Unitsd States
              Environmental Protection
              Agency
              Office of
              Toxic Substances
              Washington DC 20460
April 1980
EPA-560/13-80-013
              Toxic Substances
&EPA
Materials
Balance for
Anilines
Review
Copy
              Level 1 - Preliminary

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                 FINAL REPORT

           LEVEL I MATERIALS BALANCE

                   ANILINES
                 Prepared for:

     U.S. ENVIRONMENTAL PROTECTION AGENCY
   OFFICE OF PESTICIDES AND TOXIC SUBSTANCES

                  Task No.  10
            Contract No. 68-01-5793
      Michael Callahan - Project Officer
      Elizabeth F. Bryan -  Task Manager
                 Prepared by:

             JRB ASSOCIATES,  INC.
             8400 Westpark Drive
           McLean, Virginia  22102

    Project Manager:          Karen Slimak
        Task Leader:          Robert L.  Hall
Contributing Writer:          Ronald Burger
             Submitted:   May 9,  1980

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                                   ABSTRACT

     This report presents a Phase I materials balance study of a group of anilines
specified in a Task Order from the Office of Toxic Substances, U.S. Environmental
Protection Agency.  The compounds studied were aniline, aniline hydrochloride,
aniline hydrobromide, _p_-, m, and £-nitroanilines, 16 other nitroanilines, and
15 other chloro- and bromoanilines.  Areas of major interest were production
quantities, producers, consumption quantities, and emissions to air, land, and
water related to these processes.  The estimated amounts of 1978 production (where
available) were as follows: aniline, 279,000 kkg; aniline hydrochloride,
4.6 - 100 kkg; £-nitroaniline, 3641 kkg; m-nitroaniline, 0-2.3 kkg; _p_-nitroaniline,
13,000 kkg.  Emissions were estimated when direct data were unavailable.  The results
(in kkg/year) were: aniline, 20 kkg to air, 0.08 - 5.6 kkg to water; aniline hydro-
                                        _3
chloride,   0 kkg to air, 4.6 - 100 x 10   kkg to water; £-nitroaniline, 0.13 kkg to
air, 117 kkg to water.  Throughout the report, estimates and assumptions were made
where justified, in lieu of direct data.  Types of information required for future
studies are noted.

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                            TABLE OF CONTENTS

                                                                     Page
Abstract

List of Tables                                                       vi

List of Figures                                                     viii

Executive Summary                                                   ix

1.0  Introduction                                                     1-1

2.0  Aniline                                                          2-1

     2.1  Physical Properties                                         2-1

     2.2  Materials Balance for Aniline                               2-1

     2.3  Direct Production of Aniline                                2-3

          2.3.1  Production Processes, Producers,  and Locations       2-3

          2.3.2  Amounts Produced                                     2-4

          2.3.3  Emissions Due to Direct Production                   2-6

     2.4  Indirect Production                                         2-11

          2.4.1  Degradation of Products Derived From Anilines        2-11

          2.4.2  Petroleum Industry                                   2-11

          2.4.3  Automobile Exhaust                                   2-12

          2.4.4  Hydrolysis of Acetanilide                            2-12

     2.5  Imports of Anilines                                         2-12

          2.5.1  Amounts                                              2-12

          2.5.2  Emissions Due to Imports                             2-13

          2.5.3  Summary Table                                        2-15

     2.6  Consumption and Use of Aniline                              2-15

          2.6.1  Total Consumption                                    2-15

          2.6.2  Categories of Use                                    2-16

          2.6.3  Use Within Each Category                             2-16

          2.6.4  Emissions By Category of Use                         2-16

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3.0  Aniline Hydrochloride,  m-Chloroaniline Hydrochloride              3_i




     3.1  Physical Properties of Aniline Hydrochloride                3-1




     3.2  Materials Balance  for Aniline Hydrochloride                  3-3




     3.3  Direct Production                                            3-3




          3.3.1  Production  Processes,  Producers,  and  Locations       3-3




          3.3.2  Amounts Produced                                     3-4




          3.3.3  Emissions Due to Direct Production                   3-5




     3.4  Indirect Production                                         3-6




     3.5  Imports                                                     3-6




          3.5.1  Quantity Imported                                    3-6




          3.5.2  Emissions Due to Imports                             3-7




     3.6  Consumption and Use                                         3-7




          3.6.1  Emissions Due to Dye Manufacture                     3-7




          3.6.2  Emissions Due to Photographic Chemical Manufacture   3-8




          3.6.3  Summary of  Emissions Due to Consumption              3-9




     3.7  Emissions Due to Exports                                    3-9




4.0  Aniline Hydrobromide                                             4-1




5.0  _o - Nitroaniline                                                 5-1




     5.1  Physical Properties                                         5-1




     5.2  Materials Balance  for £-Nitroaniline                        5-1




     5.3  Direct Production                                            5-3




          5.3.1  Production  Process, Producers, and Locations         5-3




          5.3.2  Amounts Produced                                     5-3




          5.3.3  Emissions Due to Production                          5-4




     5.4  Indirect Production                                         5-5




     5.5  Imports                                                     5-5




          5.5.1  Amounts                                              5-5




          5.5.2  Emissions Due to Imports                             5-6
                                    ii

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     5.6  Consumption and Use                                         5-6




          5.6.1  Categories of Use                                    5-6




          5.6.2  Amounts of Use                                       5-6




          5.6.3  Emissions by Category of Use                         5-7









6.0  m - Nitroaniline                                                 6-1




     6.1  Physical Properties                                         6-1




     6.2  Materials Balance for m-Nitroaniline                        6-1




     6.3  Direct Production                                           6-3




          6.3.1  Production Processes, Producers,  and Locations       6-3




          6.3.2  Quantity Produced                                    6-3




          6.3.3  Emissions Due to Direct Production                   6-4




     6.4  Indirect Production                                         6-4




     6.5  Imports                                                     6-4




          6.5.1  Amounts Imported                                     6-4




          6.5.2  Emissions Due to Imports                             6-5




     6.6  Consumption and Use                                         6-5




          6.6.1  Total Consumption                                    6-6




          6.6.2  Emissions Due to Dye Manufacture                     6-6




          6.6.3  Emissions Due to Manufacture of Other Products       g_g




     6.7  Emissions Due to Exports                                    6-9









7.0  _£ - Nitroaniline                                                 7-1




     7.1  Physical Properties                                         7-1




     7.2  Materials Balance for p_-Nitroaniline                        7-2




     7.3  Direct Production                                           7-2




          7.3.1  Production Processes, Producers,  and Locations       7-2




          7.3.2  Amounts Produced                                     7-4
                                    iii

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          7.3.3  Emissions Due to Direct Production                   7-4




     7.4  Indirect Production                                         7-7




     7.5  Imports                                                     7-7




          7.5.1  Amounts Imported                                     7-7




          7.5.2  Emissions Due to Imports                             7-8




     7.6  Consumption and Use                                         7-8




          7.6.1  Total Consumption                                    7-8




          7.6.2  Categories of Use                                    7-9




          7.6.3  Emissions by Category of Use                         7-9




     7.7  Emissions Due to Export                                     7-16









8.0  Other Nitroanilines                                              8-1




     8.1  Properties                                                  8-1




     8.2  Materials Balance for Nitroanilines                         8-1




     8.3  Production                                                  8-1




          8.3.1  Producers and Locations                              8-1




          8.3.2  Amounts Produced                                     8-4




     8.4  Imports                                                     8-4




          8.4.1  Amounts                                              8-4




          8.4.2  Emissions Due to Imports                             8-4




     8.5  Consumption and Use                                         8-4




9.0  Chloro- and Bromoanilines                                        9-1




     9.1  Physical Properties                                         9-1




     9.2  Materials Balance for Chloro- and Bromoanilines             9-1




     9.3  Direct Production                                           9-2




          9.3.1  Production Processes, Producers,  and Locations       9-2




          9.3.2  Amounts Produced                                     9-2




          9.3.3  Emissions Due to Direct Production                   9-2




     9.4  Indirect Production                                         9-2



                                   iv

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           9.4.1  Chlorination of Waste Anilines                       9-2




      9.5  Imports                                                     9-5




           9.5.1  Amounts                                              9-5




      9.6  Consumption and Use                                         9-5




10.0  Locations of Emissions                                          10-1




11.0  Data Gaps                                                       11-1




 List of References




 Appendices                                                            A-l




                                                                       B-l

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                               LIST OF TABLES


Table #                                                                Page

  2.1           Emission Factors for Aniline Release to  the Air          2-7

  2.2           Imports of Aniline                                      2-12

  2.3           Emissions Due to Imports of Aniline                     2-35

  2.4           Industrial Consumption of Aniline, 1974-78 (kkg/yr)      2-17

  2.5           Aniline:  Consumption by Isocyanate Manufacture         2-36

  2.6           Aniline:  Consumption During Production of Rubber
                Chemicals                                               2-37

  2.7           Aniline:  Consumption by the Chemical Dye Category      2-38

  2.8           Aniline:  Consumption During the Production of
                Drugs                                                   2-39

  2.9           Aniline:  Consumption During the Miscellaneous
                Components                                              2-4Q

  2.10          Aniline:  Emissions Generated During Production
                of Isocyanates (kkg)                                    2-41

  2.11          Aniline:  Emissions Generated During Production
                of Rubber Chemicals (kkg)                               2-42

  2.12          Aniline:  Emissions Generated During Production
                of Dyes and Intermediates (kkg)                         2-43

  2.13          Aniline:  Emissions Generated During Production
                of Hydroquinone (kkg)                                   2-44

  2.14          Aniline:  Emissions Generated During Drug Manu-
                facture (kkg)                                           2-45

  2.15          Aniline:  Generated Emissions During Manufacture
                of Those Compounds in the Miscellaneous Category        2-46

  3.1           Aniline Hydrochloride:  Emissions Generated During
                Consumption                                             3-10

  5.1           Producers of £ - Nitroaniline by Year                   5-8

  5.2           Production of £ - Nitroaniline, 1978 (kkg)              5-3

  5.3           Table of Imports £ - Nitroaniline (kkg)                  5-6
                                     vi

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 5.4           Industrial Consumption of  ortho-Nitroaniline            5- 9

 6.1           Industrial Consumption of  meta-Nitroaniline (kkg)        6-6

 7.1           Producers of para-Nitroaniline by Year,  Including
               Production Where Available                              7-4

 7.2           Emissions of £ - Nitroaniline During  Synthesis           7-6

 7.3           Industrial Consumption of  para.-nitroaniline (kkg)        7-10

 7.4           Categories and Amounts of  para-nitroaniline
               Consumption 1974-78 (kkg/yr)                             7-11

 7.5           para-Nitroaniline Emissions Generated During Its Use    7-17

 8.1           Physical Properties of Nitroanilines                     8-2

 8.2           Producers of Nitroanilines, 1974-1978                   8-5

 8.3           Imports of Nitroaniline Compounds 1974 to 1978
               (kkg/yr)                                                8-8

 9.1           Physical Properties of Chloro- and Bromoanilines         9-1

 9.2           Imports of Chloro- and Bromoaniline Compounds
               1974-1978 (kkg/yr)                                      9-6

 9.3           Consumption and Uses of Chloroanilines                  9-5

10.1           Locations of Emissions                                 10-2
                                   vii

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                                 LIST OF FIGURES
Figure

 ES-1          Materials Balance for Aniline,  1978

 ES-2          Materials Balance for Aniline Hydrochloride,
               1978

 ES-3          Materials Balance for ortho-Nitroaniline,  1978

 ES-4          Materials Balance for meta-Nitroaniline,  1978

 ES-5          Materials Balance for para-Nitroaniline,  1978

 2.1           Materials Balance for Aniline,  1978                      2-2

 2.2           Process Flow for Catalytic Vapor-phase Hydro-
               genation of Nitrobenzene                                2-4

 2.3           Locations of Aniline Production Sites and
               Plant Capacities                                        2-5

 3.1           Materials Balance for Aniline Hydrochloride,
               1978                                                    3-2

 5.1           Materials Balance for £-Nitroaniline                    5-2

 6.1           Materials Balance for meta-Nitroaniline                 6-2

 7.1           Materials Balance for para-Nitroaniline                 7-3
 8.1           Locations of Nitroaniline Producers,  1978                8-3

 9.1           Chloro- and Bromoaniline Production                     9-3
                                     viii

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                               EXECUTIVE SUMMARY

     This Phase I materials balance reports on emissions due to production and
use of several representatives of the class of anilines.  The compounds desig-
nated by the Task Order for study were the three isomeric nitroanilines,  aniline
hydrochloride, aniline hydrobromide,  and a list of 38 other nitro-,  chloro-,  and
bromoanilines, plus the parent compound, aniline.  Of these compounds,  no infor-
mation was available on three (2,4,6-tribromoaniline hydrobromide,  2-bromo-4,6-
dichloroaniline, and 4-bromo-3,5-dichloroaniline).
     The anilines studied were characterized as being solids at room temperature
with very low water solubilities and relatively low vapor pressures.  The excep-
tions to this generalization were aniline itself (a water-soluble liquid) , o_-
and m-chloroaniline (liquids), and all aniline salts (very water-soluble).

Aniline

     Aniline is synthesized industrially by vapor-phase hydrogenation of nitro-
benzene.  An estimated 279,000 kkg were produced in 1978.  Generated emissions
due to direct production were estimated to be 20 kkg to air and 0.08 - 5.6 kkg
to water.  Aniline was consumed by the following six categories of uses in
1978:  isocyanate synthesis (148,000 kkg; 50% of total consumption), rubber
chemicals (80,000 kkg; 27%), dyes and intermediates (17,800 kkg; 6%), hydro-
quinone  (14,800 kkg; 5%), drugs  (8,900 kkg; 3%), and miscellaneous uses (herbi-
cides, fibers totalling 27,000 kkg; 9%).  In addition a small amount of aniline
hydrochloride was synthesized from aniline.  Between 47% and 60% of aniline
production was used captively, mostly for isocyanate synthesis.  Imports and
exports each contributed less than 1% to aniline availability and use, respect-
ively.  Generated emissions due to aniline consumption (by category of use)
were estimated to be:  isocyanate synthesis, 19 kkg to air, 3,700 kkg to water;
rubber chemicals, 20 kkg to air, 3,900 kkg to water; dyes and intermediates,
4 kkg to air, 900 kkg to water; hydroquinone, 4 kkg to air, 700 kkg to water;
drugs, 0 kkg to air, 85 kkg to water; and miscellaneous, 3 kkg to air, 680 kkg
to water.

     These data are shown on the aniline materials balance, included here as
Figure ES-1.
                                      IX

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Aniline Hydrochloride

     Aniline hydrochloride is the salt formed by neutralizing aniline base with
HC1.  Direct production data were not available from USITC or from the producers
themselves, so production was estimated on the basis of deductions and impress-
ions gained from industrial sources to be 4.6 - 100 kkg/yr.   Generated emissions
                                                                        _3
due to production were estimated to be .—'0 kkg to air and 4.6 - 100 x 10  kkg to
water.  Imports and exports made very small contributions to production and con-
sumption totals.  Aniline hydrochloride was stated by an industry source to be
used almost exclusively in the dye industry.  Based on information from these
personal communications, emissions to water during dye production were estimated
                                _2
to be in the range 2.3 - 77 x 10   kkg aniline hydrochloride per year.  Figure
ES-2 is the materials balance for aniline hydrochloride.

Aniline Hydrobromide

     Although it was judged that aniline hydrobromide was synthesized from
aniline in a manner analogous to aniline hydrochloride, no information was
available on production or consumption of aniline hydrobromide.

o-Nitroaniline

     o-Nitroaniline is synthesized by the ammonolysis of o-chloronitrobenzene.
A reported 3,641 kkg/year were produced in 1978.  Generated emissions due to
this production were estimated to be 69 kkg to water.  It was not possible to
estimate air emissions.  £-Nitroaniline has two major industrial uses;  syn-
thesis of £-phenylenediamine and synthesis of dyes.  No quantitative data were
available so estimates of generated emissions from those consumption processes
were not possible.

     Figure ES-3 displays the available information about o-nitroaniline,

m-Nitroaniline

     m-Nitroaniline is synthesized by the partial reduction of m-dinitrobenzene.
No production data were available, indicating the smaller industrial role played
by in-nitroaniline relative to the ortho and para isomers.  A rough estimate
placed production in the range 0-2.3 kkg/yr. in 1978.  47 kkg were reported
                                      x

-------
as imports in 1978.  Major uses for m-nitroaniline were as an intermediate in
the synthesis of dyes, as photographic anti-fogging agents, and in coccidio-
statics, interior paint pigments,  and synthetic sweeteners.  Quantitative con-
sumption and use data were also unavailable.  Lack of data in these areas pre-
cluded estimation of reasonable emissions due to production and consumption
processes.  Refer to Figure ES-4 for the materials balance of m-nitroaniline.

p-Nitroaniline

     2~Nitroaniline is synthesized by the ammonolysis of _p_-chloronitrobenzene.
It is quantitatively the most important of the three nitroaniline isomers, with
an estimated production in 1978 of 13,000 kkg.  Generated emissions due to pro-
duction were estimated to be 0.13  kkg to air and 117 kkg to water.  p_-Nitro-
aniline was used chiefly in the rubber chemicals industry (6,000 kkg;  40% of
total consumption).  Other uses were dyes and intermediates (20%), gasoline
additives (20%), Pharmaceuticals and veterinary (7%), agricultural chemicals
(3%), and miscellaneous (10%).  The % contributions were 1969 values.   Generated
emissions due to these uses were estimated to total 68 kkg to air and  600 kkg to
water in 1978.  These data are summarized on the materials balance for p_-nitro-
aniline, Figure ES-5.

Other Nitroanilines

     The other anilines containing a nitro group (with or without other ring
substituents) were considered as a group.  No quantitative data were available
on either production or use.  Therefore, emissions could not be estimated.  In
general, these compounds were used predominantly by the dye industry,

Chloro- and Bromoanilines

     As with nitroanilines, the halogenated anilines were considered as a group.
No quantitative data were available, so emissions could not be estimated.  These
compounds seem to be used primarily by the dye industry.
                                      xi

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     All anilines were produced in the eastern half of the U.S., with the
greatest concentrations of aniline capacity along the east coast and Gulf coast.

     This report contains many best-judgement estimates of important numbers.
Production and consumption data for nitroanilines, haloanilines, and aniline
hydrochloride will be required for meaningful emissions estimates for these
classes.  Another key quantity that was missing was a documented aqueous waste
stream analysis for an aniline production plant.  These data will be necessary
for more detailed analysis of aniline emissions.
                                      xii

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          ES-1      MATERIALS  BALANCE FOR ANILINE  (KKG)
TOTALS:
SOURCES
Direct
Production
!79,000
y"

lapott.s
L

Indirect
Production
(product break-
down; oil; auto
exhaust)
i



i: 279,000



30C
148. 000 ^i —

CONSUMPTIVE HON-CONSUhTTIVE
()SR USB CONTAMINANTS OP

Isocyanate
Production
END-PRODUCTS INCINERATION AIR

Carry-over
- — • i. ?
80,000
L

9 000
*°
Rubber
Chemicals
T
Aniline
Hydrobromlde
,J
T Carry-over
i ^ 20
	 "• 	 -1 • 	 	 ^4Xto



18,000
2 800

27.000 .
),000

Hydroqulnone

Carry-over
, . '4
j 	 	 .
Druga | ' carry-over
1 ' 	 '


Acetanlllde for
Druga

Dyes and
Intermediates

Aniline
Hydrochlorlde
Exports

Miscellaneous
Chemicals
fibers, herbl-
eldeal

Acetanlllde/
P-Nitroanlllne

' Carry-over
i ^ *
	 % x tu

5 Carry-over
^
' 3
70
                                                                                                                                                               EMISSIONS





                                                                                                                                                               LAND        WATER   TOTAL










                                                                                                                                                                 7_       3700    3719




                                                                                                                                                                 7         65.6    26










                                                                                                                                                                 7        3900    3920












                                                                                                                                                                 0     6.3 X 10"84 X 10"













                                                                                                                                                                 7        700     704










                                                                                                                                                                 7         85      85
                                                                                                                                                                          900    904
                                                                                                                                                                        Z X 10  Z X 10
                                                                                                                                                                 7         700     703
                                                                                                                                                                 7      10,000   10,070

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ES-2     1978 MATERIALS  DALANCE FOR ANILINE HYDROCHLORIDE (KKG)
                                                                                                                KNVIKONMKNTAL RKI.KASES (kky)

1



















SOUKCKS


1
Anil f lie
Hydroclilor Idc
Direct





MydrtH hlor IJc
I ml i r ec I
I'rixlucl Inn




Imports

TOTAI.S :


















-»



J


100













1 X l(

0(1
CONSUMPTIVE NONCONSUMI'TIVE Sf)I 10 WASTPS
USES AND KXPOKTS CONTAMINANTS USES AIR WATPR LAND ~ TOTAI


	 	 *" i x 10 b x in ' 6 x in"'

17 „ Dye and ~0 . v
> lnt«Bediate8 * Co,,la,,,l,m,,lB > _ () ^Q ^ ^
1 ,
. — 0 7.7 X I0~' ,o o 7.7 x ,„-'
21 l'l»togrnpl«lc ~ 1) . .,,,>.
"^ ChumlcuU ' CunlttuilimiiLs ' ' r II 0 II „
! >.
	 r ^u ~o ~o -o
^ o ? ^0 — o
0 v *** 0 ^ ±.

1 h
^oooo
r2
^" ~0 7 -~0 ---0
100 '-"" 8.7 X 10~l b X 10"' 11.7 X 10"'

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ES-3     MATERIALS  BALANCE FOR Q -  NITROANILINE (KKG)
SOURCES
                                            CONSUMPTIVE
                                                USES
NONCONSUWPTIVE
     USES	
CONTAMINANTS OF
END-PRODUCTS
                                                                                                                           INCINEKATION
   g!:VIRONMENTAL HKI.RAS".S
AIR      LAND       WATI:R      TOTAL
    Direct
    Product Ion
                   3MI
I    Imports       I  (16>    |
                                    ^__^_.^,	*
                                             0 - Plienylene-
                                                 d famine
                   	*j  Corry-over  Into
                        I  Products             I
                                                 Dyes
                          Carry-over Into
                          Products
                                                                                                                                       	>    t
                                                 Pluto
                                                 Antl-fogglng
                                                 Agent
                           Curry-over  1
                           Products
                                      Into
                                    .(36)	I      FX,,

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ES-4       MATERIALS  BALANCE  FOR M-NITP.OAfllLINE  (KKG)
                                                                                         ENVIRONMENTAL  RELEASES  (KKC)
SOURCES 1


1
DIRECT
PRODUCTION
OF
META-NITRO-
ANILINE 2

INDIRECT
PRODUCTION
O

IMPORTS
47


49.3
/
0
— V
47
»
t
>— f
"L
CONSUMPTIVE cm ,n
USES AND EXPORTS CONTAMINANTS NONCONSIIHPTIVt WATER |OLID
1 II II USES 1 . II 1 L LA"" 1 ' L '
V
" »

10.3
',

's
t v

7 v
>'
7 v
o v


DYES AND
INTERMEDIATES


SYNTHETIC
SWEETENERS
0 »

7 »


CONTAMINANTS


CONT AMI HANTS
1
r ' ' ( l
^ ~0 ^,0 . ^ (J
	 ~ ' 'V 1 X 10 2.J /^ll 2.4

f 't 7 ?

PHOTOGRAPHIC
ANT 1 FOGGING
AKFNTS
1

0-PHENYLENE-
DIAMINE
I
» ,

•> v


CONTAMINANTS


CONTAMINANTS

*• o u o o
	 V -1 t
r i i i
	 .. v , ,.
	 	 .„. . V.
> I • t T
*--
"77
^

COCCIDIOSTATIS
1

INTERIOR
PAINT PIGMENTS


EXPORTS
' v

t i.

o »


CONTAMINANTS



CONTAMINANTS


CONTAMINANTS
^ /«• 0 >vO 0 •-()
	 , V. i
^ t 7 7
^w .
~ 1 1 T
._,.- ,. . , .y.
•~* ^ ? 7 ?
^
r" ? / f
. . ..v
~ 7 7 7

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ES-  5       MATERIALS  BALANCE  FOR E-NITROANILINE (KKG)
                        CONSUMPTIVE
                        USES AND EXPORTS
                                                       CONTAMINANTS
NONCONSUHPTIVE
     USES
                                                                                                                           ENVIRONMENTAL RELEASES
                                                                                                                 AIR
                                                                                                                                  WATER
SOLID
WASTES
LAND   I
                                                                                                                                                                    TOTA1-
                                                                                                                 1.3 X 10
                                                                                                                         -1
                                                                                                                                     117
                                                                                                                                                                     117.13

Para-nitroaniline
Direct
13.000 kkg




Indirect
Production





















•






n





fJ
*














13.800
•






» j*




lOb

















6000



3000




000



400





innn



1000






Rubber
Chemicals
1

Dyes and
Intermediates
1


Gasoline
Additives
1

Pharnaceut teals
and Veterinary
Products
|



Agricultural
Chemicals
1



1

Exports
0

~Q



^-0




^-0



0





~n



,



0







Contaminants














Contaminants










r
\


r


r


V

v

V

\



v





v,

                                                                                                                       60
                                                                                                                   4  X  10
                                                                                                                        .-6
                                                                                                                                     500
                                                                                                                                     100
                                                                                                                                8.3 X  10'
                                                                                                                                       ,-3
                                                                                                                                                                     360
                                                                                                                                                                     108

                                                                                                                                                                       0
                                                                                                                                                       0     8.504   X 10
                                                                                                                                                                       -1

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                               1.0  INTRODUCTION

     This report was prepared in response to a task order from the U.S. Environ-
mental Protection Agency (EPA) for a Phase I materials balance study on anilines.
The study includes the compounds aniline, aniline hydrochloride, aniline
hydrobromide, £-, in-, and p_-nitroaniline, plus several other chloro-, bromo-,
and nitro- derivatives.  The EPA was primarily concerned with possible sources
of release to the environment and the amounts involved, since the compounds are
highly toxic.  These substances can be absorbed through skin, ingested, or
inhaled (Hawley, 1977; TRW, 1973a).

     In order to present efficiently the data on many different but related com-
pounds, each compound being studied was the topic of a separate chapter.  Within
each chapter were sections on emissions due to production, consumption, and
other processes.  Tables and figures showing 1978 data were interspersed in the
text, but data for other years were presented at the end of each chapter.

     In the tables reporting "releases"  (emissions) data, the term "releases to
soil" was defined as "material applied to the soil," as opposed to material ap-
plied to a landfill.  A landfill was interpreted as a form of waste storage
rather than as a sink.  The rationale was that anilines in solid form in a
landfill are lost to water through leaching or to air through slow evaporation.
These generalizations were particularly true of aniline itself.  Thus, the lack
of entries in a "releases to soil" column only means that if aniline-containing
solids were placed in a landfill, the amount of aniline present would have been
apportioned to air and water to reflect long-term reality.  On the other hand,
actual "release to soil" would include use of pesticides, fertilizers, or other
chemicals that would yield aniline due to microbial or photochemical degradation.
Such releases would be tabulated as sources of aniline.
                                     1-1

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                                  2.0  ANILINE

2.1  PHYSICAL PROPERTIES

     The compound aniline (aminobenzene) is the parent compound for many of the
40 anilines to be studied in this report.  It is a liquid at room temperature.
Its physical properties can be summarized as follows: (Hawley, 1977; Weast,
1977-78; Strecher, 1968):
                                Aniline
                            Mol. Wt. 93.13

     Melting point                                     -6.2°C
     Boiling point                                   184.4°C
     Solubility in Cold H20                           35 g/1 (0.38 M)
     Solubility in Boiling H20                        64 g/1 (0.68 M)
     Temperature at which vapor pressure = 1 Torr     34.8°C
     pKa                                               4.63

     Of particular interest are aniline's water solubility and vapor pressure.
Aniline is soluble even in cold water.  Its vapor pressure is low compared, for
instance, to toluene (1 Torr at -92°C) and benzene (1 Torr at -58°C).

2.2  MATERIALS BALANCE FOR ANILINE

     Figure 2.1 shows the materials balance for aniline.  It demonstrates the
sources of aniline (production, imports), the consumptive and non-consumptive
uses of aniline (e.g., isocyanate production), and the estimated emissions to
air, land, and water due to each process.  This materials balance diagram is
for the most recent year for which reasonably complete data are available:
1978.  The purpose of this chapter is to explain the assumptions and calcula-
tions that yielded the values reported in the figure.
                                     2-1

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         FIGURE  2.1  MATERIALS BALANCE FOR ANILINE  (KKG)
TOTALS:
SOURCES
148.000 o —
Direct !79,000




1

Indirect
(product break-
down; oil; auto
exhaust)



CONSUMPTIVE NON-CONSUMPTIVE
USE USE CONTAMINANTS OF

Isocyanate
Production
END-PRODUCTS INCINERATION AIR

Carry-over
r 11
80,000
L
15.000.
9 000
18,000

27,000
: 279,000 300,000

Rubber
Chemicals
. 	 J
'1 Carry-over
L_ _ .. ... 	 	 ^ 2Q
Aniline
Hydrobromlde

	 	 ^ 4 X 10



-»



-,

Hydroqulnone
Carry-over
' 	 ' 4

Drugs
.
•" Carry-over
T ' ' 	 ' i
1
Acetanlllde for
Drugs

Dyes and
Intermediates

Aniline
llydrochlorlde
Exports

Ml cellaneous
Chemicals
fibers, herbi-
cides)

->
Acetanlllde/
£-Nltroaniline

* Carry-over
> 4
	 ^ X 10

	 • 	 > Carry-over
^
r J
70
                                                                                                                                                                 EMISSIONS






                                                                                                                                                                 LAND       WATER  TOTAL











                                                                                                                                                                    ?       3700   3719




                                                                                                                                                                    ?         65.6    26











                                                                                                                                                                    ?       3900   3920
                                                                                                                                                                    0     6.3 X 10~84 X 10"6
                                                                                                                                                                             700     704
                                                                                                                                                                              85      85
                                                                                                                                                                   ?         900     904
                                                                                                                                                                   0      2 X 10~42 X 10"*
                                                                                                                                                                   ?        700     703
                                                                                                                                                                         10,000   10,070

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2.3  DIRECT PRODUCTION OF ANILINE

     The processes by which aniline is produced were divided into direct (or plan-
ned) production and indirect production.  This section discusses direct product-
ion of aniline.

2.3.1     Production Processes, Producers, and Locations

     Aniline can be synthesized industrially by the vapor-phase reduction of nitro-
benzene or by ammonolysis of chlorobenzene (TRW Systems Group, 1973b).  However,
the Stanford Research Institute Chemical Economics Handbook (McCaleb, 1979) cites
only the nitrobenzene reduction process as the current method of aniline synthesis.
Therefore, it was assumed that at least 95% of aniline production takes place by
the process:
                      cat. 250°C
           Nitrobenzene                Aniline

     The process flow for catalytic vapor-phase hydrogenation of nitrobenzene is
in Figure 2.2 (Syracuse Research Corp., 1976).  A more complete description of
the process is found in Appendix A.  The hydrogenation is carried out in the
vapor phase (i.e., the temperature is greater than 211°C, the boiling point of
nitrobenzene).

     The locations of aniline production sites and each plant's capacity are
shown in Figure 2.3.  The seven production plants are all in the eastern half
of the country, with two in New Jersey, two in West Virginia, and three on the
Gulf Coast.
                                   2-3

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                                   FIGURE  2.2

             CATALYTIC  VAPOR-PHASE HYDROGENATION OF  NITROBENZENE
                                                ]—*- W.ite witei
            1. Nitrobenzene \aporizer.
            2. Rt-iClor with fluidized catalyst bed.
            3. Cooling tubes.
            4. Catalyst filters.
            5. Product condenser.
            6. Hydrogen recvcle compressor.
 7. Aniline—water settler and decanter.
 8. Crude aniline still.
 9. Reboiler for crude aniline still
10. Condenser.
11. Aniline-finishing stilL
12. Reboiler for aniline-finishing still.
               13. Counter-current extraction column for anlline-vater.
2.3.2   Amounts Produced

     Data were available on  the production of aniline for the past several years.
The  amount of aniline produced in 1978 was estimated  to be 279,000 kkg.  This
value  was selected from the  data presented in Figure  2.3 on the basis of the
following:
      1)  Partial USITC production data  for 1979 showed that for  the eight months
from January through August,  1979, 195,416 kkg of  aniline were produced.
             '•*
      2)  The monthly production values  showed no dlscernable trend, so annual
production was  estimated by  linear extrapolation of  the 8-month  production:
(195,416  kkg/8 mo.) x (1.5)  = 293,000  kkg/12 mos. predicted for 1979.

      3)  In order  to estimate the 1978  production, equal growth  rates were
assumed for 1977-1978 and  1978-1979.  The estimated  1978 production was:
(1977 production)  + (1979  prod.) '- (1977 prod.) .

estimated 1978  production  =  265,000 + 293?00°-265?000  = 279,000 kkg produced

in 1978.  Even  though this value was based on estimated productions, it was
                                          2-4

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                                                    FIGURE 2.3  PRODUCTION OF ANILINE (kkg)



                                                                LOCATIONS
                                                                     PRODUCTION
.'UMBER
jS MAP
1


2


3





4

5


6




7




PRODUCER AND
LOCATION
American Cyana-
mid. Willow
Island, WV
American Cyana-
mld 3
Bound Brook, NJ
E.I. duPont de
Nemours
Beaumont, TX



duPont
Gibbstown, NJ
First Chemical
Corp.
Pascagoula, MS
Mobay Corp.
Nev Martlnsville,
WV


Rubicon Corp.
Geismar, LA

SUM:
USITC TOTAL
1978 1977 1976 1975 1974
PROCESS^ PRODUCTION PRODUCTION PRODUCTION PRODUCTION PRODUCTION
Hydrogenation of
nitrobenzene 23,000 23,000 23,000 23,000

Hydrogenation of
nitrobenzene

Hydrogenation of
nitrobenzene 105,000 105,000 105,000 105,000




Hydrogenation of
nitrobenzene 60,000 60,000 60,000 60,000

Hydrogenation of
nitrobenzene 115,000 45,000 45,000 45,000

Hydrogenation of *~
nitrobenzene 45,000 . 45,000 45,000 45,000

—
Hydrogenation of
nitrobenzene 27,000 27,000 25,000 25,000

375,000 305,000 303,000 303,000
265,000 247,000 185,000 250,000
PREDICTED 1980
PRODUCTION

23,000


27,000


118,000





73,000


115,000


45,000



127.000 *

528,000


REMARKS







Most is us
captively
dyes, rubb
chemicals.
ag.- chemlc



Produced f
sale


Dsed capti
ly for pol
urethanei
Dsed capti
ly for pol
urethanes


 SRI TOTAL
                                        275.000
1.  McCaleb,  (1979).   Estimates based on plant capacities.
2.  Catalytic,  Inc.  (1978).
3.  According to McCaleb (1979),  aniline production  is scheduled  to begin
    during 1978 after being  shut  down since  1974.
4.  McCaleb (1979).   Preliminary  estimate  based  on aniline  consumption.


                                                                  2-5

-------
still a more valid production value than the sum of plant capacities because it
was bracketed by two production values.  We estimated  that  the  1979 estimated
production was within  10% of what  the  true yearly  total will be.  The  uncertainty
associated with the estimated 1978 production was  estimated to  be ±20%, based on
possible variation in  the 1979 production value and a  possible  deviance from the
growth rate extrapolation between  1977 and 1979.   As noted  in the Remarks  column,
three production plants used their aniline captively,  that  is,  the aniline was
used as a feedstock for another process in the same plant.  At  least 177,000 kkg
of capacity was dedicated to captive use in 1978.  This was 47% of total capacity.
On the basis of this,  it was estimated that 47% of actual production was also
used captively.  The amount estimated  to have been used captively was
(279,000 kkg) x (0.47) = 132,000 kkg.  Lowenheim and Moran  (1975) estimated
that, in general, about 60% of aniline production  was  used  captively.  USITC
requires reporting of  all aniline  production greater than 2.3 kkg/year, whether  •
it was captively used  or not.

     As the McCaleb (1979)  estimate of  1980 production  shows (Figure 2.3), a sig-
nificant increase in aniline production is expected.  This is due largely to a
projected increase in use of aniline for  isocyanate synthesis.   Increases in the
capacities of duPont's Beaumont,  Texas, and Biggstown,  New Jersey, plants;  First
Chemical's increase;  and Rubicon's  expasnion have been  responses to this increased
demand.

2.3.3  Emissions Due to Direct  Production

2.3.3.1  Generated Emissions to Air

     Overall emissions of aniline  to air during production were considered to be
the sum of emissions due to the production process itself + those due  to product
storage + those due to product transport.  Data on emission amounts were not
readily available for  any of these steps.  We therefore estimated the  amounts of
generated emissions to air by using the following  operation for each step:
(kkg produced, stored, or transported) x (emission factor in kkg/kkg)  = kkg re-
leased due to production, storage, or  transport.   The  estimated emissions  to air
calculated by this process were:   19  kkg/yr generated during production;
1.1 kkg/yr generated due to storage; and 7 x 10    kkg/yr released during transport.
The total generated emission due to direct production  was 20 kkg in 1978.  The
emission factors used  to estimate  these amounts are summarized  in Table 2.1.
                                        2-6

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           TABLE 2.1  EMISSION FACTORS FOR ANILINE RELEASE TO THE AIR
                               DUE TO PRODUCTION
     PROCESS                                      EMISSION FACTOR

     Production                    6.9 x 10   kkg/kkg (generated emissions)

     Cleaning                           ?

     Storage                       4 x 10   kkg/kkg (generated emissions)
                                         _Q
     Transport                     7 x 10   kkg/kkg (actual emissions)

     Disposal                           ?

     Aniline can be released to the air during the following steps in the
production process (see Figure 2.2):  leaks at connections and pumps; carry-
over at finishing still vent.  The emissions factor for production was obtained
from direct data on air emissions at the Beaumont, Texas, aniline plant of
duPont.  (Hydroscience, Inc., 1977.)  We estimated its uncertainty to be
±20% (their complete report is due at the end of December, 1979).  In applying
this emission factor to yearly production, we assumed the following:  1)  All of
the aniline produced in 1978 was synthesized by hydrogenation of nitrobenzene.
2)  All plants carrying out this process have components and emission sources
similar to those at the Beaumont plant.  Emissions to air during production were
estimated to be:

     (279,000 kkg/yr) x (6.9 x 10~5 kkg/kkg) = 19 kkg/yr

Taking into account the combined uncertainties of the production value and the
emission factors, we estimated the uncertainty of the amount of emissions gen-
erated to be ±30%.
                                    2-7

-------
     The emission factor for storage was obtained from plant data by Hydroscience,
Inc. (1977).  We estimated its uncertainty to be ±20%.  In applying this emission
factor to the amount of aniline stored, we assumed the following:  1)  All aniline
plants store the same fraction of their product as the Beaumont, Texas, duPont
plant for which the emission factor was estimated.  The amount of emissions gen-
erated due to storage was:  (279,000 kkg|
emissions to air due to storage in 1978.
erated due to storage was:  (279,000 kkg) x (4 x 10   kkg/kkg) =1.1 kkg of generated
                                                               _
     The emission factor for losses due to transport was 7 x 10   kkg/kkg.  It
was estimated by using a model a study of spill/release risk in the petroleum
industry (U.S. Coast Guard, 1973-1976; U.S. Army Corps of Engineers, 1973-1976;
Science Applications, Inc., 1977; Science Applications, Inc., 1978; U.S. Depart-
ment of Energy, 1978).  The bases for this application were:  1)  The modes of
transportation for oil and aniline were basically the same  (pipes, barrels, tank
cars).  2)  The petroleum industry studies cited above predicted that approximately
7 x 10" % of the total product moved would be lost during transport and handling.
3)  This loss was estimated to be divided 10% to air and 90% to water because
of aniline's low vapor pressure, moderate solubility in water, and the likelihood
that most spills would be cleaned up by hosing down the area before significant
evaporation occurred.  4)  The amount of aniline transported was zero for plants
that used the aniline captively.  Therefore, this amount of production was sub-
tracted from the total in order to get the amount of aniline transported:
279,000 kkg produced - 132,000 kkg used captively = 147,000 kkg transported.
The amount of emissions released to air due to transport of domestic aniline
was:  (147,000 kkg transported) x (7 x 10~8 kkg/kkg) x (0.10 fraction to air) =
1 x 10~3 kkg/year.

2.3.2.2  Generated Emissions to Water

     Overall emissions of aniline to water during production were considered to
be the sum of emissions due to the production process itself plus those due to
product transport.  Data on emission amounts during these processes were un-
available.  However, emission factors were available for each category, and
these were used to estimate respective emissions.  The estimated emissions to
water were:  0.08 - 5.6 kkg/year generated by the production process; and
      _o
1 x 10   kkg/yr released during transport.  The sum of these contributions
was 0.09 - 5.6 kkg generated during aniline direct production for release to
water during 1978.
                                   2-8

-------
     In each case, the following operation was applied: (kkg produced or trans-
ported) x (emission factor in kkg/kkg) = kkg of emissions generated or released.

     Aniline may be released to water at the following points during its produc-
tion by hydrogenation of nitrobenzene (see Figure 2.2):  Leaks at connections
and pumps, purge valve of crude aniline still, condensate of final water boil-
off in finishing still, waste water from extraction column.  In the absence of
direct data on water emissions, an estimate was derived from an estimated
emission factor of 3 x 10~  kkg/kkg.  This value was based on the following:
1)  MITRE Corp. (1978) cites the following data reported by two aniline manu-
facturers:  Aniline release into the raw waste stream averaged 0.067 kg/kkg
product.  The range was 0.005 - 0.49 kg/kkg product, but there was no indication
of the number of samplings included or who the manufacturers were.  2)  This
generated release factor would be lowered by effluent treatment.  We estimated
that 95% of aniline would be removed.  3)  The discharged water, therefore,
contained (6.7 x 10~  kkg/kkg product) x (0.05 fraction not removed = 3 x 10~
kkg/kkg product.  This was the average emission factor for actual releases to
water.  The range of emission factors was 3 x 10   - 2 x 10~  kkg/kkg produced.

     Application of these emission factors to the estimation of emissions
yielded:  (279,000 kkg produced) x (3 x 10~6 kkg/kkg produced) = 0.84 kkg
released to water due to aniline production in 1978.  The range of values,
calculated in the same way, was 0.08 - 5.6 kkg released.

     The emission estimates spanned a range of 70-fold.  The uncertainties of
the minimum and maximum values were unknown.  Statistical information on the
effluent analyses that were the bases for the emission factors might be found in
the primary source:  EPA Organics and Plastics (1976), 308, Response BPR Master
File Listing.

     Because of the importance of this estimated emission to water, it should be
checked for credibility by the following steps:  1) Probably the major source of
aniline emissions to water is the wastewater effluent from the extraction
column  (process 13 in Figure 2.2).  2)  The influent contains water saturated
with aniline; therefore, the aniline concentration is approximately the physical
limit:  35 g/1 or 129 g/gal.  3)  Assume the efficiency of the extraction column
                                       2-9

-------
is 98%  (Appendix A).  4)  Obtain the yearly production of one or more plants.
5)  Obtain the flow rates of effluent water from the respective extraction
columns.  6)  Calculate the emission factor for generated emissions (i.e.,
before treatment) in this waste stream by the operation:  (129 x 10~  kkg/gal
influent) x (0.02 fraction in waste stream) x (annual waste stream volumes, gal)
4- (annual production,  kkg) = emission factor, kkg/kkg product.  7)  Comparison
of the value with the reported emission factor favg. 6.7 x 10~  kkg/kkg product
in overall raw load (MITRE Corp., 1978* would permit rough evaluation of con-
sistency or inconsistency between the two emission factors.

     Anilines may also be released to water during transport.  No data were
readily available on water emissions during transport.  Therefore, the water
emissions due to transport of aniline were estimated by the operation:  (kkg
aniline transported) x (emission factor, kkg released per kkg transported).
                                                              _2
The amount of emissions estimated by this procedure was 9 x 10   kkg/yr.
                                                                  —8
     The emission factor used to obtain this estimate was 6.3 x 10   kkg/kkg
transported.  It was estimated by using as a model a study of spill/release risk
in the petroleum industry (U.S. Coast Guard, 1973-1976; U.S. Army Corps of
Engineers, 1973-1976; Science Applications, Inc., 1977; Science Applications,
Inc., 1978; U.S. Department of Energy, 1978).  The bases for this application
were:   1)  The modes of transportation for oil and aniline were basically the
same (pipes, barrels, tank cars).  2)  The petroleum industry studies cited
above predicted that approximately 7 x 10  % of the total product moved would be
lost during transport and handling.  3)  This loss was estimated to be divided
10% to air and 90% to water because of aniline's low vapor pressure, moderate
solubility in water, and the likelihood that most spills would be cleaned up
by hosing down the area before significant evaporation occurred.  4)  The amount
of aniline transported was zero for plants that used the aniline captively.
Therefore, this amount of production was subtracted from the total in order to
get the amount of aniline transported:  279,000 kkg produced - 132,000 kkg used
captively = 147,000 kkg transported.  The amount of emissions released to water
                                                                            —8
during  transport of domestic aniline was (147,000 kkg transported) x (7 x 10
                                           _o
kkg/kkg) x (0.9 fraction to water) = 9 x 10   kkg/yr.  This value was a low-side
estimate because aniline is less vicous than oil and would therefore leak and
spill more rapidly.  We estimated the uncertainty for the release of aniline to
water during transport to be +500%, -50%.
                                     2-10

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2.3.3.3  Emissions Due to Disposal of Solid Residues

     Solid residue containing aniline could be produced at the following points
in the flow scheme (Figure 2.2):  walls of reactor; condenser surfaces; traps
at bottom of crude and finished aniline stills; sludge from wastewater treat-
ment.  We estimated that these residues would contain negligible aniline.  This
was based on the following:  1)  The solids were likely to be polymers and con-
densation products of aniline and/or nitrobenzene.  Aniline would be a vapor
or a liquid at operating temperatures.  2)  Mechanically included aniline would
be washed out of the residues by the gas or liquid flows across the residue.

     In order to better evaluate the possibility of emissions in aniline-
containing solids, the following are needed:  1)  More detailed information on
the production process (the nature of the trapped materials and other residues;
2)  chemical analysis of residues; 3)  rate of removal of residues;  4)  methods
of treatment for water wastes and solid residues.

2.4  INDIRECT PRODUCTION

2.4.1  Degradation of Products Derived from Anilines

     Several of the compounds produced from anilines have the potential to yield
anilines back by a simple reaction (usually either hydrolysis or oxidation).
Examples would be hydrolysis of acetanilide or hydrolysis of phenyl isocyanates.
Hydrolysis of even 0.01% of the 148,000 kkg of phenyl isocyanates produced in
1978 (see Table 2.4) would yield almost 15 kkg of aniline release.  This
possibility could be evaluated by studies on the rate of degradation of these
compounds and their end-products.

2.4.2  Petroleum Industry

     The following references in Chemical Abstracts might serve as a starting
point for analysis in this area:  (a) C.A. 89, abstract 149248g (1978), aniline
in coal liquefaction products;  (b) C.A. 89, abstract 113699r (1978), aniline
in tar from underground coal gasification;  (c) C.A. 89, abstract 48420b (1978),
aniline in wastewater from coal gasification.
                                     2-11

-------
2.4.3  Automobile Exhaust

     Phone conversations with EPA mobile emissions chemists lead to the sugges-
tion that anilines are present at trace levels in automobile exhaust.  Upper
bounds on releases could be obtained from the operation:  (detectability limit
in ppb) x (kkg exhaust/yr.).  This contribution (if any) may change as fuel con-
sumption patterns change to synthetic or modified fuels with different nitrogen
contents.

2.4.4  Hydrolysis of Acetanilide

     Acetanilide is described as a "very widely used over-the-counter analgesic"
(Casarett and Doull, 1975).  One of its minor reactions in vivo is deacetylation
to produce aniline (Casarett and Doull, 1975).  By using annual consumption
figures for acetanilide analgesics and biochemical data on proportion hydrolyzed
or rate of hydrolysis, the amount of excreted aniline could be evaluated.

2.5  IMPORTS OF ANILINE

2.5.1  Amounts

     The amounts of aniline imported were available in USITC publications for
four of the last five years.  Less than 1 kkg had been imported between January
and August, 1978.  Based on this, we estimated that 1 kkg of aniline was imported
in 1978.  The uncertainty of this value was estimated to be +50%, -25%.  The
other values available are presented in Table 2.2.

                   TABLE 2.2  IMPORTS OF ANILINE  (kkg/year)

     1978           1977           1976           1975           1974
       I1           n.r.           n.r.           6288           9214

      For the months January through August, 1978 (McCaleb, 1979).

SOURCE:  USITC.  n.r. = not reported
                                      2-12

-------
     The amount of aniline imported was variable, but was generally a small
fraction of total production.  The 1974 value, which was higher because of a
domestic petroleum shortage due to the oil embargo, was 3.6% of production
that year.

2.5.2  Emissions Due to Imports

2.5.2.1  Emissions to Air

     Aniline can be released to the air during the storage and transport of
imported aniline.  These emissions are due to spills, leaks, and evaporation
during transfer between containers.  No data were available on the amounts of
aniline lost to the air in these ways.  We estimated that the emissions of
aniline to the air during importing procedures was 4 x 10~  kkg in 1978.  This
value was obtained by summing the contribution of emissions during transportation
                    _Q
and handling (7 x 10   kkg/year) and the contribution of storage losses
(4 x 10~6 kkg/year).

     The emission factor used to estimate the emissions due to transportation
                       _q
and handling was 7 x 10,   kkg/kkg imported.  It was estimated by using as a model
a study of spill/release risk in the petroleum industry (U.S. Coast Guard,
1973-1976; U.S. Corps of Engineers, 1973-1976; Science Applications, Inc.,
1977; Science Applications, Inc, 1978; U.S. Department of Energy, 1978).  The
bases for this application were:  1)  The modes of transportation for oil and
aniline were basically the same (pipes, barrels, tank cars).  2)  The petroleum
industry studies cited above predicted that approximately 7 x 10  % of the total
product moved would be lost during transport and handling.  3)  This loss was
estimated to be divided 10% to air and 90% to water because of aniline's low vapor
pressure, moderate solubility in water, and the probability that most spills
would be cleaned by hosing down the area before significant evaporation occurs.
The emission factor estimated for release of aniline to air during transport
                         Q                   _q
and handling was (7 x 10  ) x (0.10) = 7 x 10   kkg/kkg.  Application of this
emission factor to the amount of aniline imported in 1978 yielded:  (1 kkg) x
       -9                  -9
(7 x 10   kkg/kkg) = 7 x 10   kkg emitted to air during transport and handling
of imports.  This estimate represented a low-side value because aniline is
significantly  less viscous than oil and would therefore leak more rapidly than
oil.  We estimated the uncertainty of aniline emission at +500%, -50%.
                                     2-13

-------
     The emission factor used to estimate emissions to air during storage was
4 x 10   kkg/kkg stored.  This factor was estimated by Hydroscience, Inc. (1977).
Pending an uncertainty estimate by the authors (their report is expected by the
end of December, 1979), we estimated the uncertainty of the emission factor to
be ±20%.  In applying this emission factor to the estimation of aniline released
to air during storage, we used the following basis:  1)  The storage of imported
aniline used the same equipment and procedures as the storage of domestic aniline.
The amount of emissions to air due to storage of imported aniline was:  (1 kkg)
x (4 10"  kkg/kkg stored) = 4 x 10~  kkg.  Based on the uncertainties of the
production data and the emission factor, the estimated uncertainty of the amount
emitted during storage was +70%, -45%.

2.5.2.2  Emissions To Water

     Emissions to water can occur during storage and transport of imported
aniline.  These releases are due to spills and leaks during transfer between
containers.  No data were available on emissions of aniline to water by these
routes.  It was estimated that the emissions of aniline to water during transport
                                 —8
of imported aniline were 6.3 x 10   kkg in 1978.

     The emission factor used to estimate the emissions due to transport was 6.3
    —8
x 10   kkg/kkg transported.  This value was estimated by using as a model a
study of spill/release risk in the petroleum industry (U.S. Coast Guard, 1973-
1976; U.S. Army Corps of Engineers, 1973-1976; Science Applications, Inc., 1977;
Science Applications, Inc., 1978; U.S. Department of Energy, 1978).  The bases
for this application were:  1) The modes of transportation for oil and aniline
are basically the same  (pipe, barrels, tank cars).  1) The petroleum industry
studies cited above predicted that approximately 7 x 10  % of the total product
moved would be lost during transport and handling.  3) This loss was estimated
to be divided 10% to air and 90% to water because of aniline's low vapor pressure,
moderate water solubility, and the likelihood that most spills would be cleaned
up by hosing down the area before significant evaporation occurred.  The amount
of emissions to water during transport of imported aniline was:  (1 kkg) x (7 x
   8                                              —8
10   kkg/kkg) x (0.9 fraction to water) = 6.3 x 10   kkg.  This value was a low-
side estimate because aniline is less viscous than oil and would therefore leak
and spill more rapidly.  We estimated the uncertainty for the release of imported
aniline to water during transport to be +500%, -50%.
                                      2-14

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2.5.2.3  Emissions Due to Disposal of Solid Residues

     It was estimated that the amount of solid residues accumulated as a result
of aniline import was negligible, and that the release of aniline due to disposal
of solid residues was zero.

2.5.3  Summary Table

     Table 2.3 (end of chapter) summarizes the estimated emissions for years
other than 1978.   No import data were available for 1976.

2.6  CONSUMPTION AND USE OF ANILINE

     Aniline is used in industry for the production of a variety of chemical
substances.  In all cases, it is a chemical intermediate (the starting point for
further synthesis) rather than an end product itself.  In general, there are
three areas to examine for aniline emissions:  1) direct emissions during
consumptive use,   2) carry-over as impurities in manufactured products, and
3) indirect emissions due to degradation of manufactured products.

2.6.1  Total Consumption

     Data were available on the percentage of aniline production that was used
in each of six major categories of use.  In addition, the amount (kkg) of
consumption by some categories was available.  This permitted calculation of
total consumption by the operation:  (kkg used by a category) -J- (fraction of
total used by that category) = total consumption (kkg).  The total con-
sumption of aniline in 1978 was 296,000 kkg, based on the fact that the
148,000 kkg consumed in isocyanate synthesis represented 50% of total con-
sumption (Chemical Marketing Reporter, 1979).  The total consumption value
estimated in this way is in parentheses in Figure 2.1.  Above it is the amount
of total available aniline.  This amount was obtained by the process:  (domestic
production) - (emissions) - (exports) + (imports) = kkg aniline available for
use.  Possible explanations for the difference between the numbers (276,000 kkg
available vs. 296,000 kkg consumed) are:  1) underestimation of imports,
2) overestimation of exports,  3) simple statistical variance:  a change in the
% contribution of isocyanate synthesis from 50% to 51% would lower the total
aniline consumption by 6,000 kkg.
                                     2-15

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2.6.2  Categories of Use

     The categories of aniline use, consuming companies, and amounts used for
the past five years are presented in Table 2.4.  The data were obtained from the
footnoted references; we had no criterion on which to base an uncertainty
estimate.

     Isocyanate synthesis was the largest use category, and the trend was
toward increasing aniline use by this category.  Increases in isocyanate synthesis
accounted for most of the increase in total aniline consumption over the past
five years.

2.6.3  Use Within Each Category

     Tables 2.5 - 2.9 (end of chapter) provide a further breakdown of aniline
use within the major categories.  In the absence of direct data on use within
each category, we estimated the breakdowns shown in the tables based on quali-
tative statements made in the chemical marketing literature.  These estimates are
described in the footnotes to the tables.  Since emissions were calculated only
for the major use categories, uncertainities in the breakdown percentages did
not affect the emissions estimates.

     An even more detailed listing of the derivatives of aniline, how they were
produced, and how they were used is found in Appendix B.

2.6.4  Emissions by Category of Use

2.6.4.1  Emissions Due to Isocyanate Synthesis

   _ Isocyanates can be formed by the reaction of amines with phosgene,
C1-C-C1.  Aniline is used to synthesize the bifunctional isocyanate p_, p_'
 - methylene-bis (phenylisocyanate), MDI.  The reaction sequence is (McCaleb,
1979):
                                        2-16
                                                                             N=C=0
                                                                MDI

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TABLE 2.4  INDUSTRIAL CONSUMPTION OF ANILINE, 1974-1978  (kkg/yr)
Category of
Use
isocyanate
synthesis

Preparation
of rubber
chemicals


manufacture
of dyes



% of Aniline
Consumption Company Product Classes Year
50% Mobay Chemical polymeric isocyanates 1979
Corp. urethane foams
Rubicon Chemicals, 1977
Inc.
Upjohn Co. 1976
Jefferson Chemical
Co. 1975
1974
1978
accelerators
27% American Cyanamid antioxidants 1977
Co. antiozanants
1976
1975
1974
6% American Cyanamid dyes and dye 1978
Co. intermediates
1977
1976
1975
1974
Amount Used (kkg)
148, OOO2
132, OOO4
101, OOO5
78, OOO5
97, OOO6
80, OOO2
83, OOO4
84, OOO5
65, OOO5
90, OOO6
18, OOO2
13, OOO4
14, OOO5
11, OOO5
15, OOO6

-------
                        TABLE 2.4  INDUSTRIAL CONSUMPTION OF ANLINE, 1974-1978  (continued)
NJ
I
00
       Category  of
            Use
% of Aniline
Consumption
Company
Product   classes
Year
Amount Used (kkg)
hydroquinone 5% Tennessee Eastman Co. antioxidants
production photodevelopers




drug manufacture 3% sulfa drugs




miscellaneous 9% fibers
(herbicides and herbicides
(fibers) other



1978

1977
1976
1975
1974
1978
1977
1976
1975
1974
1978

1977
1976
1975
1974
15.0002
[.
13,OCKT
12,0005
9.0005
15.0006
9.0002
8.0004
7,0005
6.0005
10.0006
27.0002

13.0004
22.0005
17.0005
22.0006

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Footnotes (Table 2.4)






1.   Partial list of larger users.  Source:  McCaleb, 1979.




2.   Chemical Marketing Reporter, 1979




3.   Hahn, 1970.




4.   Chemical Purchasing, 1977.




5.   Chemical Marketing Reporter, 1976.




6.   Chemical and Engineering News, 1974.
                                   2-19

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MDI polymerizes to form polyurethanes.

2.6.4.1.1  Emission to Air

     Direct data were not readily available on aniline emissions to air during
isocyanate synthesis.  A best-judgement estimate was made on aniline emissions
during this process.  The estimated amount of generated aniline emissions to air
during MDI synthesis in 1978 was 19 kkg.  This value was obtained in the absence
of data on emission factors during MDI synthesis by using the estimated emission
factor 1.25 x 10   kkg/kkg aniline consumed.  The bases for estimating this
emission factor were:  1) Only the first (aniline-consuming) step in MDI synthesis
was considered.  2) As with many industrial reactions, the yield in the first
step was considered to be 95%.  3) Of the unreacted 5% of input aniline, 50% was
recovered for re-use.  4) The remaining 2.5% of input aniline was released 0.5
part to air, 99.5 parts to water—consistent with aniline's physical properties.
The emission factor obtained was:  (0.05 fraction of aniline unreacted) x (0.5
fraction of unreacted not recovered) x (0.005 fraction to air) = 1.25 x 10   kkg/kkg.

     We estimated the uncertainty of this release to be +500%, -80% based on the
following:  I) The estimated emission would be an over-estimate if the synthesis
processes were more efficient than the estimates used.  2)  The allotment of total
 losses to air and water could be as much as 5- fold off in either direction.
2.6.4.1.2  Emissions to Water

     Direct data were not readily available on aniline emissions to water
during MDI synthesis.  A best-judgement estimate was made of aniline emissions
during this process.  The estimated amount of generated aniline emissions to
water during isocyanate synthesis in 1978 was 3700 kkg.  This value was obtained
in the absense of data on emission factors during MDI synthesis by using the estimated
                        —2
emission factor 2.5 x 10   kkg/kkg aniline used.  The basis for estimating this
emission factor was given in section 2.6.4.1.1.  It was calculated as follows:
(0.05 fraction of unused aniline) x (0.5 fraction of unused aniline not recovered)
                                                                    _2
x (0.995 fraction of unrecovered aniline in water stream) = 2.5 x 10   kkg/kkg.
The amount of aniline emissions generated was (148,000 kkg consumed) x (2.5 x
  _2
10   kkg/kkg) = 3700 kkg aniline emissions to water generated due to isocyanate
synthesis in 1978.
                                   2-20

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     Based on the reasoning described in section 2.6.4.1.1, the uncertainty of
this emission value was estimated to be +500%, -£
2.6.4.1.3  Emissions Due to Disposal of Solid Residues

     No direct data nor data on emission factors was available to permit estimation
of emissions due to disposal of solid, aniline-containing residues formed during
isocyanate synthesis.  In order to be able to estimate emissions to air, land,
and water due to this disposal, the following information would be needed:  1)
process engineering information on the sources of residues during isocyanate
synthesis; 2) quantitative analysis of the residues produced; 3) information on
waste disposal methods at each plant (i.e., landfill, incineration, activated
sludge treatment, stack gas scrubbers, etc.).

2.6.4.1.4  Carry-over of Aniline as Impurities in Products

     No data were available to permit estimation of aniline emissions due to
aniline impurities in isocyanates or polyurethanes derived from them.  In
order to estimate these emissions, the following information would be needed:
1)  proprietary information on chemical analyses of the two predominant isocyanates
manufactured;  2)  chemical analyses of consumer goods containing aniline-based
polyurethanes;  3)  production data on the isocyanates and polymers involved.

2.6.4.1.5  Summary of Aniline Emissions Due to Isocyanate Synthesis

     Table 2.10 (end of chapter) summarizes estimated emissions to air and
water generated during isocyanate synthesis for the years 1974-1978.  The
table also breaks down total emissions into those due to MDI production and
those due to polymethylene polyphenyldiisocyanate synthesis according to the
estimated percent contribution shown in Table 2.5.

2.6.4.2  Emissions Due to Rubber Chemical Synthesis

     Rubber chemicals synthesis utilized an estimated 80,000 kkg of aniline
in 1978.  This was 27% of total aniline usage (Table 2.4).  Specific compounds
and process flow schemes were not available for this category.  Therefore,
emissions were estimated for the generalized "process" of rubber chemicals
production by the operation:  (kkg aniline consumed) x (emission factor, kkg
emissions/kkg aniline consumed) = kkg total generated emissions.
                                   2-21

-------
     In the absence of data on either amounts of emissions or experimentally-
determined emission factors, an overall best-judgement emission factor for
generated emissions due to rubber chemicals synthesis was estimated.  The
                          _2
value estimated was 5 x 10   kkg/kkg.  This emission factor was for the sum
of generated air emissions + generated water emissions.  It was based on
the following considerations:  1)  In any chemical-synthesizing process, only
the first (i.e., aniline-consuming) step was of interest.  2)  On the average,
this first reaction would utilize 90% of the aniline feedstock.  3)  Of the
remaining 10% of input aniline, half was reclaimed and recycled.  4)  The
generated emissions of aniline were therefore 0.05 (or 5%) of aniline consumed:
(0.10 fraction not used) x (0.50 fraction of unused not reclaimed) = 0.05 kkg
generated/kkg aniline used.

2.6.4.2.1  Generated Emissions to Air

     In the absence of data on air emissions or emission factors during rubber
                                                                       _2
chemical synthesis, we used the estimated emission factor above (5 x 10   kkg/kkg)
to estimate the generated emissions to air during this process.  The additional
assumption required was:  1)  Total generated emissions were distributed 0.5 part
to air and 99.5 parts to water.  The estimated emissions were:  (80,000 kkg
                       _o
aniline used) x (5 x 10   kkg/kkg used) x (0.005 fraction to air) = 20 kkg
generated for release to air during rubber chemicals production in 1978.
     The uncertainty of this value was estimated to be +500%, -80%, based on
the analysis presented in section 2.6.4.1.1.

2.6.4.2.2  Generated Emissions to Water

     The method of estimating generated emissions to water during rubber chemical
synthesis was the one described in section 2.6.4.2.1 (above) with the following
exception:  since 99.5% of total emissions were estimated to enter water waste,
the value 0.995 replaces 0.005 in the calculation.  The estimated emissions were:
(80,000 kkg aniline used) x (5 x 10~2 kkg/kkg used) x (0.995 fraction to water) =
4000 kkg generated for release to water during rubber chemicals production in
1978.  The uncertainty is estimated to be +500%, -80% (see section 2.6.4.1.1).
                                    2-22

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2.6.4.2.3  Emissions Due to Disposal of Solid Residues

     No direct data nor data on emission factors were available to permit
estimation of emissions due to disposal of solid, aniline-containing residues
formed during rubber chemicals synthesis.  In order to be able to estimate
emissions to air, land, and water due to this disposal, the following information
would be needed:  1)  process engineering information on the sources of residues
during specific synthesis steps utilizing aniline as a feedstock;  2)  data on
the percent contributions of the individual processes to the total for the rubber
chemicals category;  3)  quantitative analysis of residues produced;  4)  rate
of production of residues;  5)  information on waste disposal methods at each
plant (i.e., landfill, incineration, activated sludge treatment, stack gas
scrubbers, etc.).

2.6.4.2.4  Carry-over of Aniline as Impurities in Products

     No data were available to permit estimation of aniline emissions due to
aniline impurities in rubber chemicals.  In order to estimate these emissions,
the following information would be needed:  1)  identities and amounts of
rubber chemicals derived from aniline;  2)  chemical analyses of these rubber
chemical batches.

2.6.4.2.5  Summary of Aniline Emissions Due to Rubber Chemicals Synthesis

     Table 2.11  (end of chapter) summarizes estimated emissions to air and
water generated during rubber chemicals synthesis for the years 1974-1978.
The table also breaks down total emissions into subcategories:  accelerators,
antioxidants, antiozonants, and curing agents by using the estimated percent
contributions shown in Table 2.6

2.6.4.3  Emissions Due to Manufacture of Dyes and Dye Intermediates

     Dye and dye intermediate synthesis consumed an estimated 18,000 kkg of
aniline in 1978.  This was 6% of total aniline usage (Table 2.4).  Specific
products and process flow schemes were not available for this category.
Therefore, emissions were estimated for the generalized "process" of dye and
dye intermediate synthesis by the operation:  (kkg aniline consumed) x (emission
factor, kkg emissions/kkg aniline consumed) = kkg total generated emissions.
                                    2-23

-------
     In the absence of data on either amounts of emissions or experimentally-
determined emission factors, an overall best-judgement emission factor for
generated emissions due to dye synthesis was estimated.  The value estimated
          _2
was 5 x 10   kkg/kkg.  This emission factor was for the sum of generated air
emissions + generated water emissions.  It was based on the following con-
siderations:  1)  In any chemical-synthesizing process, only the first (i.e.,
aniline-consuming) step was of interest.  2)  On the average, this first reaction
would utilize 90% of the aniline feedstock.  3)  Of the remaining 10% of input
aniline, half was reclaimed and recycled.  4)  The generated emissions of aniline
were therefore 0.05 (of 5%) of aniline consumed:  (0.10 fraction not used) x
(0.05 fraction of unused not reclaimed) = 0.05 kkg generated/kkg aniline used.

2.6.4.3.1  Generated Emissions to Air

     In the absence of data on air emissions or emission factors during dye
                                                              _2
synthesis, we used the estimated emission factor above (5 x 10   kkg/kkg) to
estimate the generated emission to air during this process.  The additional
assumption required was:  1)  Total generated emissions were distributed 0.5 part
to air and 99.5 parts to water.  The estimated emissions were:  (17,800 kkg
                       _2
aniline used) x (5 x 10   kkg/kkg used) x (0.005 fraction to air) = 4 kkg
generated for release to air during dye production in 1978.

     The uncertaintiy of this value was estimated to be +500%, -80%, based on
the analysis presented in section 2.6.4.1.1.

2.6.4.3.2  Generated Emissions to Water

     The method of estimating generated emissions to water during dye synthesis
was the one described in section 2.6.4.3.1 (above) with the following exception:
since 99.5% of total emissions were estimated to enter water waste, the value
0.995 replaced 0.005 in the calculation.  The estimated emissions were:  (17,800 kkg
aniline used) x (5 x 10~2 kkg/kkg used) x (0.995 fraction to water) = 900 kkg
generated for release to water during dye production in 1978.  The uncertainty
was estimated to be +500%, -80% (see section 2.6.4.1.1).
                                   2-24

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2.6.4.3.3  Emissions Due to Disposal of Solid Residues

     No direct data nor data on emission factors were available to permit
estimation of emissions due to disposal of solid, aniline-containing residues
formed during dye synthesis.  In order to be able to estimate emissions to
air, land, and water due to this disposal, the following information would be
needed:  1) process engineering information on the sources of residues during
specific synthesis steps utilizing aniline as a feedstock;  2) data on the
percent contributions of the individual processes to the total for the dyes
category;  3) quantitative analysis of residues produced;  4) rate of pro-
duction of residues;  5) information on waste disposal methods at each plant
(i.e., landfill, incineration, activated sludge treatment, stack gas scrubbers,
etc.).

2.6.4.3.4  Carry-Over of Aniline as Impurities in Products

     No data were available to permit estimation of aniline emissions due to
aniline impurities in dyes and dye intermediates.  In order to estimate these
emissions, the following information would be needed:  1) identities and
amounts of dye chemicals derived from aniline;  2) chemical analyses of these
dye chemical batches.

2.6.4.3.5  Summary of Aniline Emissions Due to Dye and Dye Intermediate Synthesis

     Table 2.12 (end of chapter) summarizes estimated emissions to air and
water generated during dye chemical synthesis for the years 1974-1978.  The
table also breaks down total emissions into subcategories:  azoic, indigoid,
stilbene, and triarylmethane dyes, and pre-dye treatments by using the estimated
percent contributions shown in Table 2.7.

2.6.4.4  Emissions Due to Hydroquinone Production

     Hydroquinone synthesis consumed an estimated 15,000 kkg of aniline in
1978.  This was 5% of total aniline usage (Table 2.4).  Hydroquinone is
produced from aniline in a two-step process (Kirk-Othmer, 1968):  the first
step is the oxidation of aniline to quinone and the second step is the
                                   2-25

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reduction of quinone to hydroquinone.  Further production details were not
available.  Therefore, emissions were estimated by the operation:  (kkg
aniline used) x (emission factor, kkg emission/kkg aniline used) = kkg total
generated emissions.

     In the absence of data on either amounts of emissions or experimentally-
determined emission factors, a best-judgement emission factor for generated
emissions due to hydroquinone production was estimated.  The value estimated
          _2
was 5 x 10   kkg/kkg.  This emission factor was for the sum of generated air
emissions + generated water emissions.  It was based on the following con-
siderations:  1) In the two-step process mentioned above, the aniline-oxidizing
step was judged to utilize 90% of aniline input.  2) Of the remaining 10% of
aniline feedstock, half was reclaimed and recycled.  3) The generated emissions
of aniline were therefore 0.05 (5%) of aniline consumed:  (0.10 fraction not
used) x (0.50 fraction of unused not reclaimed) = 0.05 kkg generated/kkg
aniline used.

2.6.4.4.1  Generated Emissions to Air

     In the absence of data on air emissions or emission factors during
                                                                           _2
hydroquinone synthesis, we used the estimated emission factor above (5 x 10
kkg/kkg) to estimate the generated emissions to air during this process.  The
additional assumption required was:  1) Total generated emissions were distributed
0.5 part to air and 99.5 parts to water.  The estimated emissions were:
(14,800 kkg aniline used) x (5 x 10~2 kkg/kkg used) x (0.005 fraction to air)
= 4 kkg generation for release to air during hydroquinone production in 1978.

     The uncertainty of this value was estimated to be +500%, -80%, based on
the analysis presented in section 2.6.4.1.1.

2.6.4.4.2  Generated Emissions to Water

     The method of estimating generated emissions to water during hydro-
quinone synthesis was the one described in section 2.6.4.4.1 (above) with the
following exception:  since 99.5% of total emissions are estimated to enter
water waste, the value 0.995 replaces 0.005 in the calculation.  The estimated
                                 2-26

-------
emissions were:  (14,800 kkg aniline used) x (5 x 10~2 kkg/kkg used) x (0.995
fraction to water) = 700 kkg generated for release to water during hydroquinone
production in 1978.  The uncertainty is estimated to be +500%, -80% (see
section 2.6.4.1.1).

2.6.4.4.3  Emissions Due to Disposal of Solid Residues

     No direct data nor data on emission factors were available to permit
estimation of emissions due to disposal of solid, aniline-containing residues
formed during hydroquinone synthesis.  In order to be able to estimate emissions
to air, land, and water due to this disposal, the following information would
be needed:  1) process engineering information on the sources of residues
during the synthesis step utilizing aniline as a feedstock;  2) quantitative
analysis of residues produced;  3) rate of production of residues;  4) information
on waste disposal methods at each plant (i.e., landfill, incineration, activated
sludge treatment, stack gas scrubbers, etc.).

2.6.4.4.4  Carry-Over of Aniline as Impurities in Products

     No data were available to permit estimation of aniline emissions due to
aniline impurities in hydroquinone.  In order to estimate these emissions,
the following information would be needed:  1) chemical analyses of hydroquinone
batches.

2.6.4.4.5  Summary of Aniline Emissions Due to Hydroquinone Synthesis

     Table 2.13  (end of chapter) summarizes estimated emissions to air and
water generated during hydroquinone synthesis for the years 1974-1978.

2.6.4.5  Emissions Due to Drug Manufacture

     Drug manufacture utilized an estimated 8900 kkg of aniline in 1978.
This was 3% of total aniline usage (Table 2.4).  With the exception of acetanilide
synthesis, specific compounds and process flow schemes were not available for
this category.  Therefore, emissions were estimated for the generalized
"process" of drug manufacture, excluding acetanilide-based drugs.  In both
                                     2-27

-------
cases, the estimation was obtained by the operation:  (kkg aniline consumed)
x (emission factor, kkg emissions/kkg aniline consumed) = kkg total generated
emissions.

     In the absence of data on either amounts of emissions or experimentally-
derived emission factors, an overall best-judgement emission factor for
generated emissions due to non-acetanilide-based drug synthesis was estimated.
                              _3
The value estimated was 9 x 10   kkg/kkg.  This emission factor was for the
sum of air emissions + water emissions.  It was based on the following
considerations:  1)  Only the first (aniline-consuming) step in a multi-step
drug synthesis was of interest.  2)  In the drug industry, purity of product
would be more important than recovery of yield.  Therefore, the aniline-
derivatizing reaction would be run in such a way as to minimize unused aniline
accompanying the product.  We estimated that 1% unused aniline was possible.
3)  Of this 1% of input, all but 0.1% would be removed by subsequent puri-
fications and emitted to waste streams.  4)  The estimated overall emission
factor was therefore (0.01 fraction of aniline unused) x (0.9 fraction of
                        _0
unused emitted) = 9 x 10   kkg/kkg aniline used.

     The emission factor for acetanilide-based drug synthesis was estimated
            _2
to be 1 x 10   kkg/kkg.  This emission factor was for the sum of air emissions
+ water emissions.  It was based on the following considerations:  1) Acetani-
lide synthesis would be made to use at least 99% of input aniline.  2) Analysis
of technical grade acetanilide showed 0.2% aniline carryover (Kirk-Othmer,
                                       1 IS
1968).  This corresponds to (0.2%) x ( ±^- ) =0.3% of input aniline (135 and
93 are the respective molecular weights of acetanilide and aniline).  3)
Therefore, 0.7% of input aniline was emitted to water and air.  4) The 0.3%
input aniline occurring as an impurity in technical grade acetanilide was
removed during production of USP acetanilide, which contained no aniline
(Kirk-Othmer, 1968).  It was tabulated as an additional emission.  The
                                            _o
estimated overall emission factor was 1 x 10   kkg/kkg aniline used.

2.6.4.5.1  Emissions to Air

     It was estimated that emissions to air were negligible during drug synthesis.
This was because we judged that:  1) each aniline-derivatizing reaction would
                                    2-28

-------
take place efficiently in aqueous solution, and  2) purification of drug
intermediates often would involve crystallization of the desired compound and
discarding of the separated impurities in the aqueous mother liquor.

2.6.4.5.2  Emissions to Water

     As described in section 2.6.5.5.1 (above), all aniline emissions due to
drug synthesis were considered to be aqueous emissions.  The total aqueous
emissions were the sum of emissions due to non-acetanilide synthesis plus
acetanilide synthesis.  In the absence of data on the relative contributions
of these two processes to the total, we used a distribution of 50% aniline
consumption by each route.  The total emissions were estimated to be:
[(0.50 fraction contribution) x (8900 kkg total aniline used) x (9 x 10~3
kkg/kkg used)] + [(0.50) x (8900 kkg) x (1 x 10~2 kkg/kkg)] = 40 kkg (non-
acetanilide) + 45 kkg (acetanilide) = 85 kkg aniline generated for emission
to water during drug synthesis.

     The uncertainty of this emission was estimated to be +100%, -50% based
on the following:  1) The emissions were relatively insensitive to changes in
allocation between acetanilide and non-acetanilide drugs because the emission
factors were similar in size.  2) The emission factors were estimated to be
accurate to within a factor of 2 in each direction.

2.6.4.5.3  Emissions Due to Disposal of Solid Residues

     No direct data on emission factors were available to permit estimation of
emissions due to disposal of solid, aniline-containing residues formed
during drug synthesis.  In order to be able to estimate emissions to air,
land, and water due to this disposal, the following information would be
needed:  1) process engineering information on the sources of residues during
specific synthesis steps utilizing aniline as a feedstock;  2) data on the
percent contributions of the individual processes to the total for the drug
category;  3) quantitative analysis of residues produced;  4) rate of production
of residues;  5) information on waste disposal methods at each plant (i.e.,
landfill, incineration, activated sludge treatment, stack gas scrubbers,
etc.).
                                       2-29

-------
2.6.4.5.4  Carry-Over of Aniline as Impurities in Products

     It was estimated that aniline content in drugs derived from aniline would
be zero, based on purity controls required in the pharmaceuticals industry.

2.6.4.5.5  Summary of Aniline Emissions Due to Drug Synthesis

     Table 2.14  (end of chapter) summarizes estimated emissions to air and water
generated during drug synthesis for the years 1974-1978.

2.6.4.6  Emissions Due to Miscellaneous Consumption

     Synthesis of miscellaneous compounds consumed an estimated 27,000 kkg of
aniline in 1978.  This was 9% of total aniline usage (Table 2.4).  With the
exception of j^-nitroaniline synthesis via_ acetanilide, specific compounds
and process flow schemes were not available for this category.  Therefore,
emissions were estimated for the generalized "process" of miscellaneous
chemicals production by the operation:  (kkg aniline consumed) x (emission
factor, kkg emissions/kkg aniline consumed) = kkg total generated emissions.

     In the absence of data on either amounts of emissions or experimentally-
determined emission factors, an overall best-judgement emission factor for
generated emissions due to non-acetanilide-based miscellaneous chemicals
                                                        _2
synthesis was estimated.  The value estimated was 5 x 10   kkg/kkg.  This
emission factor was for the sum of generated air emissions + generated water
emissions.  It was based on the following considerations:  1) In any chemical-
synthesizing process, only the first (i.e., aniline consuming) step was of
interest.  2)  On the average, this first reaction would utilize 90% of the
aniline feedstock.  3) Of the remaining 10% of input aniline, half was reclaimed
and recycled.  4) The generated emissions of aniline were therefore 0.05  (or 5%)
of aniline consumed:  (0.10 fraction not used) x (0.50 fraction of unused not
                   _2
reclaimed) = 5 x 10   kkg generated/kkg aniline used.

     The emission factor for acetanilide-based-p_-nitroaniline synthesis was
                        _2
estimated to be 0.7 x 10   kkg/kkg.  This emission factor was for the sum of
air emissions + water emissions.  It was based on the following considerations:
1) Acetanilide synthesis would be made to use at least 99% of input aniline.
                                    2-30

-------
2) Analysis of technical grade acetanilide showed 0.2% aniline carry-over
                                                     ns
(Kirk-Othmer, 1968).  This corresponds to (0.2%) x ( ~j ) =0.3% of input
aniline (135 and 93 are the respective molecular weights of acetanilide and
aniline).  3) Therefore, 0.7% of input aniline was emitted to water and air.
4) The 0.3% input aniline occurring as an impurity in technical grade acetanilide
was removed as nitroaniline during subsequent nitration of the acetanilide.
This would also be true of hydrolyzed acetanilide formed by the strongly
acidic conditions of nitration.  These were not tabulated as additional
emissions.  The estimated emission factor for the acetanilide synthesis step
            _2
was 0.7 x 10   kkg/kkg aniline used.

2.6.4.6.1  Generated Emissions to Air

     Emissions to air due to synthesis of miscellaneous chemicals were estimated
to total 3 kkg in 1978.  This estimate was obtained using the emission factors
derived above (section 2.6.4.6) plus the following considerations:  1) In the
absence of data on breakdown of consumption within the miscellaneous category,
we assumed that 50% of the 27,000 kkg was used in non-acetanilide-based
syntheses and 50% was used to synthesize ^-nitroaniline via acetanilide.  2)
Total emissions were distributed 0.5 parts to air and 99.5 parts to water.
3) For the reasons discussed in section 2.6.4.5.1, emissions to air during
acetanilide synthesis were estimated to be zero.  The estimated emissions to
air were:  (13,500 kkg aniline used) x (5 x 10~  kkg/kkg) x (0.005 fraction
to air) = 3 kkg of aniline emissions generated for release to air during
miscellaneous chemicals synthesis in 1978.

     The uncertainty of this value was estimated to be +500%, -80% based on
the analysis presented in section 2.6.4.1.1.

2.6.4.6.2  Generated Emissions to Water

     Total generated emissions to water were the sum of emissions due to non-
acetanilide-based miscellaneous chemicals synthesis plus those due to p-
nitroaniline synthesis via acetanilide.  The bases for estimation of emissions
are given in section 2.6.4.6.1. (above).  The estimated emissions were:
(13,500 kkg aniline used) x (0.05 kkg/kkg) x (0.995 fraction to water) = 700
kkg due to non-acetanilide-based miscellaneous chemicals syntheses; and
                                    2-31

-------
(13,500 kkg used) x (0.7 x 10~2 kkg/kkg) x (1.00 fraction to water) = 900
                                                 s
kkg due to acetanilide-based p-nitroaniline synthesis.  The sum was 700 kkg +
900 kkg = 1600 kkg generated emissions to water during miscellaneous chemicals
synthesis in 1978.

     The uncertainty of each of these values was estimated to be +500%, -80%
based on the analysis presented in section 2.6.4.1.1.

2.6.4.6.3  Emissions Due to Disposal of Solid Residue

     No direct data nor data on emission factors was available to permit
estimation of emissions due to disposal of solid, aniline-containing residues
formed during miscellaneous chemicals synthesis.  In order to be able to
estimate emissions to air, land, and water due to this disposal, the following
information would be needed:  1) process engineering information on the
sources of residues during specific synthesis steps utilizing aniline as a
feedstock;  2) data on the percent contributions of the individual processes
to the total for the miscellaneous chemicals category;  3) quantitative
analysis of residues produced;  4) rate of production of residues;  5) in-
formation on waste disposal methods at each plant (i.e., landfill, inciner-
ation, activated sludge treatment, stack gas scrubbers, etc.).

2.6.4.6.4  Carry-Over of Aniline as Impurities in Product

     With the exception of acetanilide, no data were available to permit
estimation of aniline emissions due to aniline impurities in miscellaneous
chemicals.  In order to estimate these emissions, the following information
would be needed:  1) identities and amounts of miscellaneous chemicals
derived from aniline;  2) chemical analyses of these miscellaneous chemical
batches.  In the case of acetanilide, it was estimated that the amount of
aniline emissions due to carry-over would be zero.  This was based on the
judgement that even though technical grade aniline carries 0.2% aniline as an
impurity (Kirk-Othmer, 1968), this aniline would not survive the subsequent
nitration step and would be quantitatively converted to nitroanilines.
                                      2-32

-------
2.6.4.6.5  Summary of Aniline Emissions Due to Miscellaneous Chemicals Synthesis

     Table 2.15 (end of chapter) summarizes estimated emissions to air and water
generated during miscellaneous chemicals synthesis for the years 1974-1978.
The table also breaks down total emissions into subcategories:  pesticides,
herbicides, resins, corrosion inhibitors, petroleum additives, and other
uses by using the estimated percent contributions shown in Table 2.9.

2.6.4.7  Generated Emissions Due to Exports

2.6.4.7.1  Amount of Exports

     Data were not available on the amount of aniline exported in 1978.
McCaleb (1979) cites industry sources as estimating exports to be 1% of pro-
duction in 1968.  In the absence of contrary or confirmatory data, it was
assumed that exports were 1% of production in 1978, also.  The amount exported
would be (279,000) x (0.01) = 2800 kkg.  No criteria were available to aid in
estimating the uncertainty of this value.

2.6.4.7.2  Emissions to Air

     Emissions to air due to export were considered to be due entirely to
transport of aniline.  No data were available on amounts of emissions or on
emission factors.  Therefore, a best-judgement estimate was made using the
operation:  (kkg exported) x (emission factor, kkg released/kkg exported) =
emissions to air due to export.

     In the absence of data on emission factors, the emission factor for air
                                                                   _q
emissions due to transport during export was estimated to be 7 x 10   kkg/kkg.
It was estimated by using as a model a study of spill/release risk in the
petroleum industry (U.S. Coast Guard, 1973-1976; U.S. Army Corps of Engineers,
1973-1976; Science Applications, Inc., 1977; Science Applications, Inc.,
1978; U.S. Department of Energy, 1978).  The bases for this application were:
1) The modes of transportation for oil and aniline are basically the same
(pipes, barrels, tank cars).  2) The petroleum industry studies cited above
predicted that approximately 7 x 10  % of the total product moved would be
                                      2-33

-------
lost during transport and handling.  3) This loss was estimated to be divided
10% to air and 90% to water because of aniline's low vapor pressure, moderate
solubility in water, and the  likelihood that most spills would be cleaned up
by hosing down the area before significant evaporation occurred.  The amount
of emissions released to air  due to transport of exported aniline was:
(2,800 kkg transported) x (7 x 10~8 kkg/kkg) x  (0.10 fraction to air) = 2 x
10~5 kkg in 1978.

2.6.4.7.3  Emissions to Water

     As described in section  2.6.4.7.2, transport of aniline was considered
to be the only source of emissions during export.  The amount of emissions
                                                                           —8
was calculated as described in that section:  (2800 kkg exported) x  (7 x 10
                                            -4
kkg/kkg) x (0.90 fraction to water) = 2 x 10    kkg emissions to water during
export in 1978.
                                       2-34

-------
                   TABLE 2.3  EMISSIONS DUE TO IMPORTS  OF ANILINE  (kkg)J
Year
Releases to Air During -
Releases to Water During -






NJ
1
OJ
Ln
Storage Transport Storage
1978 4 x 10~6 7 x 10~9
1977 2 x 10"4 4 x 10~7
1976
1975 4 x 10~4 7 x 10~7
1974 400 x 10~4 600 x 10~7
Calculation methods discussed in sections 2.5.2.1 and 2.5.2.2.
Transport

4 x 10~6

6 x 10~6
600 x 10~6


-------
                     TABLE 2.5  ANILINE:  CONSUMPTION BY ISOCYANATE MANUFACTURE
Isocyanate
 Synthesis
% of Aniline Used
 Within Category
1978 (kkg)      1977 (kkg)
Diphenylmethane-
 4,4-diisocyanate

Polymethylene
  Polyphenyl
  Isocyanate
          60

          40
 89,000

 59,000
79,000

53,000
1976 (kkg)


 61,000

 40,000
1975 (kkg)


 47,000

 31,000
1974 (kkg)


 58,000

 39,000
     TOTAL
  (Isocyanate
   Production)
                         148,000
               132,000
              101,000
                78,000
                97,000
 A review of references (McCaleb, 1979; Hancock, 1975; Hahn, 1970; Kirk-Othmer, 1968; Simonds and Church, 1967)
 indicated that diphenylmethane-4, 4-diisocyanate used to be the dominant isocyanate; however, within the last
 five years polymethylene polyphenyl isocyanate has become commercially prominent.  Therefore, it was estimated
 that diphenylmethane-4, 4-diisocyanate now only makes up 60 percent of the isocyanates manufactured from
 aniline.  It was assumed that the manufactured amounts of these two isocyanates did not vary relative to each
 other over the five year period.  Also, it was assumed that no other aniline-derived isocyanate had been
 manufactured on a commercial scale during this five year period.

-------
                          TABLE 2.6  ANILINE:   CONSUMPTION DURING PRODUCTION OF  RUBBER CHEMICALS
           Rubber
         Chemicals

     Accelerators

     Antioxidants

     Antiozonants

     Curing Agents
% of Aniline Used
 Within Category

     40

     30

     20

     10
1978 (kkg)
32,000
24,000
16,000
8,000
1977 (kkg)
33,000
25,000
17,000
8,000
1976 (kkg)
34,000
25,000
17,000
8,000
1975 (kkg)
26,000
20,000
13,000
7,000
1974 (kkg)
36,000
27,000
18,000
9,000
OJ
           TOTAL
      (Rubber Chemical
         Production)
                          80,000
83,000
84,000
65,000
90,000
      A review of  the references (Hancock,  1975;  Hahn,  1970;  Lowenheim and Moran,  1975;  Kirk-Othmer,  1968;
      Snell and Hilton,  1967)  indicated that rubber accelerators  make up  the  greatest  percentage of  the  use  of
      aniline  as a single use  in rubber chemicals industry.   However,  antidegradants,  which is  composed  of anti-
      oxidants and antiozonants, appeared to have the greatest usage as a group  of  aniline in the manufacture  of
      rubber chemicals.   (Lowenheim and Moran,  1975; Kirk-Othmer,  1968.)   The curing agents which are composed
      primarily of stabilizers,  agents  and  retarders appeared to  be produced  in  smaller  quantities than  antioxidants
      and  antiozonants.   (Lowenheim and Moran,  1975; Kirk-Othmer,  1968.)   A review  of  aniline derivatives based
      on number, apparent quantities commercially manufactured, and uses  also supported  the estimated percent
      breakdown of aniline consumption  in the rubber chemical industry (Hancock,  1975; Hahn,  1970; Lowenheim and
      Moran  1975; Kirk-Othmer,  1968; Snell and Hilton,  1967).  No indication was  obtained from the  literature
      that  would  indicate a change in  the  percent of usage  of aniline among  the rubber  chemicals or  with changes
      in the total production  of rubber chemicals over a five year period.

-------
                          TABLE 2.7  ANILINE:  CONSUMPTION BY THE CHEMICAL DYE CATEGORY
 I
OJ
00
           Types of
         Dye Chemicals    	


      Dyes & Intermediates

           Azoic               58

           Indigoid             4

           Stilbene            31

           Triarylmethane       5

           Pre Dye Fiber
           Treatment            1
                TOTAL
        (Dye Chemicals Produced)
% of Aniline Used
 Within Category
1978 (kkg)




 10,000

    700

  6,000

  1,000


    200


 17,900
1977 (kkg)




  8,000

    500

  4,000

    800


  1,000


 14,300
1976 (kkg)




  8,000

    600

  4,000

    900


    100


 13,600
1975 (kkg)




  6,000

    400

  3,000

    700


    100


 10,200
1974 (kkg)




  8,000

    600

  5,000

    900


    100


 14,600
       Calculation of the aniline usage by Chemical Class and year was based upon Benzenoid Dye production
       (Hancock, 1975).  The Chemical Classes were selected by using process descriptions from (EPA, 1977) and
       compilation of dyes mentioned in (Kirk-Othmer, 1968; Snell and Hilton, 1967; Hancock, 1975).  The production
       of each of the four chemical types of dyes was totaled and a percent of the total for each type of dye was
       calculated.  Based on a review of the references (TRW, 1973a; Hancock, 1975; Kirk-Othmer,  1968; TRW, 1973c;
       Snell and Hilton, 1967; EPA, 1977) it was felt that these percents reflect the aniline production percent
       usage in these chemical classes.  Also based on the preceding references it was assumed that pre dye fiber
       treatment does not use more than one percent of the aniline production.  It was assumed based on references
       (Hancock, 1975; Kirk-Othmer, 1968; Snell and Hilton, 1967; EPA, 1977) that percent usage of aniline per
       chemical dye class will not change drastically over the five year period 1974 to 1978.

-------
By Category
70
14
14
2

1978 (kkg)
6,000
1,000
1,000
200
8,000
1977 (kkg)
6,000
1,000
1,000
200
(8.000)1
1976 (kkg)
5,000
1,000
1,000
100
7,000
1975 (kkg)
4,000
800
800
100
6,000
1974 (kkg)
7,000
1,000
1,000
200
10,000
                    TABLE 2.8  ANILINE:   CONSUMPTION  DURING  THE  PRODUCTION OF  DRUGS1'2


        Type of Drug        % of Aniline  Used
        Manufacture

        Sulfa Drugs

        Antipyretic

        Analgesic

        Local Anesthetic


             TOTAL
         Drug Manufacture

ro
u>       i
^°        The 1977 miscellaneous category  included  drugs, hydroquinone, herbicides,  fibers,  and  other compounds.
         This category used 34,000 kkg of aniline.  The  1976 and 1978 figures  were  averaged to  arrive at  a
         realistic estimate for use of aniline  in  the Drug Manufacture.

        2
         Determination of the quantity of aniline  utilized in  the production of  drugs was arrived  at by analyzing
         (USITC, 1976-1979; Kirk-Othmer,  1968;  Snell  and Hilton,  1967).  Prior to the late  1960's  antifebrin
         (acetanilide) was widely used as an antipyretic and analgesic hence representing the major  usage of aniline
         in the drug industry.  After the late  1960?s antifebrin was replaced  by another compound, hence  reducing
         the aniline usage as an antipyretic and analgesic product  (Snell  and  Hilton, 1967).  During the  late 1960's,
         the sulfa drugs became a dominant  end  product consumer  of  aniline in  the drug  industry.   In the  last five
         years it has maintained its dominant position while the anitpyretic and analgesic  aniline based  compounds
         have been relegated to secondary consumers of aniline.   With the  demise of  the antipyretic  and analgesic
         aniline compounds, aniline based local anesthetic compounds have  become a  minimal  consumer  of aniline
         (Kirk-Othmer, 1968).

-------
                   TABLE 2.9  ANILINE:  CONSUMPTION DURING PRODUCTION OF THE MISCELLANEOUS COMPONENTS
                                                                                                     2,3
ISJ
I
•e-
o
           Types of
           Miscellaneous  % of Aniline Used
           Compounds       Within Category
Pesticides

Herbicides

Resins

Corrosion
Inhibitors

Petroleum
Additives

Other Uses
30

30

15


10


 5

10
1978 (kkg)

  8,000

  8,000

  4,000


  3,000
1977 (kkg)J

  4,000

  4,000

  2,000


  1,000
1976 (kkg)

  6,000

  6,000

  3,000


  2,000
1975 (kkg)

  5,000

  5,000

  3,000


  2,000
1974 (kkg)

  7,000

  7,000

  3,000


  2,000
                TOTAL
           Miscellaneous Production
1,000
3,000
27,000
600
1,000
13,000
1,000
2,000
22,000
800
2,000
17,000
1,000
2,000
22,000
           1
            The miscellaneous category  included drugs, hydroquinone, herbicides, fibers and other compounds.  This
            category used 34,000 kkg of aniline.  The annual aniline usage figures for 1976 and 1978 in the Drugs and
            hydroquinone product groups were averaged to determine the potential use of aniline in these product areas.
            These figures were subtracted from the  1977 reported miscellaneous aniline consumption category.  The remain-
            ing quantity of aniline is  the aniline  consumed in the miscellaneous products grouping for 1977.

            The two dominant consumers  in the miscellaneous category are Pesticides and Herbicides.  (McCaleb, 1979;
            Lowenheim and Moran, 1975; Kirk-Othmer,  1968; Snell and Hilton, 1967).  Based on the number of references that
            cited a particular usage and the significance attributed to that usage by each reference, the endproduct uses
            of aniline in the miscellaneous category were selected (McCaleb, 1979; Lowenheim and Moran, 1975; Kirk-Othmer,
            1968; Snell and Hilton, 1967; Hancock,  1975).
           3
            No definitive ordering of the endproducts was attainable in those uses cited under OTHER USES heading in the
            miscellaneous uses of aniline.  These products include:  catalysts, explosives, organic synthesis, rocket
            fuel, and synthetic sweetening agents.

-------
                      TABLE 2.10  ANILINE:  EMISSIONS GENERATED DURING PRODUCTION OF ISOCYANATES (kkg)
                                1978
                       1977
                       1976
                       1975
                       1974
       Isocyanate
       Synthesized
 Emissions
air    water
 Emissions
air    water
 Emissions
air    water
 Emissions
air    water
 Emissions
air    water
N3
I
       Diphenylmethane-
       4,4-diisocyanate

       Polymethylene
         polyphenyl
         diisocyanate

       Total Emissions
         Per Year
 11     2200
  8     1500
 19     3700
 10     2000
  7     1300
 17     3300
  8     1500
  5     1000
 13     2500
  6     1200
         800
 10     2000
  7     1400
  5     1000
 12     2400

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                     TABLE 2.11  ANILINE:  EMISSIONS GENERATED  DURING PRODUCTION OF RUBBER CHEMICALS (kkg)
•ts
t-0
                                  1978
1977
1976
1975
1974
Rubber
Chemicals
Accelerators
Antioxldants
Antiozonants
Curing Agents
Total Loss
Per Year
Emissions
air water
8
6
4
2
20
1600
1200
700
400
3900
Emissions
air water
8
6
4
2
20
1600
1200
800
400
4000
Emissions
air water
9
6
4
2
21
1700
1200
800
400
4100
Emissions
air water
7
5
3
2
17
1300
1000
600
300
3200
Emissions
air water
9
7
5
2
23
1800
1300
900
400
4400

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TABLE 2.12  ANILINE:  EMISSIONS GENERATED DURING PRODUCTION OF DYES AND  INTERMEDIATES  (kkg)
Dyes and
Intermediates

Azoic
Indigoid
Stilbene
Triarylmethane
Pre Dye-
Treatment
NJ
co Total Loss
Per Year
1978
Emissions

air
3
0
1
0

0


4

water
500
40
300
50

9


900
1977
Emissions

air
2
0
1
0

0


3

water
400
30
200
40

6


680
1976
Emissions

air
2
0
1
0

0


3

water
400
30
200
40

7


680
1975
Emissions

air
3
0
1
0

0


3

water
300
20
200
30

5


550
1974
Emissions

air
2
0
1
0

0


3

water
400
30
200
40

7


680

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TABLE 2.13  ANILINE:  EMISSIONS GENERATED DURING  PRODUCTION OF HYDROQUINONE  (kkg)






                                     Emissions




     Year                     Air                 Water






     1978                      4                    700




     1977                      3                    600




     1976                      3                    600




     1975                      2                    400




     1974                      4                    700
                                     2-44

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TABLE 2.14  ANILINE:  EMISSIONS GENERATED DURING DRUG MANUFACTURE (kkg)






                                     Emissions




Year                          Air                 Water






1978                           0                   85




1977                           0                   76




1976                           0                   67




1975                           0                   53




1974                           0                   92
                                  2^5

-------
NJ
I
                    TABLE 2.15  ANILINE:   GENERATED EMISSIONS  DURING MANUFACTURE  OF  THOSE  COMPOUNDS

                                             IN THE MISCELLANEOUS  CATEGORY
Miscellaneous
Compounds
Pesticides
Herbicides
Resins
Corrosion
Inhibitors
Petroleum
Additives
Other Uses
1978
Emissions
air water
1
1
0.5
0.4
0.1
0.4
200
200
100
80
20
80
1977
Emissions
air water
0.5
0.5
0.3
0.1
0.05
0.1
100
100
50
30
10
30
1976
Emissions
air water
0.8
0.8
0.4
0.3
0.1
0.3
150
150
70
50
25
50
1975
Emissions
air water
.9
.9
0.3
0.3
0.1
0.3
170
170
50
50
25
50
1974
Emissions
air wate
0.6
0.9
0.4
0.3
0.1
0.3
120
170
70
50
25
50
        Total  Emissions
        Per Year        3.4
680
1.6
320
2.7
500
2.8
520
2.6
490

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         3.0  ANILINE HYDROCHLORIDE,  m-CKLOROANILINE HYDROCHLORIDE
3.1  PHYSICAL PROPERTIES OF ANILINE HYDROCHLORIDE AND m-CHLOROANILINE
     HYDROCHLORIDE
Chemical Formula
C,H,N-HC1
 b /
C.H C1N-HC1
 6 6
Chemical Structure
Molecular Weight

Melting Point

Boiling Point

Solubility

Vapor Pressure

Density
129.60
198°C
245 C at 760 Torr
1,070 g/1 of H20
none available
1.22 g/cc
164.04
221.5°C
none available
very soluble
none available
none available
The physical properties were abstracted from Stecher,  1968 and Weast,  1972.

     Two physical properties of aniline hydrochloride  aid in determining the
environmental medium to which aniline hydrochloride may be released.   The high
solubility of aniline hydrochloride in water (1,070 g/1 of H-0) suggests that
much of the aniline hydrochloride lost during the manufacturing process  and
its application would probably be lost to the environmental water medium. If
the vapor pressure were known for aniline hydrochloride, it would aid  in
estimating the quantity of aniline hydrochloride that  could be released  to
the air during production and consumption.
                                     3-1

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3.2  MATERIALS BALANCE FOR ANILINE HYDROCHLORIDE

     Figure 3.1 shows the materials balance for aniline hydrochloride  for  the
year 1978.  The purpose of the following text is to explain the  basis  of our
estimates and calculations that yielded the values reported in the  figure.

3.3  DIRECT PRODUCTION OF ANILINE HYDROCHLORIDE

3.3.1  Production Processes,  Producers and Locations

     Aniline hydrochloride is produced by the direct reaction of aniline with
hydrochloric acid.  (Kirk-Othmer, 1968)
     The literature cited two methods by which the direct reaction occurs:   dry
hydrogen chloride gas is passed through an ethereal solution of  aniline;  and
concentrated hydrochloric acid is used to neutralize aniline which has  been
heated  to  100 C with  the mixture then being allowed to crystallize (Hawley,
1977).

     The literature did not indicate which of the methods was the dominant one
used in commercial production nor was there any discussion of the production
process.

     From discussions with American Cyanamid it was learned that their  produc-
tion process for aniline hydrochloride consisted of liquid aniline plus as
aqueous solution of hydrochloric acid in the presence of a metallic catalyst
(Personal Communication).  The ratio of the reactants was not disclosed.
Similar information about the production of aniline hydrochloride was not
revealed by Tennessee Eastman Chemical.

     USITC and EPA (1977) reported the following production information.  The
aniline hydrochloride report was confirmed by company spokesmen.
                                        3-2

-------
FIGURE 3.1   1978 MATERIALS BALANCE FOR ANILINE HYDROCHLORIDE  (KKG)
                                                                                                                    ENVIRONMENTAL RELEASES (kkg)





















SOURCES


1

Hydrochloride
Direct





Hydrochloride
Indirect
Production




Imports

TOTALS :












•*





•»



J


100













1 X 1(

100
CONSIT.IPT1VE NONCONSUMPTIVE SOLID WASTES
USES AND EXPORTS CONTAMINANTS USES AIR WATER LAND TOTAL


	 ^~ 1 X 10 b X lu ft X IU

77 Dye and ~0 . 	 v
* Intermediates * a,.,Uu,i,,a,.ts > ~0 ~0 ~0 -'O
1 >
*" ./~0 7.7 X 10~* ~0 7.7 X 10"*
23 ^ Photographic ~ 0 V r . i >
1"^ Chemicals ' CouLaiuli,Bnt- T u 0 0 0
| ^
^ ~0 ~u /~0 -0
~07 ~0 -0
0 v '^^ 0 »^ c_

1 	 *.
L — ^^ ^ oooo
r2
^ —0 7 —0 ~0
100 '""O 8.7 X 10"1 5 X 10"1 13.7 X lo"1

-------
                                                       Years Listed     Production
Compound         Company              Location         as Producer         (kkg)
aniline      American Cyanamid    Bound Brook, NJ       1974-1978         n.a.
   -.,     Tennessee Eastman    Kingsport, TN         1974-1978         n.a.
 chloride      _,                     & r   »
               Chem.

m-chloro-    Alliance Chem.       Newark, NJ               1977                0
  aniline    Blackman-Uhler       Spartanburg, SC          1977            0.5-5
  hydro-       ~i_    T>.I
   *    .,      Chem. Div.
  chloride
No other information on producers and locations was available.

3.3.2  Amounts of Aniline Hydrochloride Produced

     No production or capacity figures were available in the references reviewed.
Discussions with American Cyanamid and Tennessee Eastman Chemical suggested that
the production of aniline hydrochloride was somewhere between 4.6 kkg and 100
kkg.  The lower estimate was derived from the fact that companies are required
to report to USITC when production exceeds 2.3 kkg or $5,000.  Two companies
reported production of aniline hydrochloride, indicating that at least 4.6 kkg
of this were manufactured.

     The higher value was selected based on discussions with American Cyanamid
about the plant capacity at Bound Erook, New Jersey.  The source indicated that
the aniline hydrochloride capacity was considerably below the aniline plant
capacity of 30,000 kkg, yet above 30 kkg.  From this conversation it was deter-
mined that the production of aniline hydrochloride may be as high as 77 kkg.

     Information was obtained on the production of aniline hydrochloride from
Tennessee Eastman Chemical.  The USITC reports from 1974 through 1978 indicate
that Tennessee Eastman Chemical did not report the production of aniline.  Since
aniline hydrochloride was made from aniline, it would be more economical to
manufacture large quantities of aniline and captively consume them in aniline
hydrochloride production than to buy it from an outside source.  Based on this
reasoning, and discussions with a spokesman from Tennessee Eastman Chemical, it
was estimated that the Eastman production of aniline hydrochloride constitutes
a range from 2.3 kkg to 23 kkg.  Thus, the total production of aniline hydro-
chloride was estimated to fall within the range 4.6-100 kkg/yr.
                                         3-4

-------
3.3.3  Emissions of Aniline Hydrochloride Due to Direct Production

     Based on a conversation with American Cyanamid, it was learned that the
only waste from the production of aniline hydrochloride is in the form of a
liquid waste stream.  A spokesperson for Tennessee Eastman Chemical stated that
no liquid or solid residues were produced during manufacture.  He also felt no
emissions to air occurred during productions. These assertions should be tested
when further data are available.

3.3.3.1  Air Emission

     Personal communication with American Cyanamid revealed that there is pro-
bably no release of aniline hydrochloride to the air pathway during production.
If the vapor pressure and more information about the production process machi-
nery were available a numerical estimate might be calculated.  We believe that
releases of aniline hydrochoride to the air during production were minute.

3.3.3.2  Water Emissions

     Conversations with American Cyanamid indicated that the manufacture of
aniline hydrochloride does produce a liquid waste stream.  No information as to
the character, constituents, and quantity of the liquid wastestream was obtained.
However, the waste stream was treated by a central treatment plant at the American
Cyanamid, Bound Brook (NJ) plant.  The central treatment plant consists of a
primary, secondary-biological, and tertiary-activated carbon treatment facilities.
The loss of aniline hydrochloride to the environmental water medium was
probably very small at this plant due to the treatment facilities.

     It was estimated that 0.1% of the total aniline hydrochloride was lost
to the water pathway:
            0.1% x 4.6 kkg  (low production parameter) = 4.6 x 10~  kkg
            0.1% x 100 kkg  (high production parameter) = 1 x 10   kkg

      The aniline hydrochloride production figures were derived in section 3.3.2.

3.3.3.3  Disposal of Solid Waste

     An American Cyanamid source stated that no solid waste was created during
the production of aniline hydrochloride.  However, it is believed that some ani-

                                     3-5

-------
line hydrochloride would be found in the sludge of the first treatment process
of the plant water treatment facility.  Based on the primary treatment process
which was probably some type of settling method, it was estimated that 0.5% of the
annual aniline hydrochloride was lost to the water pathway.
           0.5% x 4.6 kkg  (low estimate of production) = 2.3 x 10   kkg
           0.5% x 100 kkg  (high estimate of production) = 5 x 10"1 kkg

     The annual production values were derived in Section 3.3.2 of this report.

3.4  INDIRECT PRODUCTION OF ANILINE HYDROCHLORIDE

     Aniline hydrochloride will be produced in the environment if the pH of the
surrounding water is below aniline's pKa value.  If chloride ions are present,
then aniline hydrochloride would result.  No estimates of the quantity of aniline
hydrochloride formed in this way were possible because of the lack of data on pH
and aniline concentration in environmental water samples.  We estimated that very
small quantities of aniline hydrochloride would be produced in this manner.

3.5  IMPORTS OF ANILINE HYDROCHLORIDE
3.5.1  Quantity Imported

     The USITC report on Imports of Benzenoid Chemicals and Products for 1974
through 1978 did not cite any import data for aniline hydrochloride.  These
                                          _2
reports did indicate that less than 1 x 10   kkg of aniline hydroehloride could be
imported and this figure would not be reported in the USITC reports.  Secondly,
those values used in the USITC reports were only taken from the major east and
Gulf coast ports of entry.  Therefore they represent a statistical coverage
value, depending on the year, from 76 to 99 percent.  It was estimated that the
                                                                              _2
average annual imports of aniline hydrochloride during 1974 to 1978 was 1 x 10   kkg.
This figure was determined by calculating the average statistical coverage value
for "intermediates" and then multiplying the average times the maximum amount of
chemical that was not reported.
   84%
four year average of the
USITC statistical coverage
           value
x 1 x 10~2 kkg
maximum amount of aniline
hydrochloride that could be
imported without appearing
in the USITC reports
                              1 x 10~2 kkg
                                      3-6
                                    [estimated four year average annual]
                                    [aniline hydrochloride imports    _|

-------
3.5.2  Emissions Due to Imports

     The estimated quantities imported were very small; therefore the contribu-
tion of aniline hydrochloride to the environmental media would be exceedingly
small.

3.6  CONSUMPTION AND USE OF ANILINE HYDROCHLORIDE

     The literature reviewed suggested several commercial uses for aniline
hydrochloride:  synthesis of diphenylamine dyes, N-ethylaniline, diethylaniline,
and 2,4,6-tribromoaniline (Hahn, 1970; Hancock, 1975; Hawley, 1977; Kirk-Othmer,
1975; Snell and Hilton, 1967).

     An American Cyanamid official stated that all of the aniline hydrochloride
produced at its Bound Brook (NJ) plant between 1974 through 1978 was used in the
manufacture of dyes and related products.  The source further stated that all of
the alkyl anilines are manufactured from aniline rather than aniline hydrochloride
for economic reasons.

     The aniline hydrochloride produced at the Tennessee Eastman Chemical was a
transitory product in a long series of steps to produce photographic chemicals.
(Personal communication with Tennessee Eastman Chemical.)

     Based on the economic premise that the alkyl anilines were manufactured from
aniline, it was felt that almost all of the annual aniline hydrochloride was
used to manufacture dyes and related products, and photographic chemicals.

     The spokespersons for American Cyanamid and Tennessee Eastman stated that
the demand for aniline hydrochloride has not changed significantly for the
period 1974 through 1978.

3.6.1  Emissions of Aniline Hydrochloride Due to the Manufacture of Dye and
       Related Products

     The amounts and types of constituents used to manufacture dyes are so varied
among dye classes and within the same dye class that it was impossible to estimate
releases to air and water.  The calculations and estimates below represented
very broad emissions figures of aniline hydrochloride to the environmental
                                        3-7

-------
pathways.  Discussions with an industry expert on dyes and dyestuffs revealed
the manufacturing process for mono-azo dyestuffs.  (Personal Communication.)
This information provided the background information for the estimates on emissions.

     To get the dye out of its manufacturing solution, the solution is heated
and then sodium choride is added.  The dye precipitates out of solution with
sodium chloride as a contaminant in ppb.  The dye precipitate is filtered and
pressed to form a dye cake.  The dye cake is air dried down to a three to four
percent water content.  This process suggests three points where emissions can
occur:
     1)   After the dye was precipitated from the solution, the mother liquid was
probably pretreated and then released to the municiple sewage system.  Because
of the high solubility of aniline hydrochloride in water it was conceivable that
one percent of the annual production of aniline hydrochloride could enter the
environmental water medium.
                                                             —2
           1% x 2.3 kkg (low estimated production) = 2.3 x 10   kkg
           1% x 77 kkg (high estimated production) 7.7 x 10   kkg

The production estimates for aniline hydrochloride were calculated in section 3.3.2.

     2)   The quantity of aniline hydrochloride lost to the air pathway during
drying was unknown, because the vapor presssure of aniline hydrochloride was not
stated in the literature.  However, we feel that it was probably insignificant.
     3)   The free aniline hydrochloride that may contaminate the dye was esti-
mated to be insignificant.  This premise was based on a discussion with an in-
dustrial dyestuff expert.
3.6.2  Emissions of Aniline Hydrochloride Due to the Manufacture of Photographic
       Chemicals

     In the absence of process flow diagrams or data on emissions or emission
factors, it was difficult to estimate the types and quantities of emissions.
                                      3-8

-------
     It was estimated that Insignificant emissions to air and water media occur
during the manufacturing process.  This was based on the following:  1)  Aniline
hydrochloride was a transitory compound in a long series of processes.   2)  A
spokesperson at Tennessee Eastman stated that there was no liquid wastes and
probably no emissions to air during the use of aniline hydrochloride.

3.6.3  Summary of Aniline Hydrochloride Emissions Due to Its Uses

     Table 3. 1 summaries the estimated emissions to air and water generated
during the manufacture of products.

3.7  EMISSIONS DUE TO EXPORTS

     An investigation conducted by the Foreign Trade Commision consisting of a
search of the July 1978 invoices revealed no exports of any of the aniline
compounds.
                                      3-9

-------
                     TABLE  3.1   ANILINE HYDROCHLORIDE:   EMISSIONS  GENERATED DURING CONSUMPTION
                                  1978                1977                 1976                 1975                1974
         Product
         Manufactured            Emissions  kkg       Emissions kkg       Emissions kkg       Emissions kkg       Emissions kkg
         from                  air        water    air       water    air       water    air        water    air        water


         Dyes and Dye
         Intermediates  '                7.7 x  10            7.7 x 10              7.7 x 10            7.7 x 10           7.7 x 10


         Photographic
         Chemicals
CO
M         TOTAL
o
              The  high  estimated  production value was  used  to calculate  the  losses in water.  The formula used
              for  the caluclations  is  derived  in section 3.6.1.
              2
              It was assumed  that the  production of  aniline hydrochloride and  dyes did not change over the time period.

-------
                    4.0  ANILINE HYDROBROMIDE

     No informantion and data were found either in the literature or contacts
with industry which suggest that aniline hydrobromide was commercially manufactured
or used to produce end products in the United States.

     To ascertain if aniline hydrobromide was manufactured, a canvassing of the
organic chemical industry must be undertaken.

     In the absence of any data, we estimated that an insignificant quantity of
aniline hydrobromide may be produced as a speciality chemical.
                                      4-1

-------
                            5.0  o-NITROANILINE

5.1  PHYSICAL PROPERTIES

       The physical properties of o^-nitroaniline are summarized below (Hawley,
1977; Weast, 1977-78; Strecher, 1968).  Quantitative data on water solubility
were not available; qualitative information is presented instead as a general
guide.
                                  o
                              o-nitroaniline
                              mol. wt. 138.12

          Melting point                                71.5°C
          Boiling point                                284°C
          Solubility in  cold HO                      slight
          Solubility in boiling H20                    soluble
          Temp, at which vapor pressure = 1 Torr       104°C
          pKa

       ^-Nitroaniline is a solid at room temperature.  It is characterized as
soluble in hot water and has a vapor pressure lower than that of aniline (section
2.1).

5.2  MATERIALS BALANCE FOR £-NITROANILINE

       Figure 5.1 shows the materials balance for £-nitroaniline.  It points out
the sources of ^-nitroaniline (production, imports),  the uses of the compound
(consumption categories), and the estimated emissions to air, land, and water
due to each process, when possible.  This figure describes the most recent year
for which data were available:  1978.  The purpose of this chapter is to explain
the assumptions and calculations that yielded the values reported in the materials
balance.
                                     5-1

-------
FIGURE 5.1   MATERIALS BALANCE FOR Q - NITROANILWE (KKG)
SOURCES





Direct
Production






Imports











-



3641
y






(16)

















•





































(361

CONSUMPTIVE
USES


dlamlne













Photo
Antl-fogglng
Agent




NUNUINbUMrilVK umi.iuiiiiimiu ui — 	 -• -
USES END-PRODUCTS INCINERATION i AIR LAND WATER TOTAL


Products




> T 7 69 69 +




Products
	 > 77 71

1111
Cat ov
Products

77 7 7




-------
5.3  DIRECT PRODUCTION OF o-NITROANILINE

5.3.1  Production Process, Producers, and Locations

     o-Nitroaniline was reported to be synthesized by high-pressure ammonolysis
of o-chloronitrobenzene (Hancock, 1975):
               o
                              NIL
175°C,  40 Atm
o
5.3.2  Amounts Produced

       Only Monsanto and duPont were listed as producers  in 1978  (Catalytic, Inc.,
1978).  Producers  in years previous to  1978 are listed in Table 5.1  (end of
chapter).  The amounts of jD-nitroaniline produced  in 1978 by duPont  and Monsanto,
respectively, are  shown in Table  5.2.   These results were reported in Catalytic,
Inc.,  1978, with no information on the  method used to obtain them or an estimate
of  their accuracy.
              TABLE 5.2  PRODUCTION OF o-NITROANILINE, 1978 (kkg)
Producer and Location

E. I. duPont de Nemours
Deepwater, NJ

Monsanto Chem. Co.
Sauget, IL

     SUM
                       Reported Production (% of total)
                            248
                           3393
                           3641
                           (7%)
                          (93%)
     The total production for 1978 was reported to be 3641 kkg, with Monsanto
producing the vast majority of that amount.
                                        5-3

-------
5.3.3  Emissions Due to Production

5.3.3.1  Emission to Air

     An industrial process flow chart was not available for the ammonolysis of
o^chloronitrobenzene, nor were data on emissions or emission factors during
production of o-nitroaniline.  Therefore, it was not possible to reasonably
estimate air emissions due to this process.  To fill this data gap, the follow-
ing information is needed:   1) air monitoring data, especially near the major
production facility in Sauget, Illinois;  2) process information to permit
pinpointing of emission sources;  3) information on waste treatment at Monsanto
(incinerators, scrubbers, etc.).

5.3.3.2  Emissions to Water

     Emissions to water can  occur during synthesis (process water).  Direct data
were not available on o-nitroaniline emissions during this step.  A best judgement
estimate was made.  69 kkg o-nitroaniline were estimated to be released to water
during production in 1978.   This value was obtained by the operation:  (kkg o-
nitroaniline produced) x  (emission factor, kkg/kkg) = kkg emission.

     In the absence of data  on emission factors, we estimated an emission factor
                               _2
for this process to be 1.9 x 10   kkg/kkg.  This value was estimated using the
following steps:  1)  Fed. Reg. (1976) lists proposed rules for effluent limita-
tions guidelines as limiting the 30-day average for o-nitroaniline to 27 kg
COD/kkg product.  2)  This effluent guideline measured in kg COD was converted
to kg o-nitroaniline by assuming that (a) all of the COD was due to o-nitroaniline
and  (b) the o-nitroaniline was quantitatively oxidized to 6 CO- in the COD
measurement.  Therefore,  6 (32) = 192 g. (6 moles) of oxygen was equivalent to
138 g. (1 mole) of o-nitroaniline.  The effluent limitation was expressed as
(27 kg COD/kkg product) x (  j-38 kg product       ) = 19 kg o-nitroaniline released/kkg
     0         r             192 kg oxygen demand         ° -                         &
£-nitroaniline produced.  3)  This value was considered to be the maximum
emission factor for aqueous  discharge of o-nitroaniline by assuming that production
facilities obeyed the effluent guidelines.  The emisssion factor was thus 0.019
kkg/kkg.
                                      5-4

-------
     The uncertainty of this emission factor was estimated to be +50%, -90% based
on the following:  1) It was an overestimate if (as seems likely) less than 100%
of the COD was due to o-nitroaniline.  2) It was an underestimate if the chromic
acid oxidation did not stoichiometrically degrade all of the o-nitroaniline in a
COD measurement.

     Application of this emission factor yielded:  (3641 kkg produced) x (1.9 x
  _2
10   kkg/kkg) = 69 kkg o-nitroaniline generated for release to water during
production in 1978.

5.3.3.3  Emissions Due to Disposal of Solid Residues

     No direct data on emissions nor data on emission factors were available to
permit estimation of emissions due to disposal of solid, o-nitroaniline-containing
residues formed during production.  In order to be able to estimate emissions to
air, land, and water due to this disposal, the following information would be
needed:  1) process engineering information on the sources of residues during
the synthesis process;  2) quantitative analysis of residues produced;  3) rate
of production of residues;  4) information on waste disposal methods at each
plant  (i.e., landfill, incineration, activated sludge treatment, stack gas
scrubbers, etc.).  Since o-nitroaniline is a solid and is only slightly water-
soluble at room temperature, the chance of having solid o-nitroaniline residues
is substantial.

5.4  INDIRECT PRODUCTION

     Although opportunities for indirect production of o-nitroaniline undoubtedly
exist, no information was available in this area.

5.5  IMPORTS OF o-NITROANILINE

5.5.1  Amounts

     Table 5.3 shows available data on imports of o-nitroaniline for the past
five years.
                                     5-5

-------
          TABLE 5.3  IMPORTS OF o-NITROANILINE (kkg)L

          1978      1977      1976      1975      1974

          n.a.      n.a.      16        n.a.       91

      Source:  USITC, Imports ofBenzenold Chemicals and Products,
               n.a. = not available
          A datum was not available for 1978 imports, so the 1976 value
     was used in the  Materials  Balance (Figure 5.1).

5.5.2  Emissions Due to Imports

     Data were not available on emissions due to transport and storage of
imported o-nitroaniline.  Furthermore, the oil spill/risk model described in
section 2.5.2.1 was not considered applicable to a solid compound like £-nitro-
aniline.  Therefore, estimates of emissions must await the availability of the
following information:  1) more complete importation statistics;  2) monitoring
data or a measured emission factor applicable to air, water, or total emissions.

5.6  CONSUMPTION AND USE

5.6.1  Categories of Use

     o-Nitroaniline had two major industrial uses:  1) It was a starting reactant
in the synthesis of o-phenylenediamine; and  2) It was used in the formation of
dyes an dye intermediates.  Table 5.4  (end of chapter) lists companies associated
with each category.  Of the two categories, o-phenylenediamine production was
reported to be predominant (Hancock, 1975) but no percentage breakdown was
given.

5.6.2  Amounts of Use

     No data were available on amounts of o-nitroaniline consumed either in toto
or by each of the major categories of  use.  Exports were estimated (McCaleb, 1979)
to account for 1% of production, or 36 kkg in 1978.  We had no criterion to
evaluate the uncertainty of this value.
                                       5-6

-------
5.6.3  Emissions by Category of Use

     Data on emissions during o-nitroaniline use were not readily available.  In
order to be able to report these emissions, one or more of the following would
be needed:  1)  Previously estimated emissions values from the literature;
2)  Quantitative data on consumption of o-nitroaniline (total or by plant);
3)  Process flow diagrams for consumption steps;  4)  Measured effluent data on
air and water waste streams at each consumption site;  5)  Information on solid
residue handling procedures at each consumption site;  6)  Chemical analyses of
solid residues containing o-nitroaniline;  7)  Chemical analyses of products
synthesized using o-nitroaniline.
                                    5-7

-------
                  TABLE 5.1  PRODUCERS OF o-NITROANILINE BY YEAR
1978
1977
1976
1975
1974
duPont
Deepwater, NJ
Monsanto
Sauget, IL
duPont
Monsanto
(450-4500 kkg)

X2

Salsbury Labs
Leland, NC

GAF Corp.
Rennselaer, NY
(5-450 kkg)

Blackman-Uhler
Chem. Div.
Spartanburg, SC
(5-450 kkg)
Synalloy Corp.
Blackman-Uhler
Chem. Div.
Monsanto
duPont
                                                      Monsanto
Monsanto
      Sources:  Catalytic, Inc., 1978;  USITC, 1976-1978; EPA, 1977

      Manufacturer declined to be identified.
                                        5-8

-------
                               TABLE 5.4   INDUSTRIAL  CONSUMPTION  OF  ORTHO-NITROANILINE
            MANUFACTURING
                 PROCESS

            production of
            oj-phenylene-
            diamine
                                   COMPANY
                                E. I. du Pont de
                                   Nemours & Co.,
                                   Inc.
                                Sherwin Williams
                                   Co.
                                Toms River Chemical
                                   Co.
                              PRODUCTS PRODUCED

                              dyestuffs
                              pharmaceutical products
                              rubber chemicals
                              veterinary products
Ul
i
preparation
of azo and
anthroquinone
dyes
Alliance Chemical
   Corp.
American Color and
    Chemical Corp.
GAP Corp., Chem. Division
Synalloy Corp.,
  Blackman-Uhler
  Chemical Div.
                                                                           dyes  and  dye
                                                                           intermediates
        USITC,  1976-79.
                                                                           photo  anitfogging
                                                                           agents
        TRW,  1973a;  Hancock,  1975;  Snell & Snell,  1962;  Patty,  1963.

-------
                     6.0  meta-NITROANILINE
6.1  PHYSICAL PROPERTIES OF meta-NITROANILINE
     Chemical Formula
W2°2
     Chemical Structure
     Molecular Weight
     Melting Point
     Boiling Point
     Solubility
          Water
          Alcohol
          Ether
          Methanol
     Vapor Pressure
     Density
138.12
114°C
306 °C


1.1  g/liter
  50 g/liter
  56 g/liter
  87 g/liter


1.43 g/cc at 4°C
     The physical properties were extracted from Stecher, 1968, and Weast, 1972.

     Two physical properties of nt-nitroaniline may be useful in estimating the
quantity and medium by which m-nitroaniline may be released.  The slight solubility
of m-nitroaniline in water suggests that only small emissions could be accommodated
dissolved in liquid wastestreams from manufacture and consumption.  The low
vapor pressure of m-nitroaniline suggest that spontaneous sublimation would be
slow.
6.2  MATERIALS BALANCE FOR meta-NITROANILINE
     Figure 6.1 shows the materials balance for in-nitroaniline for the year 1978.
The following text explains the assumptions and calculations.
                                        6-1

-------
EMRE6.1    MATERIALS BALANCE FOR M.-N1TROANILIME (KKG)
                                                                                           ENVIRONMENTAL  RELEASES  (KKG>
, SOURCES |


1
DIRECT
PRODUCTION
OF
META-NITRO-
ANILINE 2

INDIRECT
PRODUCTION
0

IMPORTS
47


49.3
J
0
	 >
47
	 >
k
>-/•
1
CONSUMPTIVE ,.„, ,n
USES AND EXPORTS CONTAMINANTS NON CONSUMPTIVE UACTFQ
* • i .• IKF<^ A1K WAItn WAolto TnTAl
' t \ II USES J I II II \_wn 1 1 T°TAL ,
V
" >

10.3
7 .

7,
? »

7 v
? v
o v


DYES AND
INTERMEDIATES
0 »


CONTAMINANTS
1

SYNTHETIC
SWEETENERS
7 ,

CONTAMINANTS

1
r ' I 1 ?
/%• 0 xvO ^v 0
	 ..,., .y 1 X 10 2.3 ^~> 0 2.4

f '1 ? ?

PHOTOGRAPHIC
ANT I FOGG ING
ARFNTS.
7 y


CONTAMINANTS
1

0-PHENYLENE-
DIAMINE
I .
7 y



CONTAMINANTS

<• u o o o
-..^. ,
r^ ? ? /
,„ 	 v •. .»
^ , y ?
	 	 .^
r '! 1 7
•" ? ?

COCCIDIOSTATIS
1

INTERIOR
PAINT PIGMENTS
7 v

? v

CONTAM I NANTS




CONTAMINANTS
|


EXPORTS
0 .


CONTAMINANTS
r ~ 0 'VQ 0 ~0
. .-V
^7 7 ?
V
" •"' 	 ' '?• ? 7 7
__.,. 	 	 V-
-^ ^ 7 ? 7
	 ^
: r i i ?
	 v
^ ? ? 7

-------
6.3  DIRECT PRODUCTION OF meta-NITROANILINE

6.3.1  Production Process, Producers and Locations

     The literature revealed three methods by which m-nitroaniline may be
manufactured.  E. G. Hancock stated that the normal production process was the
partial reduction of m-dinitrobenzene with sulfides:
               o
                         (reduction)
                      N02
     A second method of production was from m-nitrobenzoic acid, but the chemical
steps were not available from the literature  (Stecher, 1968).  meta-Nitroaniline
is produced from aniline by nitration after acetylation.  The acetyl group is
removed by hydrolysis yielding m-nitroaniline  (Hawley, 1977).  No mention was
made in the literature as to the quantity of m-nitroaniline manufactured by the
respective processes.

     The USITC reports for 1974 through 1978 indicated that there was one producer
of m-nitroaniline for 1974, 1976 and 1977.  The producer was unknown because they
requested not to be identified in the USITC reports.  Further attempts at identifying
the producer have been unsuccessful.

6.3.2  Quantity Produced

     The amount of rj-nitroaniline produced during the years 1974, 1976, and 1977
was not reported in the USITC due to its policy of not revealing production
figures of an individual producer.  However, the quantity produced during these
years had to be greater than 2.3 kkg because companies are required to report
production of products that exceed 2.3 kkg or  $5,000.000.
                                      6-3

-------
     The upper limit on the production of m-nitroaniline was difficult to estimate.
Since only one company reported production, it was probably a small use commodity.
Therefore, it was roughly estimated that no more than 45 kkg were produced.

     Although production was not reported to the USITC during 1975 and 1978,
this did not necessarily indicate that no m-nitroaniline was produced.  It did
suggest that from 0 kkg to 2.3 kkg was produced during these years.

6.3.3  Emissions Due to Direct Production

     No information was available in the literature reviewed nor was it possible
to create a production model on which emission estimates could be formulated.

6.4  INDIRECT PRODUCTION OF meta-MITROANILINE

     No method of indirect production was stated or could be inferred from the
references reviewed.

6.5  IMPORTS OF meta-NITROANILINE

6.5.1  Amounts Imported

                              Statistical
                              Coverage
     Year                     Value	              Quantity kkg
     1978                       76%                         47
     1977                       81%                         15
     1976                       80%                         95
     1975                       94%                         48
     1974                       99%                         86

     These values were calculated based on the USITC Imports of Benzenoid
Chemicals and Products for 1974 through 1978.  Each of these reports contained a
"statistical coverage value" which represented an estimate of the percentage of
the imports that were actually reported.  The values in the table have been
corrected to represent the total imports.  The calculation to arrive at the
                                       6-4

-------
corrected value is shown below:
                ,  ^ ,nn,,   ,     USITC imported quantity x 100%	
 Import compound at 100% value = „„_„,-—.*"  .—-—•*=	*	:	—„
   *       *                     USITC statistical coverage value in %

The corrected import figures did not reflect imports due to air transportation
(personal communication with U.S. Department of Commerce).

6.5.2  Emissions Due to Imports
     The quantity of emissions to air, land, and water of m-nitroaniline was
difficult to assess due to the dearth of information in the literature reviewed.
Releases to air and water would occur during the storage and transportation of
imported m-nitroaniline.  These emissions would be due to spills and damaged
containers.  Losses to the water medium probably made up 80 percent of the loss
and 20 percent was lost to the air medium.  Spills were probably cleaned up by
shoveling the chemical back into the container or hosing the area down.

     Losses to the air were probably in the form of particulate matter.  Air
movements near spills would cause the crystals to become airborne.  In the
absence of any data on emissions during transportation an overall best-judgement
indicated that the loss was insignificant.  This was based on the premise the
m-nitroaniline was shipped in metal 55 gallon drums requiring very little subsequent
transfer or handling of contents.

6.6  CONSUMPTION AND USE OF meta-NITROANILINE

     A review of the literature indicates that the predominant use of m-nitro-
aniline was as a dye intermediate (Hancock, 1975; Hawley, 1977; Strecher, 1968;
and TRW Systems Group,  1973).  m-Nitroaniline has also been used to manufacture
photographic antifogging agents, coccidostatics, interior paint pigments and
synthetic sweeteners (Hawley, 1977; Kirk Othmer, 1968; Snell, 1963; and Snell
and Hilton, 1964).

     There are two areas to examine for m-nitroaniline emissions:  1) direct
emissions during consumptive use and  2) carry-over as impurities in the
manufactured products.
                                         6-5

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6.6.1  Total Consumption

     Data were not available on the breakdown of the consumptive use of
m-nitroaniline.  Therefore, estimates of m-nitroaniline production were made
based on the criteria used by USITC in reporting production and a general
definition of what "small amounts" of production were to industry.  These two
limits were discussed in Section 6.3.2 of this report.

     The major source of m-nitroaniline was imports.

     The total m-nitroaniline available for consumption is presented in Table 6.1.

     It was assumed that the m-nitroaniline produced and imported was consumed
during that calendar year.
       TABLE 6.1  INDUSTRIAL CONSUMPTION OF meta-NITROANILINE (kkg)
     Year
Estimated
Domestic
Production
Low   High
Imports
Total
                                                       Low    High
1978
1977
1976
1975
1974
0
2.3
0
2.3
2.3
2.3
45
2.3
45
45
47
15
95
48
86
47
17.3
95
50.3
47.3
49.3
60
97.3
93
131
6.6.2  Emissions Due to Dye Manufacture

     The predominant consumer of m-nitroaniline was probably the manufacture
of dyes.  The basis for this assumption was the literature reviewed.   Several
references cited the manufacture of dyes as the only use of m-nitroaniline
                                       6-6

-------
(Hancock, 1975; Patty, 1963; Snell, Snell, 1962; and Stecher, 1968).  In the
absence of any data on the consumption by the different endproducts, our best
estimate was that 80 percent of the m-nitroaniline was used in dye manufacture.
The remaining 20 percent was used to manufacture all other products made from
m-nitroaniline.  In the absense of data on the amounts of emissions or emission
factors, an overall best-judgement emission factor for emissions generated
                                                                   _2
during dye synthesis was estimated.  The value estimated was 5 x 10   kkg/kkg.
This emission factor represented the sum of the air and water emisssions.  It
was based on the following considerations:  1) In any chemical synthesizing
process, only the introduction and initial chemical reaction of m-nitroaniline
was significant.  2) The average initial reaction would utilize 90% of the
m-nitroaniline feedstock.  3) Of the remaining 10% of m-nitroaniline; 5% was
reclaimed and recycled and the other 5% was lost to water and air media as
emissions.  Therefore, the emission factor for m-nitroaniline emissions generated
during dye manufacture was calculated as follows: (0.10 fraction not used) x
(0.50 fraction of unused not reclaimed) = 0.05 kkg generated/kkg m-nitroaniline
consumed.

6.6.2.1  Generated Emissions to Air

     Due to lack of data on air emissions or emission factors during dye
manufacture, the estimated factor derived in the preceding section  (5 x 10~  kkg/kkg)
was applied to estimate the generated emissions to air during dye manufacture.
To determine the emissions to air, it was estimated that 95% of emissions of
m-nitroaniline were through the water medium and 5% of the air medium.  The loss
to air would be in the form of particulate matter.  The loss would primarily
occur during the emptying of the drums containing the crystals of m-nitroaniline
into the dye manufacturing vessel.  The calculations for emissions to air are
presented below:
                                                      _2
(49 kkg m-nitroaniline, high estimate use)   x (5 x 10   kkg/kkg used) x
(0.5 fraction to air) = 1.1 x 10   kkg generated for release to air during dye
production in 1978.
The calcualted emission to air did not change significantly when the low estimate
of m-nitroaniline usage for 1978 was used.
                                      6-7

-------
     No data were available on the make up of the 20% of m-nitroaniline production
that was not used in dye manufacture.  Therefore, no attempts at estimating the
emissions of m-nitroaniline to the air, land and water media were made.

     In order to estimate emissions accurately the following data would be
necessary:  1) The percent of the total m-nitroaniline annual production consumed
by each product.  2) Diagrams of the manufacturing processes with explanation on
how these processes work and sources of emissions within the process.  3) The
types, quantities, and compositions of wastes from the manufacturing processes.
4) The waste treatment facilities at each plant and their efficiencies.  5) The
final disposition of the wastes.

6.6.2.2  Generated Emissions to Water

     The approach to estimating emissions generated during dye manufacture was
described in Section 6.6.2.1 (above).  The only value which changed in the
calculation was the percent loss:  From 5% air to 95% water.  The emissions to
the water medium were calculated as follows:
                                                  _2
(49.3 kkg m-nitroaniline, high estimate) x (5 x 10   kkg/kkg consumed) x
(0.95 fraction to water) =2.3 kkg generated for release to water during dye
production in 1978.

6.6.2.3  Emissions Due to Disposal of Solid Wastes
     No data nor emissions factors were available to permit an estimate of
emissions due to solid, m-nitroaniline-containing residues formed during dye
synthesis.  For an accurate estimate of emissions to air, land and water media
as a result of this disposal, the following would be needed:  1) Process engineering
information on the sources of residues during each process utilizing m-nitroaniline;
2) Information on the present contributions of the individual processes to the
total for that dye class:  3) Quantitative analysis of residues produced; quantities
of residue produced;  4) The waste treatment facilities and their efficiency;
5) The disposition of the solid residue (landfill, incineration, etc.).
                                      6-8

-------
6.6.3  Emissions Due to Manufacture of Other Products from m-Nitroaniline

     The consumption of m-nitroaniline for manufacture of other products was
estimated to be 20% of annual production.  Refer to Section 6.6.2 of this
report for the basis of this estimate.

     Other products manufactured from m-nitroaniline included:   photographic
antifogging agents; o-phenylenediamine; coccidiostatics; interior paint pigments;
and synthetic sweeteners (Hawley, 1977, Kirk-Othmer, 1968; and Snell-Hilton,
1967).

6.7  EMISSIONS DUE TO EXPORTS OF meta-NITROANILINE

     An investigation conducted by the Foreign Trade Commission consisting of a
search of the July 1978 invoices revealed no exports of m-nitroaniline.
                                      6-9

-------
                               7.0  para-fllTRQANILINE

7.1  PHYSICAL PROPERTIES OF para-NITROANILINE

     para-Nitroaniline is also known as para-nitraniline and l-amino-4-nitrobenzene.
It is a fine needle yellow powder at room temperature.  (Hawley, 1977).   Its
physical properties are summarized below:
                                                            NH^
                                                          o
Chemical Structure


Chemical Formula                        NO^C-H.NH^

Molecular Weight                        138.13

Melting Point                           146°C

Boiling Point                           332°C

Solubility in:

     cold H20                           0.8 g/1

     warm H20                           22 g/1

     alcohol                            40 g/1

     ether                              33 g/1

Density                                 1.424 g/cc at 4°C

Temp at which vapor pressure = 1 Torr   142.4°C
     The physical properties that were of particular value in estimating
emissions were the solubility in cold water and the vapor pressure.
                                      7-1

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7.2  MATERIALS BALANCE FOR para-NITROANILINE

     Figure 7.1 depicts the materials balance for p_-nitroaniline for the year 1978,
It shows the sources of p_-nitroaniline  (production and imports), the consumptive
uses and exports, and the estimated emissions to air, water, and land due to
each process.

7.3  DIRECT PRODUCTION OF para-NITROANILINE

7.3.1  Production Processes, Producers, and Locations

     Literature indicated five methods  for the synthesis of p_-nitroaniline.
E. G. Hancock (1975) stated that it was manufactured under pressure by the
ammonolysis of p_-chloronitrobenzene.  The production process may be either
batch or continuous (Hahn, 1970, Hawley, 1977 and Snell-Hilton, 1967).
An alternate procedure was by the nitration of acetanilide followed by hydrolysis
(Hancock, 1975; Snell and Hilton, 1967; and Stecher,  1968).

     The other three methods were:   1)  nitration of  aniline and then acetylation;
2)  reaction of p_-dinitrobenzene with alcoholic ammonia; and  3)  acid-catalyzed
addition of hydrazoic acid to carboxylic acids (Hawley,  1977; Snell, Snell,
1962; and Stecher, 1968).  These methods were probably not used to any great
extent in the commercial synthesis of p_-nitroaniline.  The first method mentioned
(ammonolysis) was estimated to produce 80 percent and the second method  (nitration)
20 percent of the annual domestic p_-nitroaniline production.
                                       7-2

-------
      FIGURE 7.1  MATERIALS BALANCE  FOR E-N1TROAN1LINE (KKG)
SOURCES
                              CONSUMPTIVE
                              USES AND EXTORTS
                                                             COHTAHI HANTS
NONCONSUXPTIVE
     USES
                                                                                                                                 ENVIRONMENTAL RELEASES  (kk«)
                                                                                                                       AIR

1

Para-nit roanlllne
Direct
13.000 kka




'ara-nlr roanlline
Indirect
Production Q





laport*
800























•>





*J
>
















13.800
»











104

~\


	 ,














6000



3ooo




000



400




innn



1000









Rubber
Chealcali
1

Dye* «nd
Intern edJ^trs
1


'Caroline
Additive*
!

Fharaiceuttcali
•nd Veterinary
Product"
|


Agricultural
Chealcalt
1


Hlacellanroua
|

Exports
0
1



~0



~0




'V.O



0




~n



t



0






Contaalnanta



Contaminant •



Contanlnanta









Contanlnanta














V in

v



t- u




. . . i,. ,, t. .





+ T

> T

1 t
. \.
' t

' 0
	 : 	 v Q
                                                                                                                                        WATER
                                                                                                                                           117
                                                                                                                                           SOO
                                                                                                                                           100
                                                                                                                                             0
                                                                                                                                           ~0


                                                                                                                                             t
                                                                                                                                      e.) x 10'
                                                                                                                                             ,-3
SOLID
WASTES
LAND   I
                                                                                                                                                                          TOTAL
                                                                                                                                                           ~ 0
                                                                                                                                                                           117.13
                                                                                                                                                                           360
                                                                                                                                                                          ~0
                                                                                108
                                                                                  0
                                                                                                                                                              0     8.504  X 10



                                                                                                                                                              J               t


                                                                                                                                                              t               T
                                                                                  ,-J

-------
7.3.2  Amounts Produced

     Data on the production of p_-nitroaniline were difficult to obtain.  There
were four producers of £-nitroaniline in 1978.  The production for only two of
these companines was reported, and it was 6534 kkg for 1978 (Table 7.1).  No
production figures were available for the other two.  The actual production was
probably about twice this value or 13,000 kkg.  The two companies for which no
production was available were estimated to be similar in size to those that did
supply data.  Therefore, the estimated value represented twice the known value.

     Refer to Table 7.1 for a list of the producers, and quantities produced
where known from 1974 to 1978.

          TABLE 7.1  PRODUCERS OF para-NITROANILINE BY YEAR,
                 INCLUDING PRODUCTION WHERE AVAILABLE1

Compound       1978           1977           1976           1975           1974
p_-Nitro-
aniline        duPont         duPont         Monsanto       American       American
                Deepwater, NJ                                Color &        Color &
                                                             Chemical       Chemical
               American       Monsanto
                Color &       4500-23,000 kkg
                Chemical                                    duPont         duPont
                Lockhaven, PA
                1825 kkg      Salsbury Labs                 Monsanto       Monsanto
                produced      Leland NC
               Monsanto       Process Div.,
                Sauget, II    UOP Inc.
                4709 kkg      Shreveport, LA
                produced
               Signal Companies
                Shreveport, La

      The manufacturing process used was the aramonolysis of ^-nitrochlorobenzene.

7.3.3  Emissions Due to Direct Production

     The lack of data on production, processes, manufacturing flow diagrams, and
emission data and factors prevented calculation of precise estimates.  However,
in an attempt to provide some guidance, rough estimates were calculated for air
and water emissions.

                                        7-4

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7.3.3.1  Generated Emissions to Air

     Emission figures of pj-nitroaniline to air during production were the sum
of emissions due to:  production, product storage, and product transport.  We
estimated the amounts of emissions generated to air by the following equation:
(estimated kkg produced, stored and transported) x (emission factor in percent
of annual production) = kkg released due to production, storage or transport.
                                                                            _c
The estimated emissions to air are calculated below:   13,000 kkg/yr x 1 x 10   =
1.3 x 10~  kkg loss of £-nitroaniline for 1978.  The loss might be in the form
of particulate matter due to the small size of the ^-nitroaniline crystals.
                                  _3
     The emission factor of 1 x 10   percent represented our best estimate of
the likely loss to the air by a powdery substance, during production, storage
and transport in closed containers.

7.3.3.2  Generated Emissions to Water

     Emission figures of ^-nitroaniline to water during production, product
storage, and product transport were not readily available.  The primary loss was
estimated to be due to the production liquid waste stream, with minor amounts
occurring due to spillage and container damage.

     The effluent limitation guidelines for £-nitroaniline were used to estimate
the loss to water.  The proposed effluent limitation for £-nitroaniline  (30 day
average) is 13 kg COD/kkg of product.  (Environmental Protection Agency, Organic
Chemicals Manufacturing Paint Source Category, 1976.)  The COD value was converted
to kg £-nitroaniline by making the following assumptions;  1)  All of the COD
was due to p_-nitroaniline.  2)  The ^-nitroaniline was quantitatively oxidized
to 6 CO. in the COD measurement.  The resulting equivalence of oxygen was
6(32) = 192 g oxygen and 138 g of £-nitroaniline.  With an effluent limitation
of 9 kg £j-nitroaniline/kkg product (0.9% release), the maximum allowable emission
factor would be calculated as:  (13,000 kkg annual production) x (9 kg/kkg release
factor based on COD) = 117 kkg of p_-nitroaniline lost to the water medium during
production, storage and transport.
                                        7-5

-------
     The uncertainties of the estimate were:  1)  it would be an overestimate
if less than 100% of the COD were due to £-nitroaniline;  2)  it would be
understated if the chromic acid oxidation did not completely degrade all of
the nitroaniline during COD measurements;  3)  it assumed compliance with the
guidelines by producers.  The emission figure's uncertainty was estimated at
+50%, -90%.

     The ^-nitroaniline lost to the liquid waste stream of the manufacturing
plant was probably treated by a central treatment facility.  In the worst
instance, it would be treated only by a gross filtering or settlement treatment
procedure removing at most 40% of the chemical waste.  The liquid waste stream
would then be released to a municipal sewage system.

     Table 7.2 summarizes the estimated emissions (calculated as described above)
due to production for the years 1974-1978.

        TABLE 7.2  EMISSIONS OF £-NITROANILINE DURING SYNTHESIS

                                   EMISSIONS (kkg)
YEAR                          AIR                 WATER

1978                     13.0 x 10"2              117
1977                      9.8 x 10~2               85
1976                      4.7 x 10"2               42
1975                     11.2 x 10~2              101
1974                     11.2 x 10~2              101
      The production estimates upon which the emissions estimates were based
      are tabulated and footnoted in Table 7.1.
                                         7-6

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7.3.3.3  Disposal of Solid Residue

     The lack of available data and emission factors prevented estimates of solid
residue disposal.  The information needed for an estimate on solid waste disposal
would be:  the quantity, type, and character of wastes generated during manufacture
and waste treatment, and the methods used by each ^-nitroaniline-producing plant.

7.4  INDIRECT PRODUCTION OF para-NITROANILINE

     Analysis of the accessible literature and chemical synthesis possibilities
did not indicate any indirect production method.

7.5  IMPORTS OF para-NITROANILINE

7.5.1  Amounts of para^Nitroanjline Imported

YEAR                STATISTICAL COVERAGE VALUE         QUANTITY, kkg

1978                     76%                              795
1977                     81%                             1620
1976                     80%                              984
1975                     94%                             1310
1974                     99%                              857

     USITC Imports of Benzenoid Chemicals and Products for 1974 through 1978
was the source used to calculate the values above.  By applying the statistical
coverage value to the reported USITC value, the corrected import value was
obtained.

     Import Compound at _ USITC imported quantity x 100%
     100% Value         ~ USITC statistical coverage value in %

     The import values in the table above do not reflect air transported imports
(Personal Communication with U.S. Department of Commerce).
                                         7-7

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7.5.2  Emission Due to Imports

     Data on emissions and emission factors were not available for the determin-
ation of emissions to air, water and land media.

     Emissions to air and water could occur during the storage and transportation
of imported £j-nitroaniline.  These releases would be due to spills and leaks
from damaged containers.  Of the total loss, 80 percent was estimated to be lost
to water and 20 percent lost to air.  Spills would probably be cleaned up by
shoveling the compound back into the container and hosing the area down.
Emissions to the air would probably be in the form of particulate matter because
p_-nitroaniline is a crystalline solid.

     £-Nitroaniline was probably imported in 55 gallon drums or similar container
which would limit the amount of emissions.  In the absence of any data on spills
or container damage, it was estimated that the emissions from imports would be
insignificant.

7.6  CONSUMPTION AND USE OF p_-NITROANILINE

     Current data on the consumption and uses of ^-nitroaniline were not available.
Therefore, the following assumptions are made, in an effort to provide estimates
on quantities consumed by consumption categories:  1)  In lieu of more recent
figures, the consumption apportionment for 1969 was applied to 1974 through 1978
total j^-nitroaniline domestic production and imports:  rubber chemicals, 40%;
dyes and intermediates, 20%; gasoline additives, 20%; Pharmaceuticals and
veterinary, 7%; agricultural chemicals, 3%; and miscellaneous, 10% (TRW Systems
Group, 1973a).  2)  There were no significant consumption changes among the
product groups during this time period.  3)  All of the j^-nitroaniline produced
and imported during a given calendar year was used during that year.

7.6.1  Total Consumption

     Complete consumption and use figures were not available for the period
1974 through 1978.  In order for estimates to be calculated, the following
assumptions were necessary:  1)  Consumption = production for the years under
consideration.  2)  The production of jv-nitroaniline has remained constant from
                                        7-8

-------
1974 through 1978.  3)  The Monsanto production for 1978 of 4709 kkg also
represents the estimated amount produced by duPont.  4)  The American Color and
Chemical Company production for 1978 of 1825 kkg also represents the estimated
amount produced by Signal Companies.  The estimated domestic production for 1978
is 13,000 kkg + 795 kkg imports = 13,795 kkg the total available £-nitroaniline
for consumption.  Refer to Table 7.3 for consumption estimates 1974 through 1978.

7.6.2  Categories of Use

     The categories of £_-nitroaniline use, consuming companies, and amounts
used for the past five years are presented in Table 7.4.  The data were
obtained from the footnoted references; we had no criterion on which to base
an uncertainty estimate.

     The rubber chemicals will probably increase the market share of jj_-nitro-
aniline, while dyes and dye intermediates and agricultural chemicals demand
will steadily decrease.  A detailed listing of the production processes,
derivatives and uses are cited in Appendix B.

7.6.3  Emissions by Category of Use

7.6.3.1  Emissions Due to Rubber Chemicals

     The estimate of emissions of j^-nitroaniline from the production of rubber
chemicals was based on the following assumptions:  1)  para-Phenylenediamine was
the feedstock for all the rubber chemicals.  2)  The yield of jj-phenylenediamine
from £-nitroaniline was 90%.  3)  para-Nitroaniline synthesis of para-phenylene-
diamine was a single step process.  4)  para-Phenylenediamine contained no
nitroaniline as impurity.  5)  The 10% difference in actual and theoretical
yield represented the ^-nitroaniline lost to the environment.  6)  Of the 10%
lost to the environment, 90% was emitted to the water and 10% was emitted to
the air.  The emissions to air and water were calculated to be:

(6000 kkg, 1978 ^-nitroaniline used to manufacture j>-phenylenediamine) x (0.10 loss
due to production of ^-phenylenediamine) x (0.90 loss to the water) = 500 kkg lost
to the water media during 1978.  (6000 kkg, 1978 p_-nitroaniline used to manu-
facture £-phenylenediamine) x (0.10 loss due to production of £-phenylenediamine)
x (0.10 loss to air) = 60 kkg, lost to the air media during 1978.
                                         7-9

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TABLE 7.3  INDUSTRIAL CONSUMPTION OF PARA-NITROANILINE (kkg)
Year
1978
1977
1976
1975
1974




Estimated
Domestic
Production Imports
13.0001
9.4002
4.7003
H.,0004
ll.OOO4
Calculations :
2
Calculations :
Calculations:
4
Calculations
795
1620
984
1310
857
Producer
duPont
Monsanto
American Color
and Chemical
Signal Companies
Producer
duPont
Monsanto
Producer
Monsanto
Producer
Total
13,795
11,020
5,684
12,310
11,857
Quantity kkg
4709 (estimated)
4709
1825
1825 (estimated)
13,068
Quantity kkg
4709 (estimated)
4709
9418
Quantity kkg
4709
Quantity kkg
              American Color
                and Chemical
              duPont
              Monsanto
  1825
  '4709 (estimated)
  4709
11,243
                          7-10

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                       TABLE 7.4  CATEGORIES AND AMOUNTS OF para-NITROANILINE CONSUMPTION

                                        1974-1978 (kkg/year)
Manufacturing
Process	

Several
Different
Compounds
% of Para-
Nitroaniline
Consumed
   40
Several
Different
Compounds
   20
Company

(No Users
  Cited)
               Products Produced
               rubber chemicals
               dyes and dye
               intermediates
Allied
 Chemical
 Corp.
American Color
 & Chemical Corp.
Atlantic Chemical
 Corp.
E.I. duPont
 de Nemours & Co., Inc.
Fabricolor Manu-
 facturing Corp.
GAF Corp.
Harshaw Chemical
 Co., Div. of
 Kewanee Oil Co.
Mobay Chemical
 Corp.
Southern Dyestuff
 Co.
Year


1978

1977

1976

1975

1974

1978

1977

1976

1975

1974
Amount Used


  6000

  4000

  2000

  5000

  5000

  3000

  2000

  1000

  3000

  2000

-------
Manufacturing
                 TABLE  7.4  CATEGORIES AND AMOUNTS OF ja_ra-flITROANILINE  CONSUMPTION

                                              (continued)
% of Para-
Nitroaniline
Process Consumed
Several 20
Different
Compounds



Several 7
•jj Different
•- Compounds



Several 3
Different
Compounds



Company Products Produced Year
(No Users agricultural chemicals 1978
Cited)
1977
1976
1975
1974
(No Users gasoline additives 1978
Cited)
1977
1976
1975
1974
(No Users Pharmaceuticals and 1978
Cited) veterinary products
1977
1976
1975
1974
Amount Used
3000
2000
1000
3000
2000
1000
1000
400
1000
1000
400
300
200
400
400

-------
                        TABLE 7.4  CATEGORIES AND AMOUNTS OF para-NITROANILINE CONSUMPTION

                                               (continued)
       Manufacturing
       Process	

       Several
       Different
       Compounds
% of Para-
Nitroaniline
Consumed

   10
Company Products Produced
(No Users miscellaneous
Cited)



Year
1978
1977
1976
1975
1974
Amount Used
1000
1000
600
1000
1000
I
I—•
OJ
             Sources:  USITC, 1976-79; TRW, 1973a.

-------
     The 500 kkg was considered generated emissions instead of actual emissions,
because the aqueous waste stream would be at least primary-treated before release
to environmental waters.

     The quantity of solid waste generated from the manufacture of rubber
chemicals was unknown.

     Accurate estimates of emissions can be calculated only with the following
knowledge:  1)  production processes and descriptions of the processes for each
product;  2)  emissions data or factors from manufacturing plants;  3)  accurate
production figures;  4)  the types, character, and amounts of waste streams
generated;  5)  the types, efficiency and final disposition of waste treatment.

7.6.3.2  Emissions Due to Dyes and Dye Intermediates

     Data were not available on air and water emissions or emission factors during
dye synthesis.  Estimates were calculated based on the following considerations:
1)  The step that introduces £_-nitroaniline into the multi-step process was
the only step considered.  2)  The yield was 90%, based on general engineering
and economic considerations.  3)  Of the remaining 10% of £-nitroaniline, 5% was
reclaimed and recycled and the other 5% was lost to water and air media as
emissions.  Therefore, the emissions factor for £j-nitroaniline emissions generated
during dye manufacturing was  calculated as follows:  (0.10 fraction not used) x
(0.05 fraction of unused not reclaimed) = 0.05 kkg generated/kkg £-nitroaniline
consumed.

7.6.3.2.1  Generated Emissions to Air

     In the absence of data on air emissions or emission factors during dye
                                                                         -2
manufacture, the emission factor derived in the preceding section (5 x 10   kkg)
was applied to determine the emissions to air during dye manufacture.  It was
estimated that 95% of the emissions of _p_-nitroaniline were to the water medium
and 5% to the air medium.  The loss to air would be mostly in the form of
particulate matter and would occur during the emptying of drums into the dye
reaction vessel.  The calculations for emissions to air are presented below:
                                                          _2
     (3000 kkg jv-nitroaniline used to make dyes) x (5 x 10   kkg/kkg used) x
     (.05 fraction to air) = 8 kkg generated for release to air during dye
     production in 1978.

                                       7-14

-------
7.6.3.2.2  Generated Emissions to Water

     The approach to estimating emissions generated during dye manufacture was
described in section 7.6.3.2.1 (above).  The only value which changed in the
calculation was the percent loss to water: 95%.  The emissions to the water
                                                                       _2
medium were calculated as follows:  (3000 kkg £-nitroaniline) x (5 x 10   kkg/kkg
consumed) x (0.95 fraction to water) = 100 kkg generated for release to water
during dye production in 1978.

7.6.3.2.3  Emissions Due to Disposal of Solid Wastes

     No data nor emissions factors were available to permit an estimate of
emissions due to solid, jv-nitroaniline containing residues formed during dye
synthesis.  For an accurate estimate of emissions to air, land and water media
as a result of this disposal, the following is needed:  1)  Process engineering
information on the sources of residues during each process utilizing m-nitro-
aniline;  2)  Information on the percent contributions of the individual
processes to the total for that dye class;  3)  Quantitative analysis of residues
produced; quantities of residue produced;  A)  The waste treatment facilities
and their efficiency;  5)  The disposition of the solid residue .(landfill,
incineration, etc.).

7.6.3.3  Emissions Due to Agricultural Chemicals

     No data on emissions or emission factors were readily obtainable.  Refer
to section 7.6.3.7 for further remarks.

7.6.3.4  Emissions Due to Gasoline Additives

     No data on emissions or emission factors were readily obtainable.  Refer
to section 7.6.3.7 for further remarks.

7.6.3.5  Emissions Due to Pharmaceuticals and Veterinary Products

     In the absence of data on emissions and emission factors no estimates were
made.  Refer to section 7.6.3.7 for further remarks.
                                        7-15

-------
7.6.3.6  Emissions Due to Miscellaneous Uses

     In the absence of data on emissions and emission factors no estimates were
made.  Refer to section 7.6.3.7 for further remarks.

7.6.3.7  Summary of £-Nitroaniline Emissions

     Refer to Table 7.5 for a summary of the emissions during manufacture of  the
products from £_-nitroaniline.

     Emissions for those products manufactured from £-nitroaniline could be
calculated if the following data were available:   1)  Consumption data on
p_-nitroaniline for each of the products.  2)  The  production flow diagram with
explanation of each of the processes and product yields.  3)  Data on the types,
character, and quantity of waste streams.  4)  The type and efficiency of the
waste treatment facilities.

7.7  EMISSIONS DUE TO EXPORTS OF para-NITROANILINE

     An investigation conducted by the Foreign Trade Commission consisting of
a search of the July 1978 invoices revealed no exports of £.-nitroaniline.
                                        7-16

-------
                           TABLE 7.5  para-NITROANILINE EMISSIONS GENERATED DURING ITS USE
I
(—•
-~l
Product 1978
Manufactured
from para-nitro- Emissions kkg
aniline by
category air water
Rubber
Chemicals 60 500
Dyes and Dye
Intermediates 8 100
Agricultural
Chemicals
Gasoline
Additives
Pharmaceuticals
and Veterinary
Products
Miscellaneous
1977 1976 1975 1974

Emissions kkg Emissions kkg Emissions kkg Emissions kkg
air water air water air water air water

40 400 20 200 50 500 50 400
6 100 3 50 6 100 6 100






           TOTAL
68
600
46
500
23
250
56
600
56
500

-------
                          8.0  OTHER NITROANILINES

     This materials balance also reported readily available information on
sixteen nitroanilines in addition to the three mononitroanilines  considered
separately in Chapters 5, 6, and 7.   For the purposes of  the present  chapter,
a nitroaniline was defined as any aniline containing a nitro group, whether
or not a halogen was present in addition.  The haloanilines are considered in
Chapter 9.

8.1  PROPERTIES

     Table 8.1 summarizes the physical properties of the  nitroanilines being
considered.  Neither data on vapor pressures nor quantitative data on solu-
bilities were available; qualitative characterizations of solubility  are  pre-
sented only as a general guideline.   These compounds are  solids at room temp-
erature and exhibit almost no solubility in cold water.

8.2  MATERIALS BALANCE FOR NITROANILINES

     In view of the lack of data available on the nitroanilines of interest
here, neither individual nor a composite materials  balance diagram was
constructed.

8.3  PRODUCTION OF OTHER NITROANILINF.S

8.3.1  Producers and Locations

     Figure 8.1 shows the locations  and names of the producers of nitroanilines
considered in this chapter.  The producers are located in the eastern half of
the country, mostly along the east coast and gulf coast.

     Table 8.2 (end of chapter) lists producers for the past five years.  In
1974 and 1975, capacity figures were presented for  three  compounds, but not by
individual producer.  These total capacities figures are  also presented in
Table 8.2.
                                      8-1

-------
           TABLE 8.1  PHYSICAL PROPERTIES OF NITROANILINES
CLASS
COMPOUND
M.P.
B.P.
SOLUBILITY IN
Dinitro-
 anilines

Chloronitro-
 anilines
BromonitTO-
 anilines

Bromochloro-
 nitroaniline
2,4-dinitro-
2,6-dinitro-

4-chloro-2-nitro-
2-chloro-4-nitro-
4-chloro-3-nitro-
2-chloro-6-nitro-
3-chloro-4-nitro—
5-chloro-2-nitro-
3-ehloro-5-nitro-
2-chloro-5-nitro-
4-chloro-2,6-din±tro-
3-ehloro-2,6-d±nitro-
2,6-dichloro-4-nitro-

2,6-dibromo-4-nitro-
2-bromo-4,6-dinitro-

2-bromo-6-chloro-
4-nitro
188°
141-142°

116.3°
107°
95-97°
76°
156-157°
126.5°
133-134°
121°
147°
112°
207°
153-154°
               insol
               insol

               insol
               slight
               partial
                                                                      sol (hot)
                                                                      sol (hot)
               slight
      Sources:  Hawley, 1977; Weast, 1977-78.
                                        8-2

-------
                          FIGURE 8.1  LOCATIONS OF NITKOAN1LINE PRODUCERS, 1978
                                            2,6-dtbromo-
                                            4-nltro-       o-nitro-
                                                           p-nitro-
                                                  6-dlchluro-
                                                                                                      dlnltro-,
                                                                                                      omo-6-chloro
                                                                                                  4-nltro-.
                                                                                                  2-bromo-4,6-
                                                                                                        dinitro-,
                                                                                                   ,6-dibromo-
                                                                                                    4-nitro-

                                                                                                   -bromo-
                                                                                                 _4,6-dtnitro-
                                                                                                 I"2-bromo-4»6-dl-
                                                                                                         nitro-,
                                                                                                  2,6-dibromo-A-
                                                                                                         nitro-,
                                                                                                  2,4-dinltro-
                                                                                                          nitro-
                                                                                               --. p-nltro-
COMPOUND

2,4-dlnltroaniIlne


2,6-dibromo-A-nItroanllIne



2,6-dichloro-4-alcroanlline

2-chloro-4,6-dlnitroanlllne

2-chloro-4-nitroanillne

4-chloTO-2-nltroanillne

2-bromo-6-chloro-4-nitroanllme

2-bromo-4,6-dlnitroaniHne
    LIST OF PRODUCERS

        PRODUCER

American Hoechat
Martlji-Marietta

American Hoechst
Martin-Marietta
Salsbury Labs

Upjohn Company

BASF Wyandotte

Allegheny Ludlam Industries

Mobay Corporation

American Hoechst

American Hoechst
Martin-Marietta
Toms River Chemical Company
    LOCATION

Coventry, RI
Sodyeco, NC

Coventry, RI
Sodyeco, NC
Charles City, IA

North Haven, CT

Rensselaer, NY

Huntington, WV

Bushy Park, SC

Coventry, RI

Coventry, RI
Sodyeco, NC
Toms River, NJ
                                                    8-3

-------
8.3.2  Amounts Produced

     Data were not available on current production of any of the nitroanilines
considered here.  These data are needed for any useful calculation of emissions
due to production.

8.4  IMPORTS OF NITROANILINES

8.4.1  Amounts

     Table 8.3 shows the data available on imports of nitroanilines.  It was
not known what fraction of domestic production these values represent.

8.4.2  Emissions Due to Imports

     Data were not available on either emission amounts or emission factors
attributable to nitroaniline imports.  Furthermore, the oil spill/risk model
described in Section 2.5.2.1 was not considered applicable to solid compounds
like nitroanilines.  Therefore, estimates of emissions must await the avail-
ability of the following information:  1.)  more complete importation statistics;
2)  monitoring data or 
-------
                                   TABLE 8.2  PRODUCERS OF NITROANILINES,  1974-1978
                                                                                   1
        Compound

        2,4-dinitro-
          aniline
                    1978

                  American Hoechst
                  Coventry, RI

                  Martin-Marietta
                  Sodyeco, NC
  1977

American Hoechst
Coventry, RI

Martin-Marietta
Sodyeco, NC

Chemtronics, Inc.
Swannanoa, NC
(^0.5 kkg)
1976
1975
  1974

Amer. Color
and Chem.

Amer. Hoechst

Martin-Marietta

Toms River Chem Co.
Toms River, NJ

Total Capacities =
262 kkg/yr
00
(Jl
2,6-dibromo-      American Hoechst
  4-nitroaniline
                  Martin-Marietta

                  Salsbury Labs
                  Charles City, IA
American Hoechst

Martin-Marietta

Salsbury Labs
                  American Hoechst

                  Martin-Marietta

                  Salsbury Labs

                  Total Capacities
                  20 kkg/yr
        2,6-dichloro-     Upjohn Co.
          4-nitroaniline  North Haven, CT
                                      Upjohn Co.

                                      Carroll Prod.
                                      Wood River Jet.,

                                      Drake Chem.
                                      Lockhaven, PA
                                        Upj ohn Co.
        2-chloro-4,6-     BASF Wyandotte
          dinitroaniline  Rensselaer,  NY

-------
                             TABLE  8.2   PRODUCERS  OF  NITROANILINES,  1974-1978   (continued)
        Compound

        2-chloro-4-
         nitroaniline
  1978

Allegheny Ludlam
  Industries
Hun ting ton, V7V
  1977

duPont Co.
Deepwater, NJ
  1976
  1975
                    duPont Co.
  1974
                     duPont Co.
00
       4-chloro-2-
         nitroaniline
Mobay Corp.
Bushy Park, SC
       2-bromo-6-         American  Hoechst
         chloro-4-nitro-
         aniline
Amer.  Cyanamid
Bound Brook, NJ
(5-45 kkg)

G.F. Smith Chem.
Columbus, OH

duPont Co.
(45-450 kkg)

Carroll Prod.
                    duPont Co.
                                                            American Hoechst

                                                            duPont
                     duPont
                                                             American Color
                                                               and Chem.
       2-bromo-4,6-
         dinitro-
         aniline
American Hoechst

Martin-Marietta

Toms River Chem.
  Co.
American Hoechst

Martin-Marietta

Toms River Chem.
  Co.

GAF Corp.
Rensselaer, NY

ICI Americas
Dighton, MA
American Color
  and Chem.

American Hoechst

Martin-Marietta
Amer. Color
  and Chem.

American Hoechst

Martin-Marietta

Terns River Chem.
  Co.
Amer Color
  and Chem.

American Hoechst

Martin-Marietta

Toms River Chem
  Co.

Total Capacities
932 kkg/yr

-------
                             TABLE 8.2  PRODUCERS OF NITROANILINES, 1974-19781 (continued)
        Compound

        4-chloro-3-
          nitroaniline
1978
  1977

Tennessee Eastman
Kingsport, TN
(45-450 kkg)
1976
1975
1974
        4-chloro-2,6-
          dinitroaniline
                  Kodak Park Div.
                  Rochester,  NY
        2-chloro-5-
          nitroaniline
                  Tennessee Eastman
                  Kingsport, TN
                  (45-450 kkg)
00
        1.  Source:  USITC, 1976-1979; EPA,  1977

-------
                                    TABLE 8.3  IMPORTS OF NITROANILINE COMPOUNDS

                                              1974 to 1978 (kkg/year)1
00
fco
1978
100
230
—
—
—
10
Commission
1977
170
270
5
50
1
—
1976
170
180
30
—
0.
—
(1974-1978).
3 2
J 1975Z
54
147
2
—
8 2
.
Imports of
1974
270
160
0.7
—
5
40
Benzenoid Chemicals and Products.
        Compound

        2,4-dinitroaniline

        2-chloro-4-nitroaniline

        2-chloro-5-nitroaniline

        4-chloro-2-nitroaniline

        4-chloro-3-nitroanlline

        2-bromo-2,6-dinitroaniline
         import figures do not reflect any imports from air transportation.  See footnote 3.

         Those places in the table where dashes occur indicate that no imports were reported for the compound during
         that year.

         The USITC Imports of Benzenoid Chemicals and Products and tables for 1974, 75, 76, 77, and 78 do not reflect the
         entire import amount.  Each report states a "statistical coverage":  the estimated fraction of the total imports
         that was actually reported.  The statistical coverage values used for the compounds in this table were the ones
         that applied to the category, "intermediates."

                                                                    Statistical Coverage
                                                Year                	Value	

                                                1978                    76 percent
                                                1977                    81 percent
                                                1976                    80 percent
                                                1975                    94 percent
                                                1974                    99 percent

-------
        Footnotes to Table 8.3 continued.


         The values in the table have been corrected for less-than-total reporting using the statistical coverage
         value.   This was attained by applying the following formula to each value in the table:


                  Import Compound at _ USITC Reported Import Quantity x 100%
                  100% Value           USITC Statistical Govefage Value (%)

        2
         The import figures for 1975 were not readily available and attempts to obtain these figures were unsuccessful.

        3
         Personal communications between Ron Burger, JR-B Associates, Inc.,  McLean, Virginia, and  Mr. Magnusson,
         Office of Rubber and Chemicals, U.S. Department of Commerce.
00
I

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                       9.0  CHLORO- AND BROMOANILINES
 9.1  PHYSICAL PROPERTIES


     The physical properties of the chloro- and bromoanilines to be reviewed

 in this chapter are shown in Table 9.1.  Quantitative solubility data were

 unavailable; qualitative characterizations are presented as a general guideline.
        TABLE  9.1  PHYSICAL PROPERTIES OF CHLORO- AND BROMOANILINES
                                                                   1
CLASS
Monochloro-
ani lines
Dichloro-
ani lines
COMPOUND
o-chloro
ra-chloro
p-chloro-
2,3-dichloro-
2,4-dichloro-
MELTING
POINT
-2.3°
-10.6°
69.5°

BOILING
POINT
208-210°
228-231°
229-233°

SOLUBILITY
IN H20
insol
insol
sol (hot)

TEMPERATURE AT
V.P. of 1 Torr
46.3°C
63.5°C
59.3°C



Trichloro-
 anilines

Tetrachloro-
 anilines
Pentachloro-
  anilines

Monobromo-
 anilines

Tribromo-
  anilines
 2,5-dichloro-
 3,4-dichloro-
 3,5-dichloro-

 2,4,6-trichloro
                                   47-50°
                                   68-72°
78.5'
2,3,4,5-tetrachloro- 118-120'
2,3,4,6-tetrachloro-
2,3,5,6-tetrachloro- 108°
2,3,4,5,6-penta-
       chloro-

 p-bromo-
 2,4,6-tribromo-
232°

66.4°


122°
          251-252°  slight
          272°      slight
262e
300'
insol
                                                       insol
          insol
insol
134°C
      Sources:  Hawley, 1977; Weast, 1977-78.


 9.2  MATERIALS BALANCE FOR CHLORO- AND BROMOANILINES

     In view of the lack of information available on the chloro- and bromo-

 anilines of interest, neither individual materials balance diagrams nor a
 composite diagram was constructed.
                                      9-1

-------
9.3  DIRECT PRODUCTION OF CHLORO- AND BROMOANILINES

9.3.1  Production Processes, Producers, and Locations

     Figure 9.1 collects the available data on the producers of chloro- and bromo-
anilines, their locations, and the organic synthetic reactions used.

9.3.2  Amounts Produced

     No quantitative data were available on amounts of chloro- or bromoanilines
produced.  This information may be available from the following sources:
1)  Chemical Marketing Reporter or other trade periodicals;  2)  By a complete
analysis, starting with amounts of end-products (e.g., specific dyes) utilizing
a particular haloaniline and working backwards to account for all consumption by
either importation or domestic production.

9.3.3  Emissions Due to Direct Production

     In the absence of production data, it was not possible to calculate useful
emissions values due to production.

9.4  INDIRECT PRODUCTION

9.4.1  Chlorination of Waste Anilines

     Chlorination is sometimes applied to waste stream in order to disinfect.  It
has long been known that Cl- reacts with activated aromatic rings to produce chloro-
aromatics.  The classic example is the Chlorination of phenol (Morris, 1975) to
produce mono-, di-, and trichlorophenols.  It is quite possible that a similar
reaction would take place on aniline, which is also quite susceptible to electro-
philic attack (note, however, that nitroanilines would be deactivated and would
probably not chlorinate).  We suggest that this might be a mechanism for production
of chloroanilines from aniline in waste streams.  The physical result could be
settling out of less-soluble chloroanilines.  Additional research is needed in
this area to evaluate the contribution of this reaction to the overall aniline
materials balance, and the relative toxicities of aniline and chloroanilines.
                                        9-2

-------
                                   FIGURE  9.1  CHLORO- AND BROMOANILDTE PRODUCTION
                                                                               2,4,6-trichloro-'(
                                                                   p-chloro-,                    ^
                                                                   3,4-dichloro-,
                                                                   o-chloro-
                                                                                                                3,4-dichloro-
                                                                                                                tn-chloro-,
                                                                                                                p-chloro-,
                                                                                                                3,4-dichloro-
                                             PRODUCERS, LOCATIONS, CHEMISTRY
COMPOUND
o-chloroaniline
I?
SYNTHESIS REACTION
^r° co , JC>
1978
duPont
Deep water, NJ
Monsanto
Luling, LA
1977
Upjohn Co,
North Havi
Bofors Lai
Inc.
                                                                                     1976
                                                                                                     1975
                                                                               duPont
                                                                             T
                                                                             y,


                                                                 (45-450  kkg)
                                                                                                duPont
                                                                  1974

                                                             duPont

                                                             Monsanto
m-chloroaniline
£-chloroaniline
duPont
duPont
Monsanto
Napp Chen.
Lodi, NJ
(0.5-5 kkg)
duPont
Monsanto
(45-450 kkg)
duPont
duPont
duPont
Monsanto
duPont
duPont
Monsanto
duPont
GAF Corp.
Linden, NJ
duPont
Monsanto
2,5-dlchloroaniline
3,4-dlchloroaniline
                duPont         n.E
                Carroll Prod.
                Hood Riv. Jet.
                  RI
                Drake Chem
                Lock Haven, PA
Blue Spruce Co. Eagle Rlv.
Bound Brook SJ    Chem.,
duPont          W. Helena, AR
Monsanto        Monsanto
                (45-450 kkg)
                duPont
                                                                                                duPont

-------
                                             PRODUCERS, LOCATIONS, CHEMISTRY
COMPOUND
                          SYNTHESIS REACTION
                                                     1978
                     1977
1976
^,1,6-Crichloroantline    n.a.
Plastifax, Inc.  Tennessee
                                                Gulfport, MI
                  Eastman
                (45-450 kkg)
                Columbia Org.
                  Chem.
                «0.5 kkg)
                Upjohn Co.
                North Haven CT
                Fike Chemicals
                Nltro, WV
                Plastifax, Inc.
                Carroll Prod,
                Chem. Systems
                  Dlv.
                San Jose, CA
                (5-450 kkg)
                Drake Chem.
     1975

duPont
Eagle River
  Chem. Co.
Helena, AR
Monsanto
                                                                                                                  1974
p_-br oman 11 Ine
                          n.a.
Aidrich Chem.    Eastman        Eastman
Milwaukee, WI      Kodak          Kodak
                Rochester, NY
           Eastman
             Kodak
              Eastman
                Kodak
7,4,6-tribromoaniline     n.a.
                Kodak Park     r
                  Dlv.
                Rochester, SY
                Great Lakes
                  Chem.
                West Lafayette,
                  IN
2,4-dlchloroaniline
                Tennessee
                  Eastmen
                Klngsport, TN
                (0.5-5 kkg)
2,3-dlchloroaniline
                                                                Monsanto
                                                                Lullng, LA
                                                                duPont
                                                                Deepvater,
                                                                  NJ
                                                    n.a.
Source:  USITC,  1976-79; Hancock, 1975; U.S. EPA, 1977

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9.5  IMPORTS OF CHLORO- AND BROMOANILINES

9.5.1  Amounts

     Table 9.2 summarizes the information on imports of chloro- and bromo-
anilines that was readily available.  Emissions due to importation of £-
chloroaniline and m-chloroaniline could be estimated by applying the oil
spill/risk model described in section 2.3.2.1.  The estimated emissions
which are obtained by multiplying a small amount of imported anilines x a
                                  _9
very small emission factor (7 x 10   kkg/kkg transported), would be very
small.  Useful emissions estimates for the solid chloro- and bromoanilines
were not possible.

9.6  CONSUMPTION AND USE

     Table 9.3 summarizes qualitative data available on consumption and uses of
haloanilines.  No quantitative data were available, so no useful estimates of
emissions could be made.

          TABLE 9.3  CONSUMPTION AND USES OF CHLOROANILINES1
COMPOUND
£-chloroaniline

in-chloroaniline

p_-chloroaniline

2,5-dichloroaniline
3,4-dichloroaniline
USES
Dye intermediate, colorimetric standard,
petroleum solvents, fungicides
Azo dyes and pigments, Pharmaceuticals,
insecticides, agricultural chemicals
Dye intermeidate, Pharmaceuticals,
agricultural chemicals
Dye intermediate
Dye intermediate, biologically active
compounds
     1
      Source: Hawley, 1977.
                                      9-5

-------
1978
240
40
50
10
—
190
1977
210
120
60
4
—
150
1976
1990
60
40
.6
10
10
19752
63
2
33
.03
—
56
1974
40
1
110
—
—
w_
       TABLE 9.2  IMPORTS OF CHLORO- AND BROMOANILINE COMPOUNDS

                        1974-1978 (kkg/year)1


Compound

o-chloroaniline

m-chloroaniline

p-chloroaniline

2,3-dichloroaniline

2,4-dichloroaniline

2,5-dichloroaniline

2,4,6-trichloroaniline               5          .06      —      —        100

p-bromoaniline                        .1      —         —      —         —


      United States International Trade Commission (1974-1978).  Imports of
      Benzenoid Chemicals and Products.  The import figures do not reflect any
      imports from air transportation.  See footnote 3.

      Those places in the table where dashes occur indicate that no imports were
      reported for the compound during that year.

      The USITC Imports of Benzenoid Chemicals and Products and tables for 1974,
      75, 76, 77, arid 78 do not reflect the entire import amount.  Each report
      sta-tes a "statistical coverage":  the estimated fraction of the total imports
      that was actually reported.  The statistical coverage values used for the
      compounds in this table were the ones that applied to the category,
      "intermediates."

                                             Statistical Coverage
                         Year                	Value	

                         1978                     76 percent
                         1977                     81 percent
                         1976                     80 percent
                         1975                     94 percent
                         1974                     99 percent

      The values in the table have been corrected for less-than-total reporting
      using the statistical coverage value.  This was attained by applying the
      following formula to each value in the table:

          Import Compound at  _ USITC Reported Import Quantity x 100%
          100% Value          ~ USITC Statistical Coverage Value (%)
                                       9-6

-------
Footnotes for Table 9.2 continued


     2
      The import figures for 1975 were not readily available and attempts to
      obtain these figures were unsuccessful.

     3
      Personal communications between Ron Burger, JRB Associates,  Inc.,  McLean,
      Virginia, and Mr. Magnusson, Office of Rubber and Chemicals,  U.S.  Department
      of Commerce.
                                       9-7

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                          10.  LOCATIONS OF EMISSIONS

     This chapter will collect the information already presented on locations of
producers of anilines in order to identify sites with a large point source or multiple
sources.  The results are shown in table form (Table 10.1).

     The table shows that the only locations with multiple compounds produced were
Bound Brook, NJ (two producers making three products); Deepwater, NJ (one producer
making three products); and Sauget, IL  (one producer making two products).  Bound
Brook, NJ, is the only city with two separate producers (American Cyanamid and
Blue Spruce Co.).  It is important to note, however, that this analysis will not
be complete until consumption sites - the major points of estimated emissions -
can be tabulated and analyzed in the same way.
                                       10-1

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                                               TABLE 10.1  LOCATIONS OF EMISSIONS
             Location
                                           Anilines
                                      Aniline  Aniline
                             Aniline    HC1      HBr   o-nitro-
                                                        m-nitro-  £-nitro  Other   Chloro- &
                                                                           nitro   bromo-
o
i
K>
Bound Brook, NJ
Deepwater, NJ
Gibbstown, NJ
Linden, NJ
Toms River, NJ
Coventry, RI
North Haven, CT
Renssalaer, NY
Rochester, NY
Huntington, WV
New Martinsville, WV
Willow Island, WV
Lock Haven, PA
Sodyeco, NC
Bushy Park, SC
Gulfport, MS
Pascagoula, MS
Geismar, LA
Luling, LA
Shreveport, LA
Beaumont, TX
Helena, AR
Kingsport, TN
Charles City, IA
Milwaukee, WI
Sauget, IL
X
X
                                X
                                X
                                                                                      X
                                                                                      X
                                                                                      X
                                                                                      X
                                                                                      X
                                                                                      X
                                                                                              X
                                                                                              X

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                                11.0  DATA GAPS

     During the preparation of this report, a series of significant data gaps
were identified.  Several of these have been mentioned in earlier chapters, and
they will be summarized here.

11.1  PRODUCERS AND AMOUNTS PRODUCED FOR LESS-WIDELY-PRODUCED ANILINES

     It was not possible to calculate emissions due to production for the com-
pounds aniline hydrochloride, m-nitroaniline, and the grouped nitroanilines and
haloanilines because of the absence of production data.  Since the actual product-
ion figures are proprietary, an estimate based on another approach (like plant
capacity analysis or back-calculation starting with consumption data) might be
needed.

11.2  CONSUMPTION AND USE INFORMATION FOR LESS-WIDELY-USED ANILINES

     Consumption data are necessary to the estimation of emissions due to consump-
tion.  These data were lacking for the compounds aniline hydrochloride, m-nitro-
aniline, and the grouped nitroanilines and haloanilines.  It might be possible to
obtain this information from a plant-by-plant analysis of 1) products marketed,
2) chemistry of a particular product's synthesis, and 3) how much of the product
was made per year.  This might be feasible in a Level II or Level III materials
balance.  Another important question about consumption is:  how much of the in-
put aniline was carried over into the product?  Chemical analyses of products
would be necessary to answer the question.

11.3  DATA ON EFFLUENT ANALYSIS OR EMISSION FACTORS FOR ANILINE PRODUCTION

     Because the estimation of emissions to water during aniline production is
a key value to obtain, it should be calculated at least two ways.  More data are
needed concerning waste stream analyses and waste treatment procedures, preferably
on a plant-by-plant basis.
                                      11-1

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11.4  ACCESS TO IMPORT AND EXPORT DATA WITHIN THE 'BASKET' CATEGORIES

     Information on relevant imports and exports are sometimes available but
hidden within the USITC's "all other" category.  It would be helpful if there were
a procedure for obtaining information from these "basket" categories on short
notice.
                                    11-2

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                            REFERENCE LIST


American Chemical Society, 1978.  "Chemical and Engineering News," July 17, 1978.
     Washington, DC.

Casarett, L. J., and Doull, J. (eds.), 1975.  Toxicology, The Basic Science of
     Poisons, McMillan Pub. Co.

Catalytic, Inc., 1978.  Environmental Protection Agency Guidelines Report;
     Plants by Product Process, U.S. Environmental Protection Agency, Washington,
     DC, [RA 383].

Chemical and Engineering News, Sept. 9, 1974.

Chemical Marketing Reporter, August 30, 1976.

Chemical Marketing Reporter, June 11, 1979.

Chemical Purchasing, June 1977.

Chemical Weekly, August 11, 1976.

Directory of Chemical Producers, USA, 1979.  Stanford Research Institute,
     Menlo Park, CA.

Federal Register 1976.  Environmental Protection Agency, Organic Chemicals
     Manufacturing Point Source Category, Title 40, Part 414, Jan. 5, Vol. 41,
     No. 2., pii  925, Washington, D.C.

Hahn, A. V., 1970.  The Petrochemical industry Market and Economics,
     McGraw-Hill Book Co., New York, NY.

Hancock, E. G. (ed.), 1975.  Benzene and Its Industrial Derivatives, John Wiley
     and Sons, New York, NY.

Hawley, G. G., 1977.  The Condensed Chemical Dictionary, 9th ed.,
     Van Nostrand Reinhold Co., New York, NY.

Howard, P. H., Santodonato, Joseph, et al., 1976.  Investigation of Selected
     Potential Environmental Contaminants;  Nitroaromatics,  U.S. Environmental
     Protection Agency (Office of Toxic Substances), Washington, DC.  [PB-275-078]

Hydroscience, Inc. 1977.  Emissions Control Options for the Synthetic Organic
     Chemicals Manufacturing Industry;  Aniline Trip, Report for E. I. duPont de
     Nemours, Beaumont, TX, Sept. 7-8, 1977.  U.S. Environmental Protection
     Agency (Office of Air Quality Planning Standards), Research Triangle Park, NC.

Kirk-Othmer, 1966. Encyclopedia of Chemical Technology, 2nd ed., Vol. XI,
     Interscience Publishers, New York, NY.

Lowenheim, F. A., and Moran, M. K.  1975.  Faith, Keyes and Clark's
     Industiral Chemicals, 4th ed., Wiley-Interscience, New York, NY.

-------
Mastendrea, J. R., and Simmons, J. A., 1978.  Deepwater Port Inspection Methods
     and Procedures, Science Applications, Inc., (DOT-CG-60670-A),  November 1978.

McCaleb, K. E., 1979. Chemical Ecnonomics Handbook, "Aniline and Nitrobenzene,"
     Stanford Research Institute, Menlo Park, CA.

Morris, J. C., 1975. Formation of Halogenated Organics by Chlorination of
     Water Supplies, U.S. Environmental Protection Agency, [P5-01-1805-J].

Ottinger, R. S. and Blumenthal, et al. 1973. Recommended Methods of Reduction,
     Neutralization, Recovery or Disposal of Hazardous Waste, Volume X, Industrial
     and Municipal Disposal Candidate Waste Stream Constituent Profile Reports  -
     Organic Compounds, U.S. Environmental Protection Agency (Office of Research
     and Development), Cincinnati, OH [68-03-0089].

Patty, Frank (ed.) 1963. Industrial Hygiene and Toxicology, Vol. II,
     Interscience Pub., New York, NY.

Personal Communication between Mr. Ron Burger, JRB Associates, McLean, Virginia
     and Mr. Magnusson, Organic and Rubber Chemicals Branch, U.S.  Department of
     Commerce, Washington, DC, October 24, 1979.

Personal Communication between Mr. Ron Burger, JRB Associates, McLean, Virginia
     and Mr. Ed Cappuccilli, Energy and Chemical Branch, U.S. International
     Trade Commission, Washington, DC, October 24 and 25, 1979.

Personal Communication between Mr. Ron Burger, JRB Associates, McLean, Virginia
     and Mrs. Hardy, Chemicals and General Manufacturing Branch, Foreign Trade
     Division, Bureau of the Census, October 29, 1979.

Personal Communication between Mr. Ron Burger, JRB Associates, McLean, Virginia
     and Mr. Fred Dorf, Manager of Manufacturing Polymer Additives, American
     Cyanamid, Wayne, NJ, October 29, 1979.

Personal Communication between Mr. Ron Burger, JRB Associates, McLean, Virginia
     and Mr. Rick Johnson, Clean Environment Program, Tennessee Eastman Chemical,
     Kingsport, TN, October 30, 1979.

Sax, N. E. (ed.) 1975.  Dangerous Properties of Industrial Materials,
     Reinhold Pub. Co.

Science Applications, Inc. 1977.  The Programatic EIS for the Strategic Petroleum
     Reserve Program Supplement, (Draft report for Department of Energy),
     December, 1977.

Science Applications, Inc. 1978.  Development of Environmental Criteria and
     Guidelines to Assess the Environmental Plan Submitted as Part of the Oil
     Purchase - Transport Contract. (DOE, CR-13-70174), June 1978.

-------
Simmonds, H. R. and Church, J. M. 1967. The Encyclopedia of Basic Materials
     for Plastics, Reinhold Pub. Co.

Snell, F. P. and Hilton, C. L., (ed.) 1967.  Encyclopedia of Industrial Chemical
     Analysis, Interscience, New York, NY.

Snell, Snell  1962. Dictionary of Commercial Chemicals, 3rd ed.
     Van Nostrand Co., Princeton, NJ.

Shreve, R. N. 1967. Chemical Process Industries, 3rd ed., McGraw-Hill, New York, NY.

Steedman, Thomas and Helper, Eleanor, 1977. Industrial Process Profiles for
     Environmental Use, Ch. 7, "Organic Dyes and Pigments Industry," U.S.
     Environmental Protection Agency, (Office of Research and Development),
     Cincinnati, OH (EPA-600/2-77-023g).

Stecher, P. G. (ed.) 1968.  The Merck Index, 8th ed., Merck and Co., Inc.,
     Rahway, NJ.

TRW Systems Group, 1973.  Recommended Methods of Reduction, Neutralization,
     Recovery of Hazardous Waste, Vol. XI, Industrial and Municipal Disposal
     Candidate Waste Stream Constituant Profile Reports, Organic Compounds
      (Continued) U.S. EPA, Washington, DC  [PB-224-590].

U.S. Army Corps of Engineers, Waterborne Commerce in the United States, 1973-1976.

U.S. Coast Guard, Pollution Incident Reporting System  (PIRS) 1973-1976.

U.S. Department of Energy, Draft EIS, Crude Oil Storage in Salt Domes in
     Southwestern Mississippi and Northern Louisiana, Department of Energy,
      [EL-78-R-01-7192].

United States International Commission. 1974-1978. Imports of Benzenoid Chemicals
     and Products. USITC Publications 762, 806, 828, 900, 990, Washington, DC.

U.S.  Environmental Protection Agency,  1979,  Computer Printout of the
      Nonconfidential Portion of the TOSCA  Inventory,   Chemical Information
      Division, Office of Pesticides and Toxic Substances, May, 1979.

U.S.  International Trade Commission 1975-1979, Synthetic Organic Chemicals,
      United States Production and Sales. Publications  776, 804, 833, 920,
      Washington, DC.

Verschueren,  K.,  1977. Handbook of Environmental Data  on Organic Chemicals,
      Van Nostrand Reinhold Co., New York, NY.

Weast, R. C.  (ed.)  1977. Handbook of Chemistry and Physics, 58th ed.,
      CRC Press, Inc., Cleveland, OH.

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                                  APPENDIX A

Description of Aniline Production by Catalytic Vapor-Phase Hydrogenation of
Nitrobenzene

Source:  Lowenheim, F. A., and Moran, M. K. (eds), 1975.  Faith, Keyes, and
Clark's Industrial Chemicals, 4th ed.  c 1975 by John Wiley and Sons, Inc.  Re-
printed by permission.

     Nitrobenzine containing less than 10 ppm thiophene is vaporized in a stream
of hydrogen and passed into a reactor containing a fluidized bed of copper catalyst.
The catalyst is made by spray-drying a silica hydrogel upon which cuprammonium
nitrate has been adsorbed.  The catalytic powder (10 to 20% copper) (20 to 150 m)
is activated in place in the reactor by treatment with hydrogen at 250°C.  The
nitrobenzene vapor-hydrogen mixture (300% excess hydrogen) is fed through a
porous distributor plate in the bottom of the fluidized bed reactor held at 270°C
and 5 psi (34.5 kPa).  Excess heat of reaction is removed by circulating a cool
heat-transfer fluid through tubes suspended in the catalyst bed.  Exit gasses
are filtered free of catalyst fines on porous stainless-steel filters in the top
of the reactor.

     The filtered product gasses are condensed, further cooled, and sent to a
liquid separator or decanter.  Excess hydrogen is recycled.  The lower layer
of liquid in the separator (crude aniline containing less than 0.5% nitrobenzene
and 5% water) is distilled to remove high boilers.  The water and aniline vapors
that pass overhead are separated by further distillation.

     The upper (aniline water) layer from the separator is pumped to an extraction
column, where it passes countercurrent to cold nitrobenzene for recovery of
dissolved aniline.  A yield of 98% is claimed for the process.

     The catalyst will produce 1500 kg aniline/kg of catalyst before regeneration
is required.  Regeneration is accomplished in place by flushing the system with
an inert gas, and then passing air through the catalyst at 250 to 350°C to burn
off organic deposits.
                                  A-l

-------
     Several different catalysts have been patented for use in aniline processes
similar to that described.  Operating procedures will of course vary with the
activity and ruggedness of the catalyst used.  An effective catalyst for a
fixed-bed hydrogenation is nickel sulfide deposited on alumina.
                                   A-2

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                              APPENDIX B   PRODUCTS DERIVED FRuM ANILINE
  PRODUCTION  PROCESS
              DERIVATIVE
                                                                                                     USES
Aniline 4- acetic anhydride or
aniline -f glacial acetic acid (27)
ACETANILIDE (27)
                                                                                Manufacture of £-nitroaniline and  o-nitro-
                                                                                  aniline (27)
                                                                                Sulphonamide Intermediate (27)

                                                                                Hydrogen Peroxide Stabilizer
                                                                                Cellulose Ester  Lacquers

                                                                                Manufacture of Dyes and  Intermediates
                                                                                Analgesic and Antipyretic Manufacture (36)

                                                                                Sulfa Drugs (33)

                                                                                Local Anesthetic  (33)
Aniline + ethylacetoacetate
Aniline -f diketene (36)
ACETOACETANILIDE (27)
                                                                                Dye Intermediate

                                                                                Manufacture of  Benzidine  Yellow Pigments (27]
Aniline + phosgene vapor or organic
solvents (27)
                                      PHENYL ISOCYANATES (27)
                                          Manufacture of Isocyanates
                                            urethanes
                                            disubstituted ureas
                                          Insecticides and Herbicides (27)
Methanol + aniline + sulphuric acid
under heat and pressure (27)

Aniline + formaldehyde reduced by
zinc and sodium hydroxide (27)
N-METHYLANILINE
N.N-METHYLANILINE (27)
                                                                               £-dimethylaminobenzaldehyde manufacture (27)
Aniline + excess methanol + acid
catalyst under heat and pressure
(27)
N.N-DIMETHYLANILINE (27)
                                                                               Dye Intermediate  (33)

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                              APPENDIX B   PRODUCTS DERIVED FRuH  ANILINE
   PRODUCTION PROCESS
              DERIVATIVE
                      USES
Aniline -f hydrochloride + ethanol
under heat and pressure (27)
N-ETHYLANILINE  (27)
Manufacture of Stabilizer For Explosives (27

Vulcanization Accelerator (36)
Aniline + sulphuric acid  (27)
SULPHANILIC ACID (27)
Manufacture of Three Sulphonilic Acids
Intermediate in Azo Dyestuffs and a Component
  in 91 Dyes (27)
Aniline 4- carbon disulphide +
sulphur heated in an autoclave (27)
2-MERCAPTOBENZOTHIZOLES (27)
Manufacture of Vulcanization Accelerators
  (27)

Sulphonamide Vulcanization'Accelerators (27)
Aniline + aldehydes + organic acid
as a catalyst (27)
ALDEHYDE-AMINE REACTION PRODUCTS (27) '
Manufacture of Vulcanization Accelerators
  (27)
Cyanogen chloride -f hot  'aqueous
aniline (27)
1,3-DIPHENYLGUANIDINE (27)
Manufacture of Vulcanization Accelerators
  (27)
Aniline + carbon disulphite (27)
THIOCARBANILIDE (27)
                                                                           I
Accelerator for Specific Rubbers (27)
Aniline + hydrochloric acid  as a
catalyst or substituted aniline with
ketones + hydrochloric acid (27)
2,2,4-TRIMETHYL-l, 2-DIlIYDROQUINOLINE
      (27)
Rubber Antioxidant (27)
Condensation of hydroquinpne and
two moles of aniline + acid catalyst
(27)
N,N-DIPHENYL-P-PHENYLENEDIAMINE (27)
Rubber Chemicals
  antiozonant (28)
  antioxidant (28)

-------
                              APPENDIX B   PRODUCTS DERIVisu KKOM ANILINE
   PRODUCTION PROCESS
             DERIVATIVE
                                                                                                      USES
Liquid phase catalytic hydrogenation
of aniline under pressure at 135°-
170°C and under 50 - 500 atmospheres
in the presence of a catalyst  (27)
(3D
                             \.
CYCLOHEXYLAMINE (27)
Major Use:  Manufacture of Sodium and
Calcium Cyclohexyl-Sulphamates used in the
Manufacture of Synthetic Sweetening Agents
(27)

Derivatives Used in the Manufacture:

Rubber Chemicals:
  vulcanization accelerators
  antioxidants
  antiozonants

Corrosion Inhibitors -
  ferric metals
                           i
Plastic Resins
Intermediate in Dyestuffs (27)

Used Directly in Boiler Water Limit Scaling
and Corrosion

Dyestuff Intermediates (27)
Vapor phase reaction with nickel
catalyst of aniline
 DICYCLOHEXYLAMINE (27)
Corrosion Inhibitors

Ferrous Metal Articles

Derivatives:  Form Sulphonamides Used as
Rubber Accelerators
Salts and Metal Compounds Used in Textile,
Paint and Varnish Industry (27)
Aniline is oxidized by manganese
dioxide or sodium dichrornate in
sulfuric acid to quinone.  Quinone
is reduced by iron in water: (31)
 HYDROQUIONONE (31)
Photographic Developer. (28)

Polymerization Inhibitors in Monomers (28)
Manufactures of BHA Food Antioxidant (28)

-------
                                  APPENDIX  B  PRODUCTS^DERIVED FROM  ANILINE
                                                                             1
       PRODUCTION PROCESS
DERIVATIVE
USES
                                           ANILINE (REFER TO FOOTNOTE 2)
Cd
                           Rubber Chemicals:
                             accelerators (36)
                             antioxidants (28)
                             antidegradant (33)
                             curing agents (33)
                             elastomers (33)
                             MDI Production (33)
                                                                                    Dyes:
                                                                                                    (39)
                             Intermediate:
                               stilbene
                               triarylmethane
                               azine dyes             '
                               indigoid dyes
                             Dyes (33)
                             Predye Fiber Treatment (33)(34)

                           Catalysts: (33)

                             polymerization reactions
                             organic reactions
                             organometallic reactions
                             metallurgical  industry
                             Patina production

                           Resins: (33)
                             production of epoxy resins
                              and Harding agents
                             production plastics (38)
                             aniline formaldehyde resins (33)

                           Petroleum: (33)
                             antiknock - gasoline
                             knock suppressor-
                              aviation fuel

-------
                                   APPENDIX B   PRODUCTS DERIVED FKOM ANILINE1
       PRODUCTION PROCESS
               DERIVATIVE
                                                                 USES
                                            ANILINE  (continued)
w
Ul
      1.  The  table presents ANILINE  and
         references.  The reference  list

      2.  The  referenced  resources  stated
         production process.   Therefore,
         directly.
ts Derivatives,  Cheir method of  product!
that applies to this  appendix only  is  at
                                           Rocket Fuels:  (33)

                                             ignition fuels
                                             self-flammable fuel mixture

                                           Explosives:  (38)

                                             detonator
                                             constituent  for gunpowder

                                           Agriculture  Uses: (33)

                                             intermediate for  pest  sprays

                                           Reagents:  (33)            f

                                             qualitative  detection  of metals
                                             papermaking  process

                                           Electronic Industry:  (33)

                                             polishing  diode and transistors

                                           Solvent  for  Organic Reactions (33)

                                        cjn and uses as  gleaned from readily available
                                         tached.
                                       djd
uses for "aniline and derivatives" but
uses stated under aniline may be from dei
  not state the 'aniline compound nor the
ivatives of aniline rather than aniline

-------
                               APPENDIX B   PRODUCTS DERIVED FKGFt ANILINE HYDROCHLORIDE
   PRODUCTION PROCESS
               DERIVATIVE
                       USES
Heating aniline and aniline hydro-
chloride at 210°-240°C at 90 pal
in the absence of. a catalyst, 30  to
35 hours (33)
 DIPHENYLAMINE  (1, 28, 31, 33)
Rubber Industry
  antioxidants (28)
  antiozonants (27)
  retarder (28)
  stabilizer (36)

Agriculture
  antihelminthics (28)
  insecticides (31)
  fungicide (33)

Dye Industry
  preparation of az.o dyes (31)
  printing (1, 30)
  dyestuff Intermediate (36)

Miscellaneous
  stabilizer for explosives (28, 36)
  metallurgy - plating baths (33)
  organic synthesis^
Keating aniline hydrochloride with
ethanol at 180°C, refluxing with
ethanol over Raney (33)
 N-ETHYLANILINE (33)
Rocket Fuel (33)
Dye Intermediate (31)
Heating aniline hydrochloride with
excess ethanol at 180.C under
pressure (31)
 DIETHYLANILINE (31)
Aniline hydrochloride plus excess
bromide (27)
 2,4,6-TRIBROMOANILINE (27)
Herbicide (10)
1.  The category "organic synethesis"
refers to the use of diphenylamine in th
synthesis of numerous organic compounds.

-------
                                  APPENDIX B   PRODUCTS DERIVED FROM ortho-NITROANILINE
      PRODUCTION PROCESS
              DERIVATIVE
                                                                                                          USES
   Reduction of o-nitroaniline with
   sodium sulphide under pressure
   (28, 36)
£-PHENYLENEDIAMINE (27, 36)
i
-j
Antioxidants
  inhibitor of copper corrosion (27)
  antifreeze preparations (27)
  lubricating oils (27)
  polishes detergents (27)

Rubber Chemicals and Intermediates (27)

Dyes
  C.I. Oxidation Base 16 (27)
  hair dyes (36)
  optical bleaches (27)
  dyestuff intermediate (27)

Pharmaceutical Products (27)
Veterinary Products
  antihelminthics (27)

Miscellaneous
  redox indicator (27)
  chemical detection of metals (27)
                                          .2-NITROANILINE
                                         Dyes
                                           preparation of azo and anthraquinone
                                                dyes (1,  3,  27)
                                           azoic diazo component 6 (27)

                                         Photographic Antifogging Agents (1, 36)
                                         Coccidostatis (1)

                                         Interior Paint Pigments (1)
                                          N-CYCLOALKENIC (27)
                                         Insecticides and Intermediates (27)

-------
                                 APPENDIX B    PRODUCTS DERIVED FROM meta-NITROANILTNE
      PRODUCTION PROCESS
              DERIVATIVE
                      USES
   Reduction  of m-nitroaniline with iron
   f.nd  dilute acid  or catalytic hydro-
   genation (31)
m-TOLUIDINE (31)
Dye Preparation (H
                                          m-NITUOANILlNE (27)
                                         Organic Synthesis (3, 31)

                                         Dye Intermediate (3, 27, 31, 36)

                                         Synthetic Sweeteners (31, 33)
a

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                              APPENDIX B   PRODUCTS DERIVED FROM  para-NITROANILINE
  PRODUCTION PROCESS
                                                    DERIVATIVE
                                                                                                      USES
Reduction of p-nitroaniline by
iron or sulfide  (27)
 N-SUBSTITUTED  p-PHENYLENEDIAMINES
Antioxidants and Antiozonants (27, 28, 31)
Hair and Fur Dye, Azo, Azine, Sulfur,
  and Cyanine DyesLuffs (27)
Dye Intermediate (27)
Deduction of p-nitroaniline with
iron and dilute acid or catalytic
hydrogenation (31)
£-TOUJIDINE  (3.1)
Dye Production (31)
Organic Synthesis (31)
Diazotization of p-nitroaniline with
HC1 and sodium nitrite (31)
JD-NITROANILINE HYDROCHLORIDE  (31)
Dyes (31)
Nitration of p-nitroaniline (27)
2,4,6-TRINITROANILINE (PICRAMIDE) (27)
Direct chlorination of p-nitro-
aniline in benzene solution at 20°C
with tert-butyl hypochlorite (33)
2,6-DICHLORO-A-NITROANILINE (33)
                                       £-NITROANILINE
                                         Corrosion Inhibitor (1)
                                         Veterinary and Pharmaceutical Products (1, 3)
                                         Agricultural Chemicals (3)
                                         Dyes and Dye Intermediates (1, 31)
                                         Gasoline Additives (1, 3)
                                         Rubber Chemicals
                                           antioxidants (1)
                                         Fungicides
                                           Botran (28)

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o
                                             REFERENCES FOR APPENDttf B ONLY
                   27.  Hancock, E.G.  (ed.),  Benzene and Its Industrial Derivatives, John Wiley
                        and Sons, NY,  1975.        ~~                      '

                   28.  Hahn, A.V., The Petrochemical Industry Market and Economics,
                        McGraw-Hill Book  Co.,  NY,  1970.
                   31.  Kirk-Othraer,  Encyclopedia of Chemical Technology. 2nd ed., Interscience
                        Publishers, NY, 1968.

                   33.   Snell-Hilton,  Encyclopedia of Industrial Chemical'Analysis, Interscience
                        Publishers,  1967.                                                     .
                   36.  . Snell,  Snfell,  Dictionary of Commercial Chemicals, 3rd ed.,
                        Van Nostrand Co.,  Princeton, NJ.               "
38.  Simonds, H.R. and Church, J.M., The Encyclopedia of Basic Materials
     for Plastics, Reinhold Pub., Co.,  1967.

39.  Industrial Process Profiles  for Environmental  Use,  Ch.  7, "Organic
     Dyes and Pigments Industry," prepared  for  Office of Research and
     Development,' U.S. Environmental Protection Agency,  Cincinnati,  OH, 1977.
                    1;  Hawley, G.G. ,  The Condensed  Chemical Dictionary, 9th ed. ,         .    .        '   ';';.!'
                        Van Nostrand  Reintjpld Co., ;New York,; 1977.••'•'.        :.          ;       '         '   i .•    !
                                                                  i                                            i
                    3.  TRW Systems Group,  Recommended Methods of Reduction. NeutralizationfRecovery, or     ;  '•
                        Disposal of Hazardous Wast^e.  Vol.  X. organic compounds.  Prepared for U.;S.Environmental;
                        Protection Agency,  Washington, D.C.

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                                    TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-560/13-80-013
                                                            3. RECIPIENT'S ACCESSION NO.
 4. TITLE AND SUBTITLE

  Level I Materials Balance:  Anilines
5. REPORT DATE
  May 9, 1980
                                                            6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
  Robert L. Hall,  Ronald Burger, and Karen Slimak
8. PERFORMING ORGANIZATION REPORT NO
 9. PERFORMING ORGANIZATION NAME AND ADDRESS
  JRB Associates,  Inc.
  8400 Westpark Drive
  McLean, VA 22102
                                                            1O. PROGRAM ELEMENT NO.
T1. CONTRACT/GRANT NO.

  68-01-5793
 12. SPONSORING AGENCY NAME AND ADDRESS
  Survey  and Analysis Division  (TS-793)
  Office  of  Pesticides and Toxic Substances
  U.S. Environmental Protection Agency
  Washington, DC  20460	
13. TYPE OF REPORT AND PERIOD COVERED
  Final Report	
14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
  Project  Officer - Michael Callahan
 16. ABSTRACT
  This  report presents a Level I materials balance study of a group of anilines speci-
  fied  in  a Task Order from the Office of Toxic Substances, U.S.  Environmental Protec-
  tion  Agency.  The compounds studied were aniline, aniline hydrochloride, aniline
  hydrobromide,  a-, m-5 and £-nitroanilines, 16 other nitroanilines, and 15 other
  chloro-  and bromoanilines.  Areas  of major interest were production quantities,
  producers,  consumption quantities,  and emissions to air, land,  and water related to
  these processes.  The estimated  amounts of 1978 production  (where available) were
  as  follows:  aniline, 279,000 kkg;  aniline hydrochloride, 4.6  - 100 kkg; o-nitro-
  aniline,  3641 kkg; m-nitroaniline,  0-2.3 kkg; _p_-nitroaniline,  13,000 kkg.  Emissions
  were  estimated when direct data  were unavailable.  The results  (in kkg/year) were:
  aniline,  20 kkg to air, 0.08 - 5.6  kkg to water; p_-nitroaniline, 0.13 kkg to air,
  117 kkg  to water.  Throughout the  report, estimates and assumptions were made where
  justified,  in lieu of direct data.   Types of information required for future studies
  are noted.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                               b.lDENTIFIERS/OPEN ENDED TERMS
              c. COSATI Field/Group
 8. DISTRIBUTION STATEMENT

  Release Unlimited
19. SECURITY CLASS
  Unclassified
"This Report)
              21. NO. OF PAGES
                  145
                                               20. SECURITY CLASS (Thispage)
                                                 Unclassified
                                                                          22. PRICE
EPA Form 2220-1 (9-73)

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