)
SIC Code.
2869
2873
2879
2899
2992
3251
3253
3291
3357.
3449
3479
3612
3621
3674
3679
3699
3812
3822
3861
4953,
7342
Source Description
Industrial organic chemicals, nee
Nitrogenous fertilizers
Agricultural chemicals, nee
Chemical preparations, nee
Lubricating oils and greases
Brick and structural clay tile
Ceramic wall and floor tile
Abrasive products
Nonferrous wiredrawing & insulating
Miscellaneous metal work
Metal coating and allied services
Transformers, except electronic
Motors and generators
Semiconductors and related devices
Electronic components, nee
Electrical equipment & supplies, nee
Search and navigation equipment
Environmental controls
Photographic equipment and supplies
Refuse systems
Disinfecting & pest control services
m-DCB (541-73-1)
0711
Soil preparation services
(continued)
A-12

-------
                    TABLE A-l.
POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
               EMSSIONS*(contiimed)
SIC Code
0721
2131
2431
2499
2511
2522
2541 __
2542
2800
2812
2819
2821
2833
2834
2851
2861
2865
2869
2873
2879
3111
3400
3412
Source Description
Crop planting and protecting
Chewing and smoking tobacco
Millwork
Wood products, nee
Wood household furniture
Office furniture, except wood
Wood partitions and fixtures
Partitions and fixtures, except wood
Fugitive emissions
Alkalies and chlorine
Industrial inorganic chemicals, nee
Plastics materials and resins
Medicinals and botanicals
Pharmaceutical preparations
Paints and allied products
Charcoal manufacturing
Cyclic crudes and intermediates
Industrial organic chemicals, nee
Nitrogenous fertilizers
Agricultural chemicals, nee
Leather tanning and finishing
General processes
Metal barrels, drums, and pails
(continued)
A-13

-------
                                 TABLE A-l.
     POTENTIAL SOURCE CATEGORIES OF CHLOROBENZENES
                          EMISSIONS (continued)
                                    Source Description
              Porcelain enamel/ceramic glaze spraying
  3444
 Sheet metalwork
  3471
 Plating and polishing
J4 /y Metal coating and allied services
3563
3612
3641
3671
3674
3679
3695
3699
3713
Air and gas compressors
Transformers, except electronic
Electric lamps ~ . j
Electron tubes
Semiconductors and related devices |
Electronic components, nee 1
Magnetic and optical recording media j
Electrical equipment & supplies, nee |
Truck and bus bodies
  3812
Search and navigation equipment
  3861
Photographic equipment and supplies
  3900
Miscellaneous industrial processes
  4953
Refuse systems
  5085
Drum cleaning/reclamation
  5511
New and used car dealers
 7532
Top & body repair & paint shops
 7534
Tire retreading and repair shops
 8299         Schools & educational
              =^===
nee - not elsewhere classified
                  services, nee
                                   A-14

-------

-------
                   APPENDIX B
TEXTILE FIBER DYEING FACILITIES WITH ANNUAL SALES
            GREATER THAN $1 MILLION
                      B-l

-------

-------
                      TABLE B-l.
TEXTILE FIBER DYEING FACILITIES (SIC 2269) WITH
           SALES GREATER THAN $1 MILLION
ANNUAL
Name
Willcox and Gibbs Inc.
Hanes Companies Inc.
PAXAR Corp.
Meridian Industries Inc.
Covington Fabrics Corp.
Morganton Dyeing and Finishing
Corp.
Valdese Manufacturing Co.
Hanes Dye and Finish Company
Inc.
Cross Mills Inc.
Spectrum Fibers Inc.
Phoenix Dye Works
US Label Corp.
Jaftex Corp. Oxford Printing and
Finishing
SMS Textile Mills Inc., Spantex
Brittany Dyeing and Printing
Company
J and C Dyeing Inc.
Garment Graphics Inc.
Duro Industries Inc., Sanford
Finishing Co
Jefferies Southern Processors Inc.
Southampton Textile Co.
Collins and Alkman Corp Home
Fabrics
CYPInc.
Address
530 Fifth Ave, New York, NY 10036
PO Box 202, Winston-Salem, NC 27102
275 N Middletown Rd, Pearl River, NY 10965
100 E. Wisconsin Ave, Milwaukee, WI 53202
267 Fifth Ave, New York, NY 10016
PO Box 1327, Morganton, NC 28655
PO Box Drawer 10, Valdese, NC 28690
PO Box 202, Winston-Salem, NC 27102
PO Box 520, Marion, NC 28752
1450 Broadway, New York, NY 10018
4755 W. 150th St, Cleveland, OH 44135
PO Box 9378, Greensboro, NC 27429
604 W. Industry Dr, Oxford, NC 27565
132 Franklin St. Norwich CT 06360
1357 E. Rodney French, New Bedford, MA 02744
PO Box 9000, Shelby, NC 28151
12862 E. Florence Ave, Santa Fe Springs, CA 90670
PO Box 550, Sanford, NC 27330
PO Box 430, Albemarle, NC 28001
520 Reese St, Emporia, VA 23847
PO Box 427, Concord, NC 28025
PO Drawer A, Tryon, NC 28782
Sales in
$ Millions
568
110
73
70
60
31*
30
25
25
21*
21*
18
16*
16
15*
14*
14*
12
12
12
11*
11
                       (continued)
                         B-2

-------
                                     TABLE B-l.
 TEXTILE FIBER DYEING FACILITIES (SIC 2269) WITH ANNUAL
            SALES GREATER THAN $1 MILLION (continued)
            Name
            •MM
 Burlington Industries Inc.,
 Burlington Versatech
                   Address
 PO Box 158, Cooleemee, NC 27014
 Travis Knits Inc.
 PO Box 65, Maiden, NC 28065
 Pharr Yarns Inc.
 PO Box 630, Belmont, NC 28012
 India Ink
 2457 E 27th St, Los Angeles, CA 90058
 Pisgah Yam and Dyeing Company
 Inc.
 PO Box 606, Old Fort, NC 28762
 Fabricut Inc.
 5920 S. Triangle Dr, City of Commerce CA 90040
 Textile Dyeing and Finishing Co.,
 Inc.
 2015 City Line Rd, Bethlehem, PA
 Providence Braid Company Inc.
 358 Lowden St, Pawtucket. RI02860
 Spinnerin Yarn Company Inc.
 30 Wesley St, South Hackensack, NJ
 Western Piece Dyers
 2845 W. 48th PI, Chicago, IL (50632
Jaunty Textile Corp. - Libbie
Trading Corp,
 15 Poplar St, Scranton PA 18501
Geltman Corp.
PO Box 717, Conover, NC 28613
Aurora Bleachery Inc. - Meridian
Industries Inc.
PO Box 70, Aurora, IL 60508
North Hickory Dyeing and -
Processing Co.
 1329 2nd St NE, Hickory, NC 28601
Wolfe dye and Bleach Works Inc.
25 Ridge Rd, Shoemakersville, PA 19555
Eagle Dyeing and Finishing Co.
PO Box 180, Mount Holly, NJ 08060
Royal Carolina Corp.
7305 W. Friendly Ave, Greensboro, NC 27410
FTC Manufacturing Group Inc.
1261 Broadway, New York. NY 10001
Globe Dye Works Company
4500 Worth St, Philadelphia, PA 1.9124
Interstate Dyeing and Finishing
Co.
35 8th St, Passaic NJ 07055
Elmore-Pisgh Inc.
204 Oak St, Spindale, NC 28160
        	==
        (continued)
                                        B-3

-------
                              TABLE B-l.
  TEXTILE FIBER DYEING FACILITIES (SIC 2269) WITH ANNUAL
          SALES GREATER THAN $1 MILLION (continued)
Name
Fine Art Pillow and Specialties
Coip.
Lisbon Textile Prints Inc.
Renco Finishing Corp.
William J Dixon Comp. Inc.
Luithlen Dye Corp.
GJ Littlewood and Son
Dyetex Inc.
Classic Draperies Corp., Lensol
Fabric-Seattle Div.
J and M Dyrs Inc.
Morgan Dyeing Company Inc.
Classic Draperies Corp., Lensol
Fabric-Phoenix Div.
Address
601 W 26th St, New York, NY 10001
PO Box 278, Jewett City, CT 06351
20-21 Wagaraw Rd, Fair Lawn, NJ 07410
756 Springdale Dr, Exton. PA
Tioga St & J St, Philadelphia, PA 19134
4045-61 Main St, Philadelphia, PA 19127
14 Stevens St, Haverhill, MA 01830
7920 S. Occidental Ave, Seattle, WA 98108
PO Box 550, Sumter, SC 29150
327 W. 36th St. New York, NY 10018
4829 S. 36th St, Phoenix, AZ 85040
=====
Sales in
$ Millions
••••••«••••
3*
3*
3*
3
2*
2
2
2*
1
1*
1*
* Indicates an estimated financial figure.
Source: Gale Research, Inc. Ward's Business Directory of US. Private and Public Companiea-1991, Volume 4,
     MI, 1991.
                                B-4

-------
                       TABLE B-2.
TEXTILE FIBER DYEING FACILITIES (SIC 2262) WITH ANNUAL
           SALES GREATER THAN $1 MILLION
Name
Gilbert Frank Corp.
TSGInc
Champagne Dye Works Inc.
Kenyon Industries Inc.
Goldtex Inc.
Marijon Dyeing and Finishing Co.
Amerbelle Corp.
Yates Bleachery Co.
Milliken and Co. Enterprise
Wansona Manufacturing Corp.
Amatex Corp.
Hampton Print Works Inc.
Oxford Textile Inc.
J and J Flock Products Inc.
Craftsmen Fabrics Industries Inc.
Duro Industries Inc., Duro Textile
Printers Inc.
Kent-Bragaline Inc.
Deep River Dyeing Company Inc.
Hemmerich Industries Inc.
AS Haight and Co.
Trio Dyeing and Finishing
Decorative Screen Prints Inc.
Quip Industries
Melville Textile Print Works Inc.
Crown Prince Inc.
Address
16 E 34th St, New York, NY 10016
1400 Welsh Rd, North Wales, PA 19454
PO Box 716, Asheboro, NC 27203
PO Box 147, Kenyon, RI 02836
401 Patetown Rd, Goldsfooro, NC 27530
219 Murray Hill Pkwy, East Rutherford, NJ 07073
PO Box 150, Vemon, CT 06066
PO Box 150, Flintstone, GA 30725
512 Pumpkintown Rd, Marietta, SC 29661
1 Wansona PI, Wadesboro, NC 28170
1032 Stanbridge St, Nomlstown PA 19401
2212 Buffalo Rd, Johnson City, TN 37604
PO Box 90, Oxford, NJ 07863
1150 Centre St, Easton, PA 18042
PO Box 1329, Concord, NC 28026
PO Box 61, Fall River MA 02724
27-35 Jackson Ave, Long Island City, NY 11101
PO Box 217, Randleman, NC 27317
PO Box 286, Denver, PA 17517
PO Box 501, Cartersville. GA 30120
440 E. 22nd St, Paterson, NJ 07509
9 Wisconsin Ave. Norwich, CT 06360
18th & Jefferson, Carlyle, JL 62231
PO Box 5420, Statesville. NC 28677
PO Box 37, Brookfield WI 530008
Sales in
$ Millions
60
28
25
24
22
21*
20
15
14*
11
10*
9*
9
8
7
7*
7
6
6
5
5
5*
5
4
4
                        (continued)
                         B-5

-------
                                  TABLE B-2.
  TEXTILE FIBER DYEING FACILITIES (SIC 2262) WITH ANNUAL
            SALES GREATER THAN $1 MILLION (continued)
              Name
  Yameli Group
                                               Address
48 W. 37th St, New York, NY 10018
                                       Sales in
                                      $ Millions
  Apollo Dyeing and Finishing Company,
  Inc.
PO Box 3072, Paterson, NJ 07509
  Bronxwood Dyeing Company, Inc.
900 E. 229th St. Bronx, NY 10466
  American Art Ltd.
95 Morton St, New York, NY 10014
  Paw Prints of California
3166 Bay Rd, Redwood City, CA 94063
                                                                         1
* Indicates an estimated financial figure.
Source: Gale Research, Inc. Ward's Business Directory of U.S. Private and Public Companies-1991, Volume 4
Detroit, MI, 1991.
                                     B-6

-------
                       TABLE B-3.
TEXTILE FIBER DYEING FACILITIES (SIC 2231) WITH ANNUAL
           SALES GREATER THAN $1 MILLION
Name
Forstmann & Co., Inc
Pendleton Woolen Mills Inc.
Asten Group Inc.
Guilford of Maine Inc.
Gilbert Frank Corp.
American Woolen Co.
Worcester Co
Carleton Woolen Mills Inc.
LW Packard & Co. Inc
Anglo Fabrics Co Inc
Eastland Woolen Mills Inc.
Dorr Woolen Co.
Stillwater Inc.
Westgate Fabrics Inc.
Cascade Woolen Mill Inc.
Faribault Woolen Mill Co.
Scapalnc
Niagara Lockport Industries Inc.
Lockport Felt
JM Voith GmbH Appleton Mills
Robinson Mfg. Co.
Stanley Woolen Co., Inc.
Astro-Dye Works, Lie.
Robinson Mfg. Co. Kezar Falls Woolen
Co.
Brooks Woolen Co., Inc.
Address
1185 Ave of the Americas, New York, NY 10036
PO Box 1691, Portland. OR 97207
PO Box 10700, Charleston, SC 29411
Oak St, Guilford. ME 04443
16 E 34th St 15th Fl. New York, NY 10016
7600 NE 69th Ave. Medley, FL 33166
Greystone Ave, Centerdale, RI 02911
51 Main St, Winthrop, ME 04364
6 Mill St, Ashland, NH 03217
561 7th Ave 16th Fl. New York, NY 10018
Main St, Corinna, ME 04928
Main St, Guild, NH 03754
151 W 40th St, New York, NY 10018
1000 Fountain Pkwy, Grand Prairi, TX 75050
PO Box 157, Oakland, ME 04963
PO Box 369, Faribault, MN 55021
PO Box 1949, Waycross, GA 31502
Hwy 12 W. Starkville, MS 39759
PO Box 1899, Appleton, WI 54913
PO Box 195, Oxford, ME 04270
140 Mendon St, Uxbridge, MA 01569
PO Box 788, Calhoun, GA 30701
Federal Road, Kexar Falls, ME 04047
PO Box 671, Lowell, MA 01853
Sales in
$ Millions
215
140*
100
75
60
46
38*
37*
35
32
27
25
20
20
16
16*
15*
14
13
12*
11
9
8
7*
                       (continued)
                         B-7

-------
                                    1 TABLE B-3.
  TEXTILE FIBER DYEING FACILITIES (SIC 2231) WITH ANNUAL
             SALES GREATER THAN $1 MILLION (continued)
               Name
                                                   Address
                                          Sales in
                                         $ Millions
  Henry Mali Co., Inc.
257 Pk Ave S, New York, NY 10010
  Charles W. House and Sons, Inc
PO Box 158, Unionville, CT 06085
  G Thomas & Sons Inc
PO Box 218, North Grosve, CT 06255
  Hickory Dyeing & Winding Co, Inc.
PO Box 1975, Hickory, NC 28603
  Ronitex Jacquard Mills Inc.
22 Spruce St, Paterson, NJ 07501
  Aetna Felt Corp.
2401 W Emmaus Ave, AUentown, PA 18103
  Boris Kroll Jacquard Looms
66 Gray St, Paterson, NJ 07501
  Striar Textile Mill
PO Box 189, Orono, ME 04473
  Anchor Dye'g & Finish'g Co., Inc
Adams Ave & Leiper St, Philadelphia, PA 19124
                                                                               3*
  Anthra Textile Co., Inc
1400 Chestnut St, Kulpmont PA 17834
  Louis Krieger Co.
2000 S. Main St, Los Angeles, CA 90007
  Jacquard Fabrics Inc.
1965 Swathmore Ave, Lakewood, NJ 08701
  Litchfield Woolen Mill
PO Box 722, Litchfield, MN 55355
  Ortega's Weaving Shop, Inc.
PO Box 325, Chimayo, NM 87522
* Indicates an estimated financial figure.
Source:  Gale Research, Inc.  Ward's Business Directory of U.S. Private and Public Companies-1991 Volume 4
Detroit, MI, 1991.
                                         B-8

-------
                      TABLE B-4.
TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
           SALES GREATER THAN $1 MILLION
Name
(SIC 2251) Women's Hosiery Exc Socks
Sara Lee Corp L'eggs Prdts Inc.
Ithaca Industries Inc.
Hanes Hosiery Inc.
Esmark Apparel Inc.
Maro Hosery Corp.
America! Corp.
Danskin Inc., Esmark Apparel Inc.
Pennaco Hosiery Inc., Esmark Apparel
Inc.
Alba-Waldensian Inc.
US Textile Corp
Ithaca Industries Inc., Robbins Div.
Camp Hosiery
Aurbum Hosiery Mills Inc.
Roane Hosiery Inc.
Kentucky Derby Hosiery Co., Inc.
Cluett Peabody & Co., Lie., Great Amer
Knitting Mills
Jockey Intl Inc., Thorobred Hosiery
Acme-McCrary Corp.
Hampshire-Designers Ihc, Hampshire
Hosiery Co.
Highland Mills Inc.
Glendale Hosiery Inc.
Holt Hosiery Mills Inc.
Knit Prdts Corp.
Bossong Hosiery Mills
Sara Lee Corp, Rice Hosiery Corp
US Hosiery Corp
Address

PO Box 2495, Winston-Salem, NC 27102
PO Box 620, Wilkesboro, NC 28697
PO Box 1413, Winston-Salem, NC 27102
111 W. 40th St, New York, NY 10018
350 5th Ave, New York, NY 10118
PO Box 1419, Henderson, NC 27536
305 State St, York, PA 17403
111 W. 40th St, New York, NY 10018
PO Box 100, Valdese, NC 28690
PO Box 5643, Charlotte, NC 28225*
PO Box 37, Robbins. NC 27325
350 5th Ave, New York, NY 10118
113 E, Main, Auburn, KY 42206
PO Box 431, Harriman, TN 37748
PO Drawer 550, HopkinsviUe, KY 42240
530 5th Ave. 8th H, New York, NY 10036
2300 60th St, Kenosha, WI 53140
PO Box 1287, Asheboro, NC 27203
PO Box 528, Spruce Pine, NC 28777
PO Box 33775, Charlotte, NC 28233
PO Box 686, Siler City, NC 27344
PO Box 1757, Burlington, NC 27215
PO Box 1126, Belmont, NC 28012
PO Box 789, Asheboro, NC 27203
PO Box 2112, High Point, NC 27261
PO Box 160, Lincointon, NC 28092
Sales in
$ Millions

480
320
220*
110
78*
75
•50*
50
47
38
38
35*
35
31*
29
28*
27
25
25
22
20
18
17
17
17*
16
                       (continued)
                        B-9

-------
                                     TABLE f-4.
  TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
            SALES GREATER THAN $1 MILLION (continued)
              Name
 Chic Hosiery Corp
                                                   Address
 PO Box 31009, Charlotte, NC 28231
 Tower Mills Inc.
 POBox 1088, Burlington, NC 27215
 Arrowood Mills Inc.
 350 5th Ave, New York, NY 10118
 Glen Raven Mills Inc., Consumer Prdts
 Div.
 1831 N. Pk Ave, Altamahaw, NC 27217
 Niota Textiles Mill Co.
 Rte 3 Indus Pk, Fort Payne, AL 35967
 Harriss & Covington Hosiery Mills
 POBox 1909, High Point, NC 27261
 No-Nonsense Inc.
 534 S. Main, Burlington, NC 27220
 Laughlin Hosiery Mills Inc.
 PO Box 517, Randleman, NC 27317
 Admiration Hosiery Mill Inc.
 PO Box 240787, Charlotte, NC 28224
 Carolina Hosiery Mills Inc.
 PO Drawer 850, Burlington, NC 27216
Hampshire Hosiery Inc.
 1412 Broadway 7th Fl, New York. NY 10018
Trimfit Inc., Bonnie Doon
 10360 Dnimmond Rd, Philadelphia, PA 19154
Willard Lisus Inc., Holiday Hosiery
Mills
 666 Main St. Hudson, NC 23683
Willis Hosiery Mills Inc.
PO Box 407, Concord, NC 28025
Willwear Hosiery Mills Inc.
2000 Stuart St, Chattanooga. TN 37406
Sidney J Kreiss Inc.
PO Box 718, Lynbrook, NY 11563
Amsco-Craftsmen Hosiery Inc.
PO Box 127, Concord, NC 28027
Amos Hosiery Cos
PO Box 127, Pilot Mounta, NC 27041
Homespun Hosiery Inc., US Hosiery
Div.
980 3rd Ave SE, Hickory, NC 28602
Lemco Mills Inc.
PO Box 2098, Burlington. NC 27215
Stimpson Hosiery Mills Inc.
PO Box 151, Statesville, NC 28677
Candor Hosiery Mill Inc.
PO Box 738, Biscoe, NC 27209
Tennaco Hosiery
PO Box 7435, Memphis, TN 38107
Huitt Mills Inc.
136 Sparta Rd, North Wikes, NC 28659
Efland Hosiery Mill Inc.
PO Box 246, Efland, NC 27243
Cabot Hosiery Mills Inc.
N Main St, Northfield, VT 05663
Keepers Indus Inc., EG Smith Socks
379 5th Ave 4th Fl, New York, NY 10016
    =====
    (continued)
                                        B-10

-------
                       TABLE B-4.
TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
      SALES GREATER THAN $1 MILLION (continued)
Name
Troydon Hosiery Mils Inc.
Address
PO Box 96, Granite Fall, NC 28630
(SIC 2252) Hosiery Nee
Adams-Mills Corp
Trimfit Inc.
RenfroCorp.
Chipman-Union Inc.
Newville Indus Inc.
Durham Hosiery Mills Inc.
Spalding Knitting Co, Inc.
Clayson Knitting Co, Inc.
Premiere
Cherokee Hosiery Mill
Charleston Hosiery Inc.
Annedeen Hosiery Mills Inc.
Trimfit Inc. Kayby Mills of North
Carolina
Johnson Hosiery Mills Inc
Brown Woolen Mills Inc.
Adams Millis Corp Silver Knit Indus
Div.
Slane Hosiery Mills Inc.
Niota Textile Mills Co. Inc.
Leroi Princeton Hosiery Mills Inc.
Jean Hosiery Mill Inc.
Parker Hosiery Co, Inc.
Ridgeview Inc.
Cooper Hosiery Mill Inc.
Golden City Hosiery Mills
Rudin & Roth Inc.
225 N Elm St. High Point, NC 27260
10450 Drummond Rd. Philadelphia, PA 19154
PO Box 908, Mount Airy, NC 27030
500 Sibley Ave. Union Point, GA 30669
200 Madison Ave, New York, NY 10016
PO Drawer 1705, Danville, VA 24541
- PO Drawer K, Griffin, GA 30224
PO Box 39, Star, NC 27356
PO Box 100, Morganton, NC 28655
208 NE 35th St, Fort Payne, AL 35967
Raider Dr, Cleveland, TN 37311
PO Box 1359, Burlington, NC 27216
208 Carmalt St, Thomasville, NC 27360
PO Box 89, Fort Payne, AL 35967
PO Box 1440, Burlington, NC 27216
401 S Hamilton St, High Point, NC 27261
PO Box 2486, High Point, NC 27261
PO Box 117, Athens, TN 37303
PO Box 589, Princeton, KY 42446
628 Old Town Rd, Villa Rica, GA 30180
PO Box 699, Old Fort, NC 28762
PO Box 8, Newton, NC 28658
PO Box 909, Fort Payne, AL 35967
PO Box 939, Villa Rica, GA 30180
350 5th Ave #2609, New York, NY 10118
Sales in
$ Millions
1*

210
91*
85
50
50
43
43*
40
37
33
32*
32
31*
30
27
27*
27*
26*
26*
22*
21
20
20*
20
19*
                       (continued)
                         B-ll

-------
                      TABLE   .
TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
      SALES GREATER THAN $1 MILLION (continued)
Name
Ellis Hosiery Mills Inc.
Influential Hosiery Inc.
Belmont Hosiery Mills
Meywebb Hosiery Mills Inc.
Royce Hosiery Mills Inc.
Mayo Knotting Mills Inc.
Mauney Hosiery Mills Inc.
Ballston Knitting Co.
Maryon Mill Co.
Crescent Hosiery Mills Inc.
Fox River Mills Inc.
Maro Hosiery Corp Thomasville
Twin City Knitting Co.
Catawba Sox Inc.
Keppers Indus Inc.
Monarch Hosiery Mills Inc.
Nation Hosiery Mills Inc.
Adams-Millis Corp Drexel Knitting
Millis
Huffman Finishing Co.
Wigwam Mills Inc.
Ithaca Indus Inc, Anderson Hosiery
Thomeburg Hosiery Co.
Candor Hosiery Mills Inc.
Lea-Wayne Knitting Mills Inc.
Spalding Knitting Mills Pittsburgh
Knitting Mills
Address
1500 13th SW, Hickory, NC 28602
PO Box 309, High Point, NC 27261
PO Box 750, Belmont, NC 28012
PO Box 266, Meridian, MS 39301
350 5th Ave, New York, NY 10118
Austin St. Torboro, NC 27886
PO Box 1279, Kings Mounta, NC 28086
Saratoga Ave, Box 30, Ballston Spa, NY 12020
PO Box 1386, Carrollton, GA 30117
PO Box 370, Niota, TN 37826
PO Box 298, Osage, IA 50461
PO Box 698, Thomasville, NC 27360
PO Box 1179, Conover, NC 28613
PO Box 517, Conover, NC 28613
20720 Manila St, Chatsworth, CA 91311
PO Box 1205, Burlington, NC 27216
PO Box 3130, Chattanooga, TN 37404
PO Box 128, Drexel, NC 28619
PO Box 170, Granite Fall, NC 28630
PO Box 818, Sheboygan, WI 53081
PO Box 525, Clinton, SC 29325
POBox 5440, Statesville, NC 28677
602 E Hwy St, Candor, NC 27229
PO Box 1026, Morristown, TN 37814
212 E 1st St, South Pittsb, TN 37380
Sales in
$ Millions
MMH^^BB
18
• 17*
17
17
17*
16
16
15
15
15
15
15*
15
15
15
15
14*
13
13
11
11*
11*
11
11*
11*
                       (continued)
                        B-12

-------
  TEXTILE FIBER DYEING
            SALES GREATER
 TABLE B-4.
FACILITIES (SIC 225) WITH ANNUAL
THAN $1 MILLION (continued)
                Name
                •••
 Fred S Kahn Co., Inc.
                Address
  1720 W End Bldg, Nashville, IN 37203
 Sales in
$ Millions
                                                                                11
 Commonwealth Hosiery Mills
  PO Box 545, Randleman, NC 27317
                                                                               10*
 Mebane Hosiery Inc.
  PO Box 427, Mebane, NC 27302
                                                                                10
 WY Shugart & Sons Inc.
  405 Season Gap Rd, Fort Payne, AL 35967
                                                                                10
 Johnson Hosiery Mills Inc.
  2808 Maim Ave NW, Hickory, NC 28601
                                                                                10
 Shogren Indus Inc, Runnymede Mills Div.
  PO Box 1239, Tarboro, NC 27886
                                                                               10*
 CM Indus Inc
  50 Willow St. Adamstown, PA 19501
                                                                                10
 Trimfit Inc., Lawler Hosiery Mills
  PO Box 158, Carroltpn, GA 30117
 Montgomery Hosiery Mill Inc.
  PO Box 69, Star, NC 27356
 Ben Berger & Sons Inc.
  417 5th Ave #600, New York, NY 10016
 Seneca Knitting Mills
  POBox 231, Seneca Falls, NY 13148
Robinson Hosiery Mill Inc.
  Rte 1 Box 230, Valdese, NC 28690
Sanmark-Stardust Inc. Fountain Mfg. Div.
  PO Box 6076, Evansville, IN 47712
   8*
Fortune Mills Inc.
  PO Box 907. La Fayette, GA 30728
Chase Hosiery Mills Inc.
  7 W 30th St, New York, NY 10001
Tennessee Machine & Hosiery
  PO Box 1507, Hickory, NC 28601
Nelson Knitting Co.
 40 3rd St SE, Hickory, NC 28601
Handcraft Co., Inc.
 PO Drawer 399. Dandridge, TN 37725
Kayser-Roth Corp Mens Knitting Div.
 909 S. Main St, Rockford, IL 61101
Southern Hosiery Mill Inc.
 Mechanic St., Princeton, WI54968
Dura-Tred Hosiery Mills
 413 Tucker St, Burlington, NC 27215
Gateway Hosiery Mills
 PO Box 789, Hickory, NC 28603
Singer Hosiery Mills Inc.
 PO Box 2288, Burlington, NC 27215
Catawba Valley Finishing Co.
 PO Box 3100. Chattanooga, TN 37404
H Glaser & Son Inc.
 POBox 758, Thomasville,NC27360
HoIe-in-None Hosiery
 PO Box 407, Newton, NC 28658
Lyerly-Morgan Co Inc.
 PO Box 5977, Holliston, MA 01746
                                      (continued)
                                        B-13

-------
TEXTILE FIBER DYEING
       SALES GREATER
 TABLE B-4.
FACILITIES (SIC 225) WITH ANNUAL
THAN $1 MILLION (continued)
Name
Bennett Corp.
Damascus Hosiery Mills Inc.
Danridge Textile Inc.
Lynne Hosiery Mills Inc.
Sweetwater Hosiery Mills Lie.
Bailey Knit Corp.
Pickett Hosiery Mills
Staley Hosiery Mill Inc.
Cormier Corp.
Pine Hosiery Mills Inc.
Allied Hosiery Mills Inc.
Superior Mills Inc.
Elizabeth-Meade hosiery Mills Inc.
Dogwood Hosiery Co., Inc.
Excel Hosiery Mills Inc.
Wrightenberry Hosiery Inc.
Crowtn Hosiery Mills Inc.
Polot Hosiery Mills Inc.
Burnsville Hosiery Mills Inc.
Fort Payne Dekalb Hosiery Mills Inc.
Walton Knitting Mills Inc.
Arlene Hosiery Mill Inc.
Bisher Hosiery Mill Inc.
VI Prewett & Son Inc.
Softspun Knitting Mills Inc.
Daisy Hosiery Mills Inc.
Burke Hosiery Mills Inc.
Address
PO Box 607, Gibsonvffle, NC 27249
PO Box 397, Damascus VA 24236
PO Box 119, Dandridge, TN 37725
PO Box 987, Mount Airy, NC 27030
818 N Main St. Sweetwater, TN 37874
1606 Sanders Ave N, Fort Payne, AL 35967
PO Box 877, Burlington, NC 27215
2445 Bellmont, Burlington NC 27215
144 Lexington Dr., Laconia, NH 03246
208 S Main St, Star, NC 27356
E Main St, Englewood, TN 37329
PO Box 732, Chilhowie, VA 243 19
PO Box 1029, Burlington, NC 27215
PO Box 39, Thomasville, NC 27360
PO Box 607, Union, SC 29379
PO Box 859, Graham, NC 27253
PO Box 14010, Archdale, NC 27263
PO Box 608, Pilot Mounta, NC 27041
PO Box 278, Bumsville, NC 28714
PO Box 318, Fort Payne, AL 35967
PO Box 1808, Hickory, NC 28603
PO Box 4036, Hickory, NC 28603
PO Box 68, Denton, NC 27239
PO Box 258, Fort Payne, AL 35967
PO Drawer 729, Henderson, NC 27536
PO Box 5165, High Point, NC 27262
PO Box 406, Hildebran, NC 28637
Sales in
$ Millions
'6
5*
5* '
5*
5
5*
5
5*
5
5*
5
5*
5
5
5
5 .
5
4
4
3
3
2*
2
2*
2
2*
2
                       (continued)
                         B-14

-------
                                      TABLE B-4.
  TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
            SALES GREATER THAN $1 MILLION (continued)
               Name
 Cricket Hosiery Inc.
                                                    Address
 112 W 34th St. New York, NY 10120
 (SIC 2253) Knit Outerwear Mills
 TultexCorp.
 POBox 5191, Maitainsville, VA 24115
 Sara Lee Knit Prdts.
 POBox 3019, Winston-Salem, NC 27102
 Chesterfield Mfg Corp.
 PO Box 732, Chesterfield, SC 29709
 Oneita Indus Inc.
 PO Drawer 24, Andrews, SC 29510
 HL Miller & Son Inc.
 PO Box 348, Schuylkill H, PA 17972
 Hampshire-Designers Inc.
 PO Box 2667, Anderson, SC 29622
 St. John Knit Inc.
 17422 Derian Ave, Irvine, CA 92714
 American Argo Corp.
 Margaretta & Market, SchuylkiU H. PA 17972
 Klear Knit Inc.
 PO Box 236, Clover, SC 29710
 Cross Creek Apparel Inc.
 USHwy 52 S, Mount Airy, NC 27030
 Spencers Inc.
 PO Box 988, Mount Airy, NC 27030
 Savoy Indus Inc.
 315 E 62nd St, New York, NY 10021
Young Stuff Apparel Group Inc.
 1411 Broadway 10th Fl, New York. NY 10018
Jasper Textiles Inc.
PO Box 472, Lake Forest. IL 60045
Kentucky Textiles Inc.
 1 20th St, Paris, KY 40361
Greenbrier Indus Inc.
333 Sylvan Ave, Englewood Cliffs, NJ 07632
Private Brands Inc.
750 Kent Ave, Brooklyn, NY 11211
Brundidge Shirt Corp.
555 S Main St, Brundidge, AL 36010
Wamaco Inc.. Warnaco Knitwear Div.
POBox 1669, Altoona, PA 16603
Somerset Knitting Mills Inc.
700 Spring Garden St. Philadelphia, PA 19123
Garland Corp.
33 Dover St, Brockton, MA 02401
Pine State Knitwear Co.
PO Box 631, Mount Airy, NC 27030
Albert & Wechsler Inc.
34 W 33rd St, New York, NY 10001
Wellmore Inc.
                                  4987th Ave Fl 15, New York, NY 10018
Heritage Sportswear
PO Box 1060, Marion. SC 29571
    =====

    (continued)
                                        B-15

-------
                       TABLE B-4.
TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
      SALES GREATER THAN $1 MILLION (continued)
Name
East-Term Mills Inc.
Russell Corp. Knit Goods
Spectex Indus Inc.
Winona Knitting Mills Inc.
Albert & Wechsler Inc.
Great American Sweater
Gloray Knitting Mills Inc.
FR Knitting Mills Inc.
Bangor America Inc.
Alpha Mills Inc.
Brinlaw Inc.
Everite Knitting Mills Inc.
Gelfo Mfg. Co., Inc.
Gramercy Mills Inc.
Reliable Knitting Works
School Apparel Inc.
AD Everitt Knitting Co.
Ruse-Rouge Mfg. Co.
Bryan Mills Inc.
AM Knitwear Inc.
Lion Knitting Mills Co.
Ohio Knitting Mills Inc.
FAB Indus Inc.
Kenthtoo Inc.
Charter Apparel Ltd.
Academy Knitters Inc.
Cullman Indus.
Address
3112 Indus Dr, Johnson City, TN 37601
PO Box 45, Sylacauga, AL 35150
505 Carroll St, Brooklyn, NY 11215
902 E 2nd St, Winona, MN 55987
34 W 33rd St, New York, NY 10001
1431 Broadway 2nd FI, New York, NY 10018
317 E Penn Ave, Robesonia, PA
PO Box 4360, Fall River, MA 02723
159 Singleton, Woonsocket, RI 02895
122 Margaretta St, Schuylkill H, PA 17972
PO Box 816, Gastonia, NC 28053
2 E Lehman St, Lebanon, PA 17042
650 Cantigue Rd, Jericho, NY 11753
39 Plymouth St, Fairfield, NJ 07006
233 E Chjcago St, Milwaukee, WI 53201
4610 Mission #300, San Francisco, CA 94112
234 W Honda St, Milwaukee, WI 53204
PO Box 749333, Dallas, TX 75374
PO Box 5439, Statesville, NC 28677
315 Seigel St, Brooklyn, NY 11206
12845 NW 45th Ave, Opa-Locka, FL 33054
230 S Poplar St, Berwick, PA 18603
3256 W 25th St, Cleveland, OH 44109
1974 E 61st, Cleveland, OH 44103
Lower Sweeney St, Amsterdam, NY 12010
60 Metro Way, Secaucus. NJ 07094
PO Box 628, Allentown, PA 18105
Sales in
$ Millions
25
24*
24
23
22*
20*
20
20*
20
19
17*
17*
17*
17*
15
15
15
15
14
14*
14*
13
13
13
12
12
12
                       (continued)
                         B-16

-------
                      TABLE B-4.
TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
      SALES GREATER THAN $1 MILLION (continued)
Name
B &B Accesories
J & M Knitting Mills Co.
Knitcraft Corp.
Travis Knits Inc.
Beth Leon Togs Inc.
Encore Textiles Inc.
Blue Bird Knitwear Co.
Lord Jeff Knitting Co, Inc.
Alps Sportswear Mfg. Inc.
Fortune Knits Inc.
Calvert Knitwear Inc.
Klear-Knit Inc.
Asheville Dyeing & Finishing
A & G Mfg Inc.
Manchester Knitted Fashion
Drasin Knitting Mills Inc.
Schuessler Knitting Mills Inc.
Genesco Inc., Capital Swimwear
Scarves by Vera Inc.
Natalie Knitting Mills Inc.
Granite Knitwear Inc.
Briar Knitting Inc.
Taren Holdings Inc.
North American Knitting Co.
Royal Knitting Mills
Kiss Knitting Mills Inc.
Apparel America Inc.
Address
15 W 37th St, New York, NY 10018
1636 Decatur St, Ridgewood, NY 11385
4020 W 6th St, Winona, MN 55987
1515 W Academy St. Cherryville, NC 28201
120-28 W Union Blvd. Bethlehem. PA 18018
PO Box 2004, Monroe, Nc 28110
112 W 34th St, New York, NY 10018
10 Maple St, Norwood, NJ 07648
5 Franklin St, Lawrence, MA 01840
142 W 36th St, New York, NY 10018
333 Scholes St, Brooklyn, NY 11206
1209 E Main St, Rock Hill, SC 29730
Farm School Rd, Swannanoa, NC 28778
183 Loraine St, Brooklyn, NY 11231
33 S Commercial St, Manchester, NH 03101
1721 Trinity St, Los Angeles, CA 90015
1523 N firemont, Chicago, IL 60622
1429 Pk St. Hartford, CT 06106
417 5th Ave. New York, NY 10016
PO Box 722, Chilhowie, VA 24319
PO Box 498, Granite Quar, NC 28072
PO Box 312, Berwick, PA 18603
PO Box 578, Tracy City, TN 37387
490 Dewey Ave, Mansfield, OH 44901
2007 S California St. Chicago, DL 60608
2 Horizon Rd #1422, Fort Lee, NJ 07024
1407 Broadway, New York, NY 10018
Sales in
$ Millions
11
11
10
10
10
10
10
10
10
10
10
10*
9*
9*
9
9 *
9
9*
8
8
8
8
8*
8*
8
8*
7
                       (continued)
                        B-17

-------
                      TABLE B;4.
TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
      SALES GREATER THAN $1 MILLION (continued)
Name
Holden Mfg. Co.
Cornish Knit Goods Mfg. Corp.
Apparel America Inc., Mayfair
Industries
Gould Fabrics Inc.
Kandel Knitting Mill
Garon Knitting Mills Inc.
Windsor Knitting Mill Inc.
Cuddle Knit Inc.
Catoosa Knitting Mills Inc.
Littlefield Adams & Co., Collegiate-
Pacific Co.
Minnesota Knitting Mills Inc.
Terry Tuck Inc.
Dehen Knitting Co.
Acker Knitting Mills
HAB Industries Inc.
OB Dyers
Oakdale Knitting Mills Inc.
Ocello Inc.
Reilly Co., Inc.
Alpha Mills Corp.
Brig A Knits Inc.
Colonial Textile Mfg. Corp.
Eckmil Knitting Inc.
Boutique Knitting Corp.
Gotthelf Knitting Mills
Fit-All Sportswear Inc.
A & R Knitting Mill Corp.
Address
216 W 2nd, Holden, MO 64040
121 Ingraham St, Brooklyn, NY 11237
41 Noble Ave, Shoemakersville, PA 19555
1457 Broadway, New York, NY 10036
4834 N Interstate Ave, Portland, OR 97217
1901 Winter St, Superior, WI 54880
202 S 3rd St, Hamburg, PA 19526
681 Grand Blvd, Deer Park, NY 11729
PO Box 526, Crossville, TN 38557
PO Box 210, Roanoke, VA 24002
1450 Medota Heights, St Paul, MN 55120
4321 Exchange Ave, Los Angeles, CA 90058
404 NW 10th St, Portland, OR 97209
112 W 34th St, New York, NY 10120
PO Box 573, Allentown, PA 18105
45 Noble St, Reading, PA 19611
101 Wyckoff Ave, Brooklyn, NY 11237
PO Box 609, Richland, PA 17087
1306 River St, Valatie, NY 12184
201 S Lancaster St, Annville, PA 17003
130 Parlin Ln, Watchung, NJ 07060
PO Box A-2093, New Bedford, MA 02741
PO Box 389, West New York, NJ 07093
37-50 57th St, Woodside, NY 11377
607 Myrtle Ave, Boonton, NJ 07005
PO Box 1428, Pilot Mounta, NC 27041
9 Wyckoff Ave, Brooklyn, NY 11237
Sales in
$ Millions
7
7
7
7
• 6
'6
6
6
6
6
6
6
5
. 5*
5
5*
5*
5*
5*
5
5
5
5*
4*
4
4
4
                       (continued)
                        B-18

-------
                      TABLE B-4.
TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
      SALES GREATER THAN $1 MILLION (continued)
Name
North Carolina Knits Inc.
Antmait n Inc.
Lewis Gallet Inc.
Kaufman Knitting Co. Inc.
Happyknit Inc.
S & R Knitting Mils Inc.
Western Sportswear Inc.
Broadway Knitting Mills Inc.
Jacques Moret Inc.
Lanz Inc. Poppy by Lanz
Andrews Knitting Mills Inc.
Crown Globe Inc.
WF Hofford Inc.
West Coast Knitting Mills
Amboy Knits Inc.
Best Knitting Mills Inc.
Wright Mfg. Co. Inc.
Worcester Knitting Co., Worcester
Spinning Co.
Hellam Hosiery Co. Inc.
TM Athletics
Centralia Knitting Mills
Wisconsin Knitting Co.
Binghamton Knitting Co.
Dependable Knits Inc.
Stanley Mfg. Co.
Apparel America Inc. Pilgrim
Sportswear Inc.
Renegade Knitwear Inc.
Address
PO Box 218, Albermarle, NC 28001
816 Farren St, Portage, PA 15946
120 Delaware Ave, Uniontown, PA 15401
123 N 3rd st, Minneapolis, MN 55401
42 Central Ave, Farmingdale, NY 11735
240 Broadway, Brooklyn, NY 11211
467 Troutman St, Brooklyn, NY 11237
2152 Sacramento St, Los Angeles. CA 90021
1350 Broadway, New York, NY 10018
8680 Hayden PI, Culver City, CA 90232
3560 Hoffman E, St Paul, MN 55110
338 Main St, Shoemakersville, PA 19555
Bridge St & Railroad St, Weissport, PA 18235
420 W 33rd Ave, Los Angeles, CA 90031
PO Box 969, Perth Amboy, NJ 08861
241 Taaffe PI, Brooklyn. NY 11205 *
114 44th St, Union City, NJ 07087
80 Chapel St, Cherry Valley, MA 01611
PO Box 6158, Hellam. PA 17406
163 S Jackson St, Seattle. WA 98104
PO Box 269, Centralia, WA 98531
904 E Pearson St, Milwaukee, WI 53202
PO Box 1646, Binghamton, NY 13902
PO Box 25, Kings Mountain, NC 28086
PO Box 152, Stanley, VA 22851
350 5th Ave, New York, NY 101 18
Rt 14 Box 542, Crossville, TN 38555
Sales in
$ Millions
4*
4*
4*
4*
4
3
3*
3*
' 3
3*
3
3
2*
2
2*
2*
2*
2*
2
2
2
1
1
1
1*
1*
1*
                       (continued)
                        B-19

-------
                      TABLE B-4.
TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
      SALES GREATER THAN $1 MILLION (continued)
Name
Penn Keystone Knitting Mills Inc.
Pronto Group
Address
1410 Broadway Ste 801, New York, NY 10018
PO Box 545, Vamville, SC 29944
(SIC 2254) Knit Underwear Mills
Sara Lee Knit Prdts.
Jockey Intl Inc.
Spring City Knitting Co. Inc.
Martin Mills Inc.
Cinderella Knitting Mills Inc.
Panola Mills Inc.
Gerber Childrenswear Inc.
JE Morgan Knitting Mill Co.
Medalist Indus Inc.
American Mills Inc.
Johnstown Knitting Mill Co.
American Mills Inc.
Rubens & Marble Inc.
Beltex Corp.
Fruit of the Loom Inc.
Indera Mills Co.
Yocom Knitting Co.
HH Fessler Knitting Co Inc.
Union Knitting Mills
Jacob Boltz Knitting Mill Inc.
Geissler Knitting Mills Inc.
Gerber Children's Wear Inc.
Classtex Knitting Mills Inc.
Swanknit Inc.
PO Box 3019, Winston-Salem, NC 27102
2300 60th St, Kenosha WI 53140
PO Box 1109, Cartersville, GA 30120
PO Box 129, St, MartinviUe, LA 70582
120 W 45th St, New York, NY 10036
PO Box 630, Bateville, MS 38606
400 W Main St, Ephrata, PA 17522
Rte 54, Tamaqua, PA 18252
PO Box 803, Piqua, OH 45356
PO Box 209, Griffin, GA 30224
309 W Montgomery St, Johnstown, NY 12095
PO Box 107, Jackson, GA 30233
2340 N Racine Ave, Chicago, JL 60614
PO Box 749, Belmont. NC 28012
130 Zenker Rd, Lexington, SC 29072
PO Box 10918, Winston-Salem, NC 27108
Race & Monroe St, Stowe, PA 19464
Church & Sherman St, Orwigsburg, PA 17961
PO Box 60, Schuylkill H, PA 17972
317 N 9th St, Pottsville, PA 19464
45 E Green St, Hazleton, PA 18201
PO Box 819, Fuquay-Varina, NC 27526
E Mifflin St, Orwigsburg, PA 17961
PO Box 675, Cohoes, NY 12047
Sales in
$ Millions
1
1*

320
250*
120
100
80
63*
50
40
26
22*
20
17*
17
12
11
10
10
8
7
5*
5*
5*
- 5
5
                       (continued)
                        B-20

-------
                             TABLE B-4.
 TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
         SALES GREATER THAN $1 MILLION (continued!
           Name
          mmmmm
Ashland Knitting Mills Inc.
              Address
Front & Chestnut Sts. Ashland, PA 17921
 Sales in
$ Millions
Tru-Health Inc.
38 St Johns Pi Freeport, NY 11520
Linden Knitwear Corp.
Centerport Rd. NohrviUe, PA 19541
(SIC 2257) Weft Knit Fabric Mills
II West Point-Pepperell Inc.. Alamac
| Knitting Div.
J Dyersburg Fabrics Inc.
I Gold Mills Inc.
	 — 	
Dixie Yarns Inc, Caro-Knit
§ Cleveland Mills Co.
Stony Creek Knitting MiU
Dixie yams Inc., Clyde Fabrics
United Piece Dye Works '
1 Stevcoknit Fabrics Co.
I BTFCorp.
1 International Paper Co.
9 Edmond Stem Inc.
j American Fabrics Co.
1 	
Gumey Industries Inc.
I Stevcoknit Fabrics Co.-Holly Plant
1 Jomac Inc.
Domestic Mfg Co.
| Mffliken & Co. Excelsior MiU
1 Guilford Mills Inc. Guilknits
Celand yam Dyers Inc.
1 Draper Bros, Co., Lie.
1 Ames Textile Corp.
Arc Knitwear Mills Inc.
' 	
1221 Ave of the Americas. New York, NY 10020
PO Box 767, Dyersburg, TN 38025
4925 W Market St, Greensboro, NC 27409
PO Box 366, Jefferson, SC 29718
101 W Main St, Lawndale, NC 28090
PO Box 2445, Rocky Mount, NC 27802
PO Box 760, Newton, NC 28658
111 W 40th St, New York, NY 10018
PO Box 64635, Fayetteville, NC 28306
450 Murray Hill Pkwy, East Rutherford, NJ 07073
335 Athena Industrial Pk, Athens, GA 30601
350 5th Ave, New York, Nr 10118
1069 Connecticut Ave, Bridgeport, CT 06607
242 Ct St, Prattville, AL 36067
601 Wilmington Rd, Wallace, NC 28466
683 Easton Rd, Warrington, PA 18976
PO Box 3548, Kinston, NC 28502
108 W Williams St, Union, SC 29379
PO Box 1645, Lumberton, NC 28358
PO Box 2220, Thomasville, NC 27360
28 Draper Ln, Canton, MA 02021
720 Suffolk St. Lowell, MA 01854
435 E 79 St #9V, New York, NY 10021
170* 1
100 I
76 ||
52 I
40
29
26
25
25* I
24 1
22*
22*
20 I
20 I
18
14 1
12
12 1
11* 1
10 1
7
5* 1
5* 1
                              (continued)
                               B-21

-------
                                     TABLE B-4.
  TEXTILE FIBER DYEING FACILITIES  (SIC 225)  WITH ANNUAL
 	SALES GREATER THAN $1 MILLION (continued)
               Name
 Clover Knit Inc.
                                                    Address
 PC-Box 539, Clover, SC 29710
                                          Sales in
                                         $ Millions
 Montex Corp.
 1101 S 6th St, Allemown, PA 18103
 National Looms Corp.
 229 W 36th St, New York, NY 10018
 Originit Fabrics Inc.
 4627th Ave, New York, NY 10018
 Schuylkill Haven Bleach & Knitting Inc.
 PO Box 307. SchuylkUl H, PA 17972
 Chapel Hill Mfg. Co.
 1807 Walnut St, Oreland, PA 19075
 Mi-Jan Fabrics Inc. .
 Washington St, Denver, PA 17517
 American Research & Knitting Inc.
 PO Box 1004, Cleveland. TN 37364
                                                                               4*
 O & H Mfg. Co., Inc.
 332 N Front St, Allentown, PA 18102
 Knitcraft Inc.
 PO Box 825, Belmont, NC 28012
 Kings Mountain Knit Fabrics Inc.
 Oak & Railroad, Kings Mountain, NC 28086
 Kenda Knits Inc.
PO Box 276, Clover, SC 29710
Jasco Fabrics Inc.
450 7th Ave, New York, NY 10123
                                                                               1*
 (SIC 2258) Lace & Warp Knit Fabric Mills
Guilford Mills Inc.
4925 W Market St, Greensboro, NC 27407
                                                                               620
Stevcoknit Fabrics Co.
PO Box 1500, Greer. SC 29652
                                                                              189*
Fab Industries Inc.
200 Madison Ave, New York, NY 10016
                                                                               168
Liberty Fabrics Inc.
295 5th Ave. New York, NY 10016
                                                                               150
Liberty Fabrics Inc. of Virginia
PO Box 308, Gordonsville, VA 22942
                                                                               75*
Carisbrook Indus Inc., Native Textiles
16 E 34th St, New York, NY 10016
                                                                               60
Glenoit Mills Inc.
                                    POBox 1157. Tarboro, NC 27886
                                           45
Liberty Penn Corp.
PO Box 279, Jamesville, NC 27846
                                                                               40
Mohican Mills Inc.
                                    POBox 190, Lincolnton, NC 28092
                                           35
Lida Mfg. Co.
2222 South Blvd. Charlotte, NC 28203
                                                                              31*
Liberty Fabrics Inc., MainDell Processing
4201 Tonnelle Ave, North Bergen, NJ 07047
                                                                              29*
Hornwood Inc.
                                    POBox 799, Wadesboro, NC 28170
                                           25
Klauber Bros. Lie.
                                    114 E 32nd St, New York. NY 10016
                                    —=====

                                      (continued)
                                           25
                                        B-22

-------
                                      TABLE B-4.
  TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
             SALES GREATER THAN $1 MILLION (continued)
               Name
              n^
 Andrex Indus Cotp.
                 Address
  1430 Broadway, New York, NY 10018
 Sales in
$ Millions
 Westchester Lace Inc.
 3901 Liberty Ave, North Bergen, NJ 07047
 Furtex Corp.
 PO Box 400, Jacksboro, TN 37757
 Charbert Inc.
                                    Church St. Alton, RI 02,894
 Clinton Mills Inc., Elastic Fabrics of
 America
 PO Box 21986, Greensboro, NC 27420
   17*
 Pottsville Bleach & Dye
 Rte 61. Schuylkill H. PA 17972
 Cpntempora Fabrics Inc.
 2451 Contempo Dr.. Luinberton, NC 28358
 Naomi Knitting Mills Inc.
 PO Box 889, Zebulon. NC 27597
 Mohican Mills Inc. Travis Knits
 PO Box 65, Maiden. NC 28650
 Quaker Lace Inc.
 4th & Lehigh Ave. Philadelphia, PA 19133
 Apex Mills Corp.
 168 Doughty Blvd. Inwood, NY 11696
 Bayeux Fabrics Inc.
 PO Box 490, Swepsonville, NC 27359
 Carolace Embroidery Co. Inc.
 501 Broad Ave. Ridgefield, NJ 07657
 Russ Knits Inc.
                                   PO Box 130, Candor. NC 27229
 Continental Fabrics Inc.
 40 E 34th St, New York, NY 10016
Roman Knit Inc.
                                   PO Box 888, Norwood. NC 28128
AUuraCorp.
 6600 Blvd E #1B, West New York, NJ 07093
Campell Mills Inc.
 1104 Southerlnd St. Graham, NC 27253
Pomona Textile Co. Inc.
 1019 S Main St, Los Angeles, CA 90015
Angier Knitting Corp.
PQ Box 128. Angier. NC 27501
Knox-Trim Inc.
                                   PO Box 50126, Knoxville, TN 37950
                                             7*
Fleisher Finishing Inc.
313 Mill St. Waterbury, CT 06720
Scranton Lace Co.
                                   1313 Meylert Ave, Scranton, PA 18501
Fablok Mills Inc.
                                   140 Spring St, Murray Hill, NJ 07974
Aridyne Corp.
PO Box 62, Graham. NC 27253
Bojud Knitting Mills Inc.
4 Willow St, Amsterdam, NY 12010
Bridgton Knitting Mill
Portland Rd, Bridgton. ME 04009
             .

    (continued)
                                        B-23

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                      TABLE B-4.
TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
      SALES GREATER THAN $1 MILLION (continued)
Name
Joseph Titone & Sons Inc.
Knit-Wear & Fabric Inc.
RCR Mill Inc.
International Veiling Corp.
Beaufab Mills Inc.
Alcor Lace Corp.
Fairystone Fabrics Inc.
Buckley & Mann Inc.
Nanray Inc.
Mohawk Fabric Co. Inc.
Paris Lace Inc.
Rue de France Inc.
Sterling Lace Inc.
United Veil Dyeing & Finishing Co.
Helmont Mills Inc.
(SIC 2259) Knitting Mills Nee
Zwicker Knitting Mills Inc.
Darlington Fabrics Corp.
El & El Novelty Co. Inc.
H Warshow & Sons Inc.
Beacon Looms Inc.
Dorothy's Ruffled Originals Inc.
Leading Lady Inc.
Novelty Textile Mills Inc.
Kleinert's Inc. of Alabama, Scott Mills
Div.
Samax Co.
Reeves Bros Inc., Comfy Div.

Address
1002 Jacksonville Rd, Burlington, NJ 08016
145 N Cobb St, Burlington, NC 27215
31 Caterine St, Shillington, PA 19607
PO Box 108, Clifton, NJ 0701 1
1901 W Main St, Stroudsburg, PA 19607
108 W 39th St, New York, NY 10018
PO Box 689, Burlington, NC 27216
PO Box 409, Franklin, MA 02038
PO Box 1362, Lumberton, NC 28358
96 Guy Pk Ave, Amsterdam, NY 12010
1500 Main Ave, Clifton, NJ 07011
78 Thames St, Newport, RI 02840
48 W 37th St 12th H, New York, NY 10018
28 Bostwick Ave, Jersey City, NJ 07305
27 Lion Ave, St Johnsville, NY 13452

PO Vox 1819, Appleton, WI 54913
1359 Broadway, New York, NY 10018
152 W 36th St, New York, NY 10018
45 W 36th St, New York, NY 10018
295 5th Ave, New York, NY 10016
6721 Market St, Wilmington, NC 28405
24050 Commerce Pk, Beachwood, OH 44122
PO Box 498, Wauregan, CT 06387
PO Box 2189, Gastonia, NC 28053
206 Carroll St, Galax, VA 24333
PO Box 68, Pageiand, SC 29728
(continued)
Sales in
$ Millions
fmm^mmmmmm
5
5
5*
5*
5
5
4*
4
4
4
4
3
3
3
1*

50
50
41
40
25
18
17
13
13
6
5*
=^===^=y
                        B-24

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                              TABLE B-4.
  TEXTILE FIBER DYEING FACILITIES (SIC 225) WITH ANNUAL
          SALES GREATER THAN $1 MILLION (continued)
Name
Flexion Fabrics Inc.
Wear-A-Knit Corp.
Sandier Sanitary Wiping Cloth
Address
PO Box 1058, Burlington, NC 27215
1306 18th St. Cloquet, MN 55720
2229 S Halsted St, Chicago, IL 60608
Sales in
$ Millions
4
1
1
* Indicates an estimated financial figure.
Source: Gate Research, Inc. Ward's Business Directory of U.S. Private and Public Companies-1991, Volume 4
Detroit, MI, 1991.
                                B-25

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                    APPENDIX C



SUMMARY OF EMISSION FACTORS LISTED IN THIS DOCUMENT
                       C-l

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C-2

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C-3

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 8
 U
 z
 i


e
o
s
fc,
o
                                        C-4

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c-s

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   1. REPORT NO.
                                ,„.      TECHNICAL REPORT DATA
                                (Mam-read Instructions on the reverse befmtt
      FLE AND SUBTITLE
                                                     •event before comp/ciing)
   Locating And Estimating Air  Emissions  From Sources Of
   Chlorobenzenes
 17. AUTHOR(S)
   V,          ORGANIZATION NAME AND ADDRESS
   TRC Environmental  Corporation
   100 Europa Drive,  Suite 150
   Chapel Hill, NC  27514
  12. SPONSORING AGENCY NAME AND ADDRESS	
   U.  S. Environmental  Protection Agency
   OAR, OAQPS,  TSD, EIB,  EFMS (MD-14)
   Research Triangle Park,  NC  27711
 IIS. SUPPLEMENTARY NOTES
                                                                  3. RtCIPfNT-S ACCESSION NO.
                5. REPORT OATF
                   March  1994.
                  PERFORMING ORGANIZATION COol	


                8. PERFORMING ORGANIZATION REPORT NO.
                 I, CONTRACT/GRANT NO.
                                                                 68-D9-0173
                 3. TYPE OF REPORT AND PERIOD COVERED
                Final
                4. SPONSORING AGENCY CODE
 M6. ABSTRACT
       Project Manager: Dennis Beauregard


17.
                 	 DESCRIPTORS

 Chlorobenzenes
 Air Emissions Sources
 Locating Air Emissions Sources
 Toxic Substances
 Emission Estimation
                                  KEY WORDS AND DOCUMENT ANALYSIS
18. DISTRIBUTION STATEMENT
  Unlimited
EPA Form 2220-1 (R.v. 4-77)   PREVIOUS EO.TION is OBSOLETE
b.lDENTIFIERS/OPEN ENDED TERMS
19. SECURITY CLASS (This Report)
  Unclassified
                                                 20. SECURITY CLASS (Tillspage)'
                                                   Unclassified
                             c. COSATI Field/Group
21. NO. OF PAGES
  178
                            22. PRICE

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