EPA 560/6-77-002
CHEMICAL MARKET INPUT/OUTPUT ANALYSIS
OF SELECTED CHEMICAL SUBSTANCES
TO ASSESS SOURCES OF ENVIRONMENTAL CONTAMINATION:
TASK I. NAPHTHYLAMINES
March 1976
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, B.C. 20460
-------
EPA 560/6-77-002 TR 76-523
CHEMICAL MARKET INPUT/OUTPUT ANALYSIS
OF SELECTED CHEMICAL SUBSTANCES
TO ASSESS SOURCES OF ENVIRONMENTAL CONTAMINATION:
TASK I. NAPHTHYLAMINES
William M. Meylan
Philip H. Howard
Milton Sack
Center for Chemical Hazard Assessment
Syracuse Research Corporation
Merrill Lane
Syracuse, New York 13210
Contract No. 68-01-3224 - Task I
SRC No. L1273-06
March 1976
Project Officer - Thomas E. Kopp
Prepared for:
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, B.C. 20460
Document is available to the public through the National Technical Information
Service, Springfield, Virginia 22151
-------
NOTICE
This report has been reviewed by the Office of Toxic Substances, EPA,
and approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the Environmental Protection
Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
ii
-------
TABLE OF CONTENTS
Page
I. Introduction 1
II. History and Future of a-Naphthylamine 2
III. Market Input/Output 5
A. Production 6
B. Importation 5
C. Use Patterns 10
D. Exportation 10
IV. Production Technology 13
A. Processing Facility 13
B. Process Description 13
C. Environmental Management 17
D. Economics 18
E. Historical Manufacturers of a-Naphthylamine 19
1. E.I. duPont de Nemours & Co., Inc. 20
2. Allied Chemical Co. 21
3. GAF Corp. 24
V. Use Process Technology 25
A. Herbicides 25
1. Processing Sites 25
2. Process Description 25
3. Environmental Management 31
4. Future Manufacturers 32
5. Herbicide Uses 32
a. Historical - Naptalam Use 32
b. Crop Protection 32
c. Areas of Usage 34
6. Economics 34
7. Alternative Final Use Products - Herbicides 38
a. Products and Usage 38
b. Comparative Cost and Persistence 38
iii
-------
TABLE OF CONTENTS
(continued)
Page
B. Dyes 44
1. Processing Sites 44
2. Process Description 44
3. Environmental Management 49
4. Use 49
5. Economics 56
6. Alternative Final Use Products - Dyes 64
7. Alternative Chemicals for Synthesis 65
C. Discontinued Uses 66
1. Substituted a-Naphthylamine Derivatives 66
a. N-Phenyl-a-Naphthylamine 67
b. N-Ethyl-ot-Naphthylamine 68
c. Sodium Naphthionate (Naphthionic Acid-Sodium Salt) 69
d. l-Naphthol-4-Sulfonic Acid (Nevile and Winther's 70
Acid)
e. o-Naphthionic Acid 72
2. Aldol-a-Naphthylamine Condensate 72
3. Rodenticide-a-Naphthylthiourea 73
VI. Material Balance - Exposure.to the Environment s 75
A. a-Naphthylamine Manufacture 75
B. Herbicides 75
C. Dyes 76
VII. Environmental Assessment 80
Appendix A 83
Appendix B 89
REFERENCES 93
iv
-------
LIST OF TABLES
Number Page
III-l Current Importation of a-Naphthylamine 8
III-2 Importation History of Naphthylamines and Compounds That 9
May Be Derived from a-Naphthylamine
III-3 Current Users of a-Naphthylamine 11
III-4 Former Users of a-Naphthylamine 12
IV-1 Data on Current a-Naphthylamine Processing Site 14
IV-2 Historical Manufacturers of a-Naphthylamine 20
V-l Processing Sites for a-Naphthylamine Herbicides 26
V-2 Annual Production of Naptalam, 1964-1974 33
V-3 Usage of Naptalam in 1971, Quantities + Acres 35
V-4 Usage of Naptalam by States in 1971 35
V-5 1971 Use of Naptalam and Alternative Herbicides 39
V-6 Chemistry of Alternative Products for Naptalam Applications 40
V-7 Alternative Herbicide Products—Comparative Cost and 43
Persistence
V-8 Processing Sites for a-Naphthylamine Dyes 45
V-9 Disposal of Dye Wastes 50
V-10 Annual Consumption of a-Naphthylamine Used in Dye 51
Production
V-ll Dyes Made Directly from a-Naphthylamine 52
V-12 a-Naphthylamine Dye Producers and Products, 1964-1973 53
V-13 0 Dyes Manufactured from a-Naphthylamine 57
V-14 1972 DuPont Production Quantities and Values for 66
a-Naphthylamine-Derived Intermediates
-------
LIST OF TABLES
(continued)
Number Page
V-15 Annual Production Quantities of Sodium Naphthionate 71
and Napthionic Acid
V-16 Annual Production Quantities of l-Naphthol-4-Sulfonic Acid 71
vi
-------
LIST OF FIGURES
Number Page
II-l Estimated Current a-Naphthylamine Use 3
II-2 a-Naphthylamine Use in 1972 4
III-l Production of a-Naphthylamine 7
IV-1 Manufacturing Process for a-Naphthylamine 15
IV-2 Simplified Version of a Partial Melter (Melt Crystallizer) 22
V-l Manufacturing Process for a-Naphthylamine-Derived Herbicides 27
V-2 Manufacturing Process for a-Naphthylamine-Derived Herbicides 28
V-3 Farm Production Regions 36
V-A Dye Process Schematic 46
vii
-------
I. Introduction
Compounds a- and 3-naphthylamine have recently been regulated by the
Occupational Safety and Health Administration (Anon., 1973; Anon., 1974 c)
because of their carcinogenic activity. The standards established by OSHA are
directed at protecting workers who might be exposed occupationally to the chem-
icals. However, little thought has been given to the amount of naphthylamines
that might be released to the environment and thus indirectly result in human
exposure. This report considers the potential for such release of naphthyl-
amines . -
Because 3-naphthylamine is a proven human carcinogen and there are other
alternatives to its use, it is no longer produced and consumed commercially in
the United States. However, a-naphthylamine, which is a suspected carcinogen,
is still manufactured for use as a chemical intermediate for dyes and herbicides.
Thus this report concentrates on the commercial production and use of et-
na? h thy lamine. Small quantities (less than 0.5%) of B-naphthylamine may be
found in the industrial grade a-naphthylamine.
-------
II. History and Future of a-Naphthylamine
The past fifteen years have been marked by a decline in the production and
in the number of producers of domestic ct-naphthylamine. DuPont is the only
current U.S. producer of a-naphthylamine, Allied Chemical Corp. and GAF Corp.
having halted production in 1970 and 1960, respectively. In the late 1960's
and early 1970's, an estimated 5-6 million pounds of a-naphthylamine were being
produced annually, but the current annual production level has fallen to an
estimated 3-4 million pounds.
Presently, a-naphthylamine is used as a chemical intermediate in the manu-
facture of pre-emergent herbicides and organic dyes and pigments (see Figure II-l).
In the past, a large percentage of the production was used to manufacture dye
intermediates (naphthionic acid, sodium naphthionate, l-naphthol-4-sulfonic acid,
N-ethyl-a-naphthylamine) and antioxidants (N-phenyl-a-naphthylamine, aldol-a-
naphthylamine condensate) (see Figure II-2). Currently, domestic production of
each of these a-naphthylamine derived chemicals has either been terminated or
replaced with a process avoiding the use of a-naphthylamine.
The decline in annual a-naphthylamine production is mainly attributable
to OSHA's temporary and final standards for a-naphthylamine handling, which were
issued May 3, 1973 (Anon., 1973) and January 29, 1974 (Anon., 1974 c), respectively.
To a lesser extent, the withdrawal of Allied Chemical Corp. from the production
market in 1970 also contributed to the decline. The OSHA standards resulted in
the termination of manufacture of all a-naphthylamine derived intermediates and
antioxidants and caused 17 of 21 domestic dye manufacturers to cease production
of a-naphthylamine derived dyes. They also had an impact upon DuPont's decision
to restrict production and handling of a-naphthylamine to the molten form only.
-------
u>
a-NAPHTHYLAMINE
100%1
31/4-41/2
million
pounds
10-20%
DYES3
25 -35% dye use
30 -40% dye use
<5%dyeuse
<5%dye use
Acid Orange
Acid Blue
Acid Black
Direct Blue
Direct Blue
Direct Blue
Disperse Black
Pigment Red
116
113
24
71
78
126
1
54
80-90%
-»• HERBICIDES
_ 1 _ Naphthylphtnalamic Acid and Sodium Salt
1 1/4 — 1/2 million pounds imported for dye use included
2 SRC Estimations
3 See Table V — 13 for chemical structures
Figure II-l. Estimated Current a-Naphthylamine Use
-------
16.5%
a-NAPHTHYLAMINE
100%'
5.6 million
pounds
DYES2 '
35 1 %
-» HERBICIDES
32.1%
-»• ANTIOXIOANTS -
RODENTICIDE
15.5%
3.1%
3.3%
2%
-«> Acid Orange
-» Acid Blue
-» Acid Black
-»• Direct Blue
-» Direct Blue
-» Direct Blue
—» Disperse Black
—» Pigment Red
-» Others
116
113
24
71
78
126
1
54
-» N 1 - Naphthylphrhalamic Acid and Sodium Salt
29.6%
-» N — Phenyl — a — Naphthylamine
-» Aldol —a - Naphthylamine Condensate
-» a — Naphthylthtourea
4.1%
DYE INTERMEDIATES
11.4%
-» N-Ethyl-a -Naphthylamine
^ Sodium Naphthionate and
Naphthionic Acid
—^ N — Phenyl — a • Naphthylamine
_^ 1 - - Naphthol - 4 - Sulfonic Acid
( Nevile - Winther's Acid)
' Includes approximately 0.1 million Ibs. imported for dye use .
See Table V 13 for chemical names and structures of dyes
Figure II-2. a-Naphthylamina Use in 1972
-------
Historically, a-naphthylamine use in domestic dyes has been stable, with
the annual consumption ranging from one-half to one million pounds during
1964-1973. The OSHA standards caused a decline from this range; however,
present a-naphthylamine use in dyes is again nearing the one-half million
pound mark and current dye manufacturers foresee a slightly expanding market.
Three of the four current dye manufacturers import a-naphthylamine in the
solid flaked form rather than use the molten form available from Dupont.
Any sizable increase in future domestic production of a-naphthylamine
is aligned directly with an increase in production of a-naphthylamine derived
herbicides, which use the molten form of a-naphthylamine. These herbicides
are used for pre-emergent protection for soybean and peanut crops and are very
competitive economically with alternative soybean and peanut herbicides. The
soybean and peanut market has expanded greatly in the past five years and, as
a result, production of a-naphthylamine derived herbicides has nearly doubled
between 1971 and the present. Almost 1.6 million pounds of a-naphthylamine
were used in 1971 for herbicides, while.approximately 3 million pounds are
presently consumed. However, industry spokesmen project only a 25% increase
in the next five years.
-------
III. Market Input/Output
A. Production
The E.I. duPont de Nemours and Co., Inc. (processing site located
in Deepwater Point, N.J.) is the only domestic manufacturer currently pro-
ducing a-naphthylamine. DuPont produces a molten form of a-naphthylamine
which sells for approximately $1.10 per pound. The current annual production
of a-naphthylamine by DuPont is estimated at 3-4 million pounds (SRC estima-
tion) .
Former a-naphthylamine producers include Allied Chemical Corp.
(Buffalo, N.Y.) and GAF Corp. (Rensselaer, N.Y.). When Allied Chemical was
manufacturing a-naphthylamine, it produced about 1 million pounds annually
(Allied Chemical Corp., 1975). The GAF production is believed to have been
much smaller than 1 million pounds per year.
Figure 11*1-1 illustrates production trends for a-naphthylamine
including estimates of future production.
B. Importation
Current and former importers of a-naphthylamine are listed in
Table III-l. The available information on past import quantities of a-naph-
thylamine and its derived intermediates is listed in Table III-2. It should
be noted that the data in Table III-2 are based only on surveys conducted
at major ports of entry. Among the overseas sources of a-naphthylamine are
Poland and Japan (Amitrano, 1975).
A high percentage of imported a-naphthylamine is sold to the dye
producers. However, Orlex Chemical Corp. (Muelluer, 1975) indicates that sales
have been made to an additional user for applications other than dyes, but
they could not disclose the application because it was considered proprietary.
-------
dr A
4
o
o
o
(C
a.
1964 1966 1968 1970 1972 1974 1976 1978 1980 1982
YtAR
Figure III-l. Production of a-Naphthylamine (SRC Estimations)
-------
Table III-l. Current Importation of a-Naphthylamine (OPD Buyer's Guide,
1975-1976; various personal communications)
Current Importers
(Amitrano, 1975; Product Shipping Current Annual
Muelluer, 1975) Grade Containers Quantities
1. Aceto Chemical Co., Inc. Flaked and Fiberboard
(Flushing, N.Y.) Fused Drums
2. Orlex Chemical Corp. Flaked Fiberboard
(Fair Lawn, N.J.) Drums _
Estimated Total Current Annual Import Quantities : \ - % million Ibs.
Former Importers
(Chavkin, 1975;
Fallek Chemical Corp., 1975)
1. Biddle-Sawyer Corp.
(New York, N.Y.)
2. Fallek Chemical Corp.
(New York, N.Y.)
-------
Table III-2. Importation History of Naphthylamines and Compounds That May Be
Derived from a-Naphthylamine* (U.S. Tariff Commission, 1967-1973)
(All figures in pounds.)
a-Naphthylamine 3-Naphthylamine N-Phenyl-a-Naphthylamine
1973
1972
1971
1970
1969
1968
1967
—
89,581
60,038
51,980
33,904
31,257
5,060 38,443
2,205
—
—
2,205
•
5,070
1973
1972
1971
1970
1969
1968
1967
Nevile-Winther's Sodium Salt
Acid** Nevile-Winther's Acid
79,466 36,949
103,449 33,687
26,103 52,381
68,445
59,390
52,982
25,519
Sodium Naphthionate
501,991
1,115,033
1,169,253
1,110,614
1,089,492
1,019,879
406,992
* Based only on surveys conducted at major ports.
** l-Napthol-4-sulfonic acid
-------
C. Use Patterns
Current users of ot-naphthylamine are listed in Table III-3, while
former users are listed in Table III-4. It can be seen from Table III-4 that
1973 was the year when most terminations occurred. These terminations were
precipitated by the issuance of OSHA's regulations (Appendix A) for a-naphthyla-
mine. Most of the users reported that it was not economically feasible to
continue use.
D. Exportation
a-Naphthylamine is not and has not been exported in recent history.
10
-------
Table III-3. Current Users of a-Naphthylamine
1.
2.
3.
4.
5.
6.
7.
User
Uniroyal Chemical Div.
of Uniroyal, Inc.
Thompson-Hayward Chemical Co . ,
Subsid., North American Philips Corp.
Helena Chemical Co.
GAP Corp.
Crompton & Knowles Corp.
American Color & Chemical Co.
Harshaw Chemical Co.,
Div. of Kewanee Oil Co.
Use
Herbicides
Herbicides
Herbicides
Dyes
Dyes
Dyes
Dyes
Pigments
Product
Grade
Molten
Molten
Molten
Flaked
Molten
Flaked
Flaked
Approximate
a-Naphthylamine
Price (per Ib)
$1.10
$1.10
$1.10
$1.45
$1.10
$1.45
$1.45
Estimated*
Current Annual
Use (in Ibs)
2 Million
% Million
% Million
<\ Million
<% Million
<% Million
<0.1 Million
* SRC Estimation
-------
Table III-4. Former Users of ot-Naphthylamine
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
User
Allied Chemical Corp.
American Cyanamid
Atlantic Chemical Corp.
Baychem Corp.
Benzenoid Organics, Inc.
Bernscolor-Poughkeepsie, Inc.
Blackman-Uhler Chemical Co.
John Campbell & Co.
E.I. duPont de Nemours & Co.
Fabricolor, Inc.
B.F. Goodrich Co.
Hercules, Inc.
ICI America, Inc.
Max Marx Color & Chemical Co.
Nyanza, Inc.
Organic Chemical Corp.
S.B. Penick & Co., unit of
CPC International, Inc.
S an do z- Wander, Inc.
Sterling Drug, Inc.
(Hilton-Davis Chemical Co.)
Tenneco, Inc.
Toms River Chemical Corp.
J.S. Young Co.
(Young Aniline Works)
Product
Dyes
Intermediates
Intermediates
Dyes
Dyes
Dyes
Dyes
Dyes
Dyes
Dyes
Intermediates
Dyes
Aldol-a-naphthylamine
condensate
Pigment
Dyes
Pigment
Dyes
Dyes
a-Naphthylthiourea
Dyes
Pigment
Dyes
Dyes
Dyes
Year
Terminated
1973
1970
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
1973
1971
1967
1973
1973
1973
1973
1973
1973
1973
1973
12
-------
IV. Production Technology
A. Processing Facility
Table IV-1 lists data for the DuPont processing site for a-naphthylamine
at Deepwater Point, N.J. The information listed includes estimated production
quantities, raw materials, production chemistry, and impurity removal and dis-
posal.
B. Process Description
The schematic flow diagram for a-naphthylamine manufacture is illustrated
in Figure IV-1.
Naphthelene and mixed acid are added simultaneously to the nitrator at
a temperature of 58-61°C. The mixed acid contains nitric acid, 35.5-36.5%, and
sulfuric acid, 41.3-42.3%, and the remainder is water. This batch is cooked for
thirty minutes at 60-65°C and is then transferred to a gravity separator. In
the gravity separator, the mixture separates into two layers, an acid layer and
a nitronaphthalene layer. The acid layer, which contains 55% sulfuric acid, is
separated off and run to a recovery system. The molten nitronaphthalene is
washed with water several times at 55-57°C and is then neutralized with sodium
bicarbonate and given a final water wash (Boyd, 1976).
The reaction product, ct-nitronaphthalene, is a light yellow, odorless
solid which melts at 52°C; the yield is 97.8% of theory (Boyd, 1976). The
product will contain 3-5% 3-nitronaphthalene and 0.3-1% dinitronaphthalenes as
impurities (Donaldson, 1958; Treibl, 1967).
Separation of the a-nitronaphthalene from the by-products is accom-
plished by a process called "melt crystallization" (Boyd, 19751976). This
13
-------
Table IV-1. Data on Current a-Naphthylamine Processing Site
Company - E.I. duPont de Nemours & Co., Inc.
Site - Deepwater Point, N.J.
Estimated Annual Production - 3-4 million Ibs (SRC estimation)
Raw Materials - Naphthalene, Nitric and Sulfuric Acid, Hydrogen Gas, Catalysts
(Nickel and Sodium Acetate)
Production Chemistry;
Step //I; Nitration of Naphthalene
N0«
3-
Step #2; Reduction of o-Nitronaphthalehe
+ 3H,
Ni
NaC2H3°2
+ 2H_0
Step //I: Impurities
H?0 and H SO
3-Nitronaphthalene
Dinitronaphthalenes
Step #2: Impurities
Ni Catalyst
Water (major portion)
(minor portion)
Still Pot Residues
Removal Method
Density Separation
Melt Crystalization
Melt Crystalization
Removal Method
Filtration
Density Separation
Vacuum Distillation
Disposal Method
To Acid Recovery
Incineration
Incineration
Disposal Method
Reusable or Buried
Incineration
Incineration
Incineration
14
-------
NITRONAPHTHALENES
MELT
CRVSTALIZER
INCINERATION
WASTE
WATER
Ni CATALYST
FILTER
INCINERATION
0-NITRO AND
DINITRONAPHTHALENE
REMOVAL
LIQUID PHASE
a-NITRONAPHTHALENE
CATALYTIC
HYDROGENATOR
HYDROGEN
GAS
Figure IV-1. Manufacturing Process for a-Naphthylamine
-------
involves a partial melting or "sweating" of the reaction product. The (3-
nitronaphthalene and dinitronaphthalenes are collected and incinerated, while
the liquid phase ct-nitronaphthalene is transferred to a catalytic hydrogenator
for reduction (Boyd, 1975-1976).
Reduction of the a-nitronaphthalene to a-naphthylamine is described by
the following description of U.S. Patent 2,105,321 which is assigned to DuPont
(Henke and Benner, 1938):
"Alpha nitronaphthalene is reduced to alpha-naphthylamine in
the liquid phase with hydrogen. The hydrogenation is preferably
carried out at 80 to 100°C and under 400 to 500 pounds hydrogen
pressure in the presence of a nickel catalyst. After hydrogen
absorption has ceased, the charge is filtered to remove catalyst,
and the alpha-naphthylamine is separated from the water layer.
The amine thus produced may be further purified by vacuum dis-
tillation through a short column. The distilled amine in this
liquid state is a colorless product which analyzes 99 to 100%
naphthylamine."
The patent proceeds to claim (Henke and Benner, 1938):
"... the presence of a nickel catalyst in which the active
nickel is about .2% to about .5% by
-------
After the a-naphthylamine has been purified as described by the patent,
the molten a-naphthylamine (m.p. 50°C) can be transferred to heated railway or
truck tankers fpr shipment to customers. The shipment requires special label-
ling and handling instructions (see Appendix B) because the final product may
contain up to 0.5% $-naphthylamine, a known human carcinogen. More commonly the
product contains 0.4% B-naphthylamine (Boyd, 1975-1976).
The wastes produced from purification of the a-naphthylamine are
incinerated to prevent environmental release (Boyd, 1975-1976).
C. Environmental Management
There is no loss or disposal of a-naphthylamine or naphthylamine by-
products to the environment from the a-naphthylamine manufacturing process. All
of the impurities or waste by-products are collected and incinerated (Boyd,
1975-1976). Some wastes have been buried in landfill approved for carcinogenic
materials (Boyd, 1976).
The only othe-r possible route for escape to the environment is from
accident or equipment failure.
17
-------
D. Economics
The following is a rough estimate of the material costs for
oi-naphthylamine production:
Raw Materials & Cost (Chemical Marketing Reporter, 1976)
Naphthalene $0.136/lb
Nitric Acid $0.06/lb
Sulfuric Acid $0.025/lb
Hydrogen $1.00/lb (Various Personal Communications)
Step #1; Nitration of Naphthalene
(m.w. 98)
(m.w. 128) (m.w. 63) (m.w. 173)
HN03 -1-= > 1 U1U J + 2H2°
Basis: 1-lb-mole a-nitronaphthalene (100% yield)
Naphthalene 128 Ib = $17.41
Nitric Acid 63 Ib = $ 3.78
Sulfuric Acid 98 Ib = $ 2.45
$23.64
a-Nitronaphthalene Cost: $23.64/173 Ibs or $0.137/lb
Step #2; Hydrogenation of a-Nitronaphthalene
NO,,
NH,
catalysts
(m.w. 173) (m.w. 2) (m.w. 143)
18
-------
Basis: 1-lb-mole of ot-naphthylamine (100% yield)
a-Nitronaphthalene 173 Ib = $23.64
Hydrogen 6 Ib = $ 6.00
$29.64
Approximate a-Napthylamine Cost: $29.64/143 Ibs or $0.21/lb
This $0.21/lb is material cost only and is an approximation at best.
Catalyst costs and sulfuric acid recovery have not been included.
The current selling price of a-naphthylamine is $1.10/lb from DuPont
(Boyd, 1975-1976). Mark-up includes costs for labor, equipment, profits, etc.
The capital value of the equipment was not available from DuPont. However,
all of the equipment used (nitrator, settling tanks, melt crystallizer, hydro-
genator, etc.) is used only for a-naphthylamine manufacture. The equipment
is not used to produce any other chemicals (Boyd, 1975-1976).
Considering the 3-4 million pound estimation for annual a-naphthyl-
amine production and the selling price of $1.10/lb, the annual value of
a-naphthylamine sales would amount to $3.3-$4.4 million.
The selling price of a-naphthylamine in 1972 was approximately
$0.55/lb. The price rise is probably attributable to the inflated price for
the naphthalene grade required for nitration, the additional safety require-
ments imposed by the OSHA standards, and diminished sales volume.
O
E. Historical Manufacturers of a-Naphthylamine
Historical manufacturers of a-naphthylamine, reporting to the
United States International Trade Commission from 1960 to 1973 are listed in
Table IV-2. Additional data on a-naphthylamine producers are listed below.
19
-------
1. E.I. duPont de Nemours & Co., Inc. (Deepwater Point, N.J.)
Dupont is the only current manufacturer. In 1972 Dupont pro-
duced nearly five and one-half million pounds of a-naphthylamine. Almost half
of that production was captively used to synthesize the following intermediates:
N-phenyl-a-naphthylamine, N-ethyl-a-naphthylamine, naphthionic acid and sodium
salt, £-naphthionic acid, and l-naphthol-4-sulfonic acid (Nevile and Winther's
Acid).. DuPont has subsequently terminated captive use of a-naphthylamine.
The present estimated (SRC estimation) production of a-naphthylamine has fallen
to 3-4 million pounds annually.
Table IV-2. Historical Manufacturers of a-Naphthylamine (United States
International Trade Commission, 1960-1973)
1973 DuPont
1972 DuPont
1971 DuPont
1970 Allied Chemical; DuPont
1969 Allied Chemical; DuPont
1968 Allied Chemical; DuPont
1967 Allied Chemical; DuPont
1966 Allied Chemical; DuPont
1965 Allied Chemical; DuPont
1964 Allied Chemical; DuPont
1963 Allied Chemical; DuPont
1962 Allied Chemical; DuPont
1961 Allied Chemical; DuPont
1960 Allied Chemical; DuPont; GAF Corp.
20
-------
2. Allied Chemical Co.
The Specialty Chemicals Division of Allied Chemical Co.,
located in Buffalo, N.Y. , terminated production of cx-naphthylamine in 1970.
Production quantities averaged approximately one million pounds per year
(Allied Chemical Corp., 1975).
In the Allied process, naphthalene was nitrated via mixed acids
(1:1 molar ratio of nitric and sulfuric acids) to nitronaphthalene in a man-
ner similar to that previously described in Section IV-B. Here again, the
nitronaphthalene product contained 95-96% cx-nitronaphthalene, 3-4% g-nitro-
naphthalene, and 0.5-1% dinitronaphthalenes. In order to obtain a purified
a-nitronaphthalene product, the B-nitronaphthalene and dinitronaphthalenes
were separated from the a-nitronaphthalene by a process of partial melting.
The flaked nitronaphthalene from the washer was transferred to the partial
melter (melt crystallizer)(see Figure IV-2) and allowed to solidify. The
melting points of the constituents are as follows: a-nitronaphthalene = 50°C,
g-nitronaphthalene = 113°C, dinitronaphthalenes = 144 to 217.5°C. Steam was
then injected through pipes which were interspersed in the mass of solidified
nitronaphthalene, and the temperature was allowed to rise to several degrees
above the melting point of the a-nitronaphthalene (50°C). The a-nitronaphtha-
lene melted, and the less dense 3-nitronaphthalene and dinitronaphthalenes
solids floated to the top of the mass and were skimmed off and incinerated.
The temperature was then dropped below the 50°C mark until solidification
began and then raised above that mark once more. A second skimming was done
to remove any remaining 6-nitronaphthalene and dinitronaphthalenes; however,
this second skimming also removed sizable amounts of a-nitronaphthalene, so
21
-------
Figure IV-2. Simplified Version of a Partial Melter (Melt Crystallizer)
22
-------
the second skimming was saved for addition to the next batch of unpurified
nitronaphthalene. It is assumed that the DuPont melt crystallization step is
very similar to the process used by Allied.
The purified a-naphthylamine was then reduced to a-naphthylamine
by the Bechamp iron reduction process. A ferrous chloride solution (made from
32% hydrochloric acid and 20% mesh iron) was charged into water and the mix-
ture was heated to a boil. Equal weights of molten a-nitronaphthalene and
fresh iron borings were added to the boiling solution. After several hours
of heating under reflux, the reduction was complete and NaJ;>CO was added to
neutralize the FeCl,,. The u-naphthylamine and water were distilled under
vacuum. The overall reaction proceeds approximately according to the follow-
ing equation (Shreve, 1963):
:oTo,
FeClr
3Fe + 4H00
+ Fe(OH)2 + FeO + Fe(OH) + (H)
Fe(OH)2 + Fe(OH)3
•* Fe3°4 + 4H2°
The a-naphthylamine was separated from the water solution by
a flash distillation process and stored in the molten state (approximately
99.7% pure). Unreacted iron borings were recovered and reused. Overall
yield of a-naphthylamine ran about" 85-90% based upon initial naphthalene
starting material.
23
-------
Approximately one-half of the Allied Chemical a-naphthylamine
was shipped in molten form via tankers to herbicide manufacturers. A large
portion of the remaining one-half was sulfonated to produce naphthionic acid
and sodium naphthionate for use in dye manufacture, especially for F & DC
Red No. 2. A very small portion of the a-naphthylamine was used to make the
dye intermediate l-naphthol-4-sulfonic acid (Nevile and Winther's Acid). The
remaining a-naphthylamine was flaked for captive dye production and for sale
(fiber drums) in the open market.
3. GAP Corp. (Rensselaer, N.Y.)
GAF Corp. terminated production in 1960. It is believed that
GAF production was used captively to produce dyes, although no production
figures were available. Because consumption was mostly for dyes, the amount
of a-naphthylamine made by GAF was probably insignificant as compared to
DuPont and Allied.
24
-------
V. Use Process Technology
A. Herbicides
1. Processing Sites
Present processing plants, which manufacture herbicide products
from a-naphthylamine, are listed in Table V-l by company, product, and estimate
of production volume.
2. Process Description
Only one herbicide ingredient derived from a-naphthylamine is
domestically produced; it is commonly called naptalam (N-1-naphthylphthalamic
acid). The various products listed in Table V-l are all formulations derived
from naptalam. The general process .flow diagrams for naptalam production are
illustrated in Figures V-l and V-2. The only major difference in the process
diagrams is the method for separating the naptalam from the reaction medium.
The a-naphthylamine, which is shipped to the herbicide producers
ti
in a molten state via railroad or truck tanker, is pumped directly from the
tanker into a stainless steel reactor. The reactor has been previously charged
with a solution of phthalic anhydride in benzene, xylene, or kerosene. The
benzene, xylene, or kerosene solvents are used because both phthalic anhydride
and a-naphthylamine are soluble in them. The a-naphthylamine and phthalic
anhydride react to produce N-1-naphthyl phthalamic acid (naptalam) according
to the following equation:
0 NHr
I
t ^-
\
0
25
N-1-naphthylphthalamic Acid
(Naptalam)
-------
Table V-l. Processing Sites for a-Naphthylamine Herbicides
Company
Site
Products
Estimated* Production,
Active Ingredients, Ibs
1. Uniroyal, Inc.
Uniroyal Chemical, division
Gastonia, NC
2. North American Philips Corp. Kansas City, KA
Thompson-Hayward Chemical Co., subs.
3. Helena Chemical Company
W. Helena, AK
Alanap Qy
Dyanap ®
Moran-Cran ®
Solo®
NPA-3
Ancrak ^
Marauder
4 Million
1 Million
1 Million
* SRC estimates
-------
BENZENF
OR
XYLENE
OR
KEROSENE
MAKE-UP
PHTHALIC
ANHYDRIDE
a-NAPHTHYLAMINE
TANKER
Figure V-l.
Manufacturing Process for a-Naphthylamine-Derived Herbicides (adapted from information
from Smith and Hoffman, 1950; various personal communications; SRC Estimations)
-------
D
I
8
CD
BENZENE
OR
XYLENE
OR
KEROSENE
MAKE-UP
to
00
PHTHAL1C
ANHYDRIDE
CHARGE
TANK
EXTRACTOR
a-NAPHTHYLAMINE
TANKER
REACTOR
SODIUM
DNBP
MIXER
HOLDING
TANK
Figure V-2. Manufacturing Process for a-Naphthylamine-Derived Herbicides (adapted from information
from Smith and Hoffman, 1950; various personal communications; SRC Estimations)
-------
The naptalam, which is nearly insoluble in the organic solvent,
precipitates out of the solution. The reaction is carried out at room tempera-
ture and atmospheric pressure (Smith and Hoffman, 1950).
The naptalam can now be separated from the organic solvent by
filtration or extraction as illustrated in Figures V-l and V-2, respectively.
In the filtration process, the naptalam is collected from the filters while
the organic solvent is recycled to the reactor and reused. The water insoluble
naptalam is now converted to water soluble naptalam (sodium N-1-naphthylphthala-
mate) by reaction with solutions of either sodium hydroxide or sodium bicar-
bonate.
(1)
Although any sodium base can theoretically be used, selection is probably
based upon cost.
In the extraction process, separation from the organic mixture
and conversion to sodium naptalam can be accomplished in a single step. The
organic solvent, containing the precipitated naptalam, is contacted with the
alkaline aqueous solution and the naptalam forms the sodium naptalam which
dissolves into the water phase. The organic solvent is recycled to the reactor
for reuse while the sodium naptalam solution, the desired product, is collected
29
-------
for formulation into the final herbicide product. The sodium naptalam solution
may be concentrated by water removal via contact evaporators or other common
water removal equipment.
It should be noted that naptalam is unstable in aqueous solutions
with s. pH greater than 9.5 and temperatures above 200°C. At a pH more alkaline
than 9.5, naptalam will hydrolyze to a-naphthylamine (Smith and Stone, 1950;
Spencer, 1968).
The sodium naptalam solution is used to formulate the herbicide
products. A straight sodium naptalam solution, two pounds sodium naptalam
®
per gallon, is marketed under the tradename Alanap by Uniroyal. However,
more than 90% of the sodium naptalam produced is formulated with the sodium
salt of DNBP (sodium 4,6-dinitro-2-sec-butylphenate) (Dowling, 1975). DNBP
(4,6-dinitro-2-sec-butylphenol) is a herbicide marketed by Dow Chemical with
the common name dinoseb. The resulting formulation is a mixture of two pounds
sodium naptalam plus one pound sodium DNBP per gallon (Anon., 1974 a). This
particular mixture is marketed under the following tradenames and companies:
(JD (ID
Dyanap (Uniroyal), Ancrakw (Ansul Co.), NPA-3 (Thompson-Hayward), and Marauder
(Helena Chemical Co.).
It should be noted that the Ansul Co. does not manufacture their
®
product (Nicklaus, 1975). The Ancrak is manufactured by the Helena Chemical Co.
for the Ansul Co. (Liggin and Holloway, 1975).
Two additional formulations utilizing sodium naptalam are pro-
duced by Uniroyal (Dowling, 1975). The one is Mor-Cran which mixes 8.1% (by
weight) sodium naptalam with 5.0% (by weight) Chloro-IPC (Isopropyl N-(3-
(S)
Chlorophenyl) Carbamate) per gallon. Another is Solo , which also formulates
Chloro-IPC with sodium naptalam. The percent by weight in the liquid formulation
30
-------
is sodium naptalam 23.6% and Chloro-IPC 22.2% per gallon. The granular solid
(S-D
Solo^mixes 10.7% sodium naptalam, 10.3% Chloro-IPC, and 79.0% inert ingredi-
ents per pound.
The liquid formulations of sodium naptalam are stored in holding
tanks which dispense them to containers for shipment to customers. The con-
tainers range from 5 gallon plastic bottles and plastic-lined cans to 30 and
55 gallon drums. Shipment can also be made via railway tankers. There are
no special shipping regulations other than labelling. Any mixture utilizing
DNBP must be labelled a Class B Poison, due to the presence of DNBP.
3. Environmental Management
There is no waste disposal during the production of naptalam
(Porter, 1975; Liggin and Holloway, 1975). From Figures V-l and V-2, it can
be seen that the entire process is carried out within a closed system. Any
a-naphthylamine which does not react with the phthalic anhydride will remain
dissolved in the organic solvent and be recycled to the charge tank and reactor.
The a-naphthylamine contamination in the final product is discussed in Section VI-B.
The only waste which occurs, other than possible pipe or valve
failure, results from the infrequent cleaning of the reactors and changing of
the organic solvent. The organic solvent will need to be changed due to build-
up of impurities. The solvent will contain a very small, but unknown, amount
of dissolved a-naphthylamine. Helena Chemical Co. (Liggin and Holloway, 1975)
transfers cleaning wastes to settling ponds for treatment. Uniroyal and
Thompson-Hayward's methods for handling cleaning wastes were not available.
However, a-naphthylamine escape to the environment via this route is probably
insignificant.
31
-------
4. Future Manufacturers
Crystal Chemical Co. of Houston, Texas, reports (Mllligan, 1975)
that plans have been proposed to begin production of a herbicide called "Naphthro"
in 1977. This herbicide will be very similar to the a-naphthylamine herbicides
already marketed.
5. Herbicide Uses
a. Historical - Naptalam Use
Table V-2 lists annual volume of naptalam production from
1964, and the corresponding amount of a-naphthylamine used to make the naptalam.
b. Crop Protection
All three naptalam producers report (Liggin and Holloway,
1975; Fox, 1975; Dowling,"1975) that almost all production is used for pre-
emergent protection of soybeans and peanuts.
(§) (E)
The formulations containing DNBP (Dyanap , Ancrak^, NPA-3,
Marauder) are applied up to the time of crop emergence for peanuts and before
crop emergence for soybeans (Anon., 1974 a).
A small percentage of the naptalam produced by Uniroyal is
(5) (§)
marketed as Alanap (Porter, 1975; Bowling, 1975). Alanap is used in liquid
formulation for control of numerous broadleaved weeds in soybeans. A 10% granu-
lar formulation is registered for use on soybeans, sweet potatoes, Irish pota-
toes, and vine crops (Anon., 1974 a).
Naptalam is unique because of its selective characteristics
favorable to cucurbit crops, soybeans, peanuts, asparagus, sweet potatoes, and
cotton. It does not kill by contact but acts rather on the seed as it ger-
minates or through the root system. Plants that are tolerant can withstand
32
-------
Table V-2. Annual Production of Naptalam, 1964-1974
1974
1973
1972
1971
1970
1969
1968
1967
1966
1965
1964
Amount of a-Naphthylamine
Naptalam Production Used To Produce Naptalam
(103 Ibs) (103 Ibs)
60001 3000
—
4000 1978
33322 1630
—
—
—
—
9992 490
—
10603 520
SRC Estimation
2
U. S. Department of Agriculture, 1974
3Wherry, 1968
33
-------
a second post-emergence treatment, thereby prolonging the control (Wherry,
1968).
c. Areas of Usage
Specific crop usage and acres treated with naptalam in
1971 are listed in Table V-3, while usage by states in 1971 is listed in
Table V-4.
6. Economics
The following is a rough estimation of the material costs for
a-naphthylamine-derived herbicide production:
Raw Materials & Cost
a-Naphthylamine $1.10/lb (Boyd, 1975-1976)
Phthalic Anhydride $0.24/lb (Chemical Marketing Reporter, 1976)
Sodium Hydroxide $0.125/lb
Step #1: Precipitation reaction of cx-naphthylamine and phthalic
anhydride:
(m.w. 148) (m.w. 143)
Basis; 1-lb-mole of naptalam (100% yield)
a-Naphthylamine 143 Ib = $157.30
Phthalic Anhydride 148 Ib = $ 35.52
$192.82
Naptalam Cost: $192.82/291 Ibs or $0.663/lb
34
-------
Table V-3. Usage of Naptalam in 1971, Quantities + Acres
Crop
Soybeans
Peanuts
Cotton
Sorghum
Others
Total
3
Quantity (10 Ibs
Active Ingredient)
2956
324
4
2
46
3332
Acres Treated
3751
349
17
2
18
4137
"U. S. Department of Agriculture, 1974
Table V-4. Usage of Naptalam by States in 1971
3
„ Quantities (10 Ibs
States Region Active Ingredient)
Delta States 1783
Southeast 747
Corn Belt 407
Appalachian 372
Northern Plains 11
Southern Plains 8
Lake States 4
Total 3332
U. S. Department of Agriculture, 1974
2
See Figure V-3 for region identification
35
-------
FARM PRODUCTION REGIONS
U.S. DEPARTMENT OF AGRICULTURE
NEC. ERS I3WA-62IB) ECONOMIC RESEARCH SERVICE
Figure V-3. Farm Production Regions
36
-------
Step #2: Conversion of naptalam to sodium naptalam
NaOH
-COONa
.CONH
(m.w. 291) (m.w. 40) (m.w> 313)
Basis; 1-lb-mole of naptalam (100% yield)
Naptalam 291 Ib = $192.82
Sodium Hydroxide 40 Ib = $ 5.00
$197.82
Sodium Naptalam Cost: $197.82/313 Ibs or $0.632/lb
This $0.63/lb is material cost only and is an approximation
at best. The xylene or benzene solvent cost of $0.50 to $0.75 per gallon has
not been included; however, it is reusable and is changed only periodically.
The current retail selling price of sodium naptalam (solution)
is $42.00/5 gals with 2 Ibs of sodium naptalam per gallon (Agway, 1975;
Woolfolk Chemical Works, Inc., 1976). This makes the retail price of sodium
naptalam approximately $4.20 per Ib. Mark-up includes costs for labor, equip-
ment, packaging, profits, distributors, etc.
Capital value of existing equipment was unavailable from the
herbicide producers.
Most sodium naptalam is sold in formulation with the sodium
salt of DNBP (sodium 4,6-dinitro-o-sec-butyIphenate). DNBP is a general con-
tact herbicide produced by the Dow-Chemical Company (Anon, 1974 a). The
37
-------
retail selling price of the sodium naptalam formulations (Dyanap , Ancrak;
is currently $7.65 per gallon (Agway, 1975; Woolfolk Chemical Works, Inc.,
1976). Using that price as a basis, the total sales of a-naphthylamine de-
rived herbicides would presently be approximately $20 million. However, herbi-
cide products are capable of having prices negotiated downwards for large volume
sales (Agway, 1975; Woolfolk Chemical Works, Inc., 1976).
7. Alternative Final Use Products - Herbicides
a. Products and Usage
Table V-5 lists the quantities of naptalam used in 1971 and
the major herbicides which could be used as alternatives in two large outlets
for naptalam. Product chemistry and producers of these alternative herbicides
are listed in Table V-6.
b. Comparative Cost and Persistence
Comparative cost to farmers and the persistence of naptalam
and the major alternatives are listed in Table V-7. Table V-7 also includes
(5) ©
the naptalam formulations of Dyanap and Ancrak .
Most of the naptalam is applied by farmers as Dyanap^ and
Ancrak . The cost (from Table V-7) of $3-$4 per acre usage is very competitive,
especially in view of the following considerations. The naptalam formulations
offer a wide range of herbicide protection, including control of most broad-
leaved weeds common to soybean crops. The formulations are easy to apply, can
be used for both pre- and post-emergent protection on soybeans, and need not be
incorporated into soil. Most of the alternatives to naptalam need to be incor-
porated into soil and cannot be used for post-emergent protection. For example,
both these requirements apply to the relatively inexpensive Linuron (Lorox\)
(see Table V-7). Furthermore, it can be used only for selective weed control.
Naptalam does, however, have limitations with certain soil types.
38
-------
Table V-5. 1971 Use of Naptalam and Alternative Herbicides
(U.S. Department of Agriculture, 1974)
Naptalam
Linuron
Alachlor
Vernolate
Amiben
Trifluralin
Total U.S. Use
in 1971 (103 Ib)
3332
1803
14754
3736
9555
11427
Soybean Use in
1971 (103 Ib)
2956
837
6308
1446
9340
5962
Peanut Use
1971 (103
324
—
56
2283
—
141
in
Ib)
39
-------
Table V-6. Chemistry of Alternative Products for Naptalam Applications (Spencer,
1968; Anon., 1974 a; Agway, 1975; Woolfolk Chemical Works, Inc., 1976)
1. Linuron (Lorox;
Chemical Name: 3-(3,4-Dichlorophenyl)-l-methoxy-l-methylurea
Manufacture: Reaction of 3,4-dichlorophenyl isocyanate and N-methyl
hydroxyl amine followed by methylation
0 CH.
II II 3
NH— C—N— 0— CH
Use: Pre-emergent weed control
Formulation: Wettable power containing 50% active ingredient;
Emulsifiable liquid (4 Ib/gal)
Basic Producer: DuPont
2. Alachlor (Lasso^)
Chemical Name: 2-Chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide
-3
0
I
CH2CH3
Use: Control of annual grasses and certain broadleaf weeds. Leaves
no residue in soil to carry over to next year. Can be pre-plant
or surface applied. Can be mixed with Linuron for soybeans.
Formulation: 4 Ib/gal Emulsifiable concentrate
Basic Producer: Monsanto Co.
40
-------
Table V-6. Chemistry of Alternative Products for Naptalam Applications (Spencer,
1968; Anon., 1974 a; Agway, 1975; Woolfolk Chemical Works, Inc., 1976)
(Cont'd)
3. Vernolate (Vernanr;
i
Chemical Name: ri-Propyl-di-n-propylthiolcarbamate
Manufacture: From di-propylcarbamylchloride and propyl mercaptan
0 CH-CH_CH
CH — CH — CH — S— C— N
Use: Control of grass weeds
CH2— CH2—
Formulation: Emulsifiable liquid (6 lb:/gal) ;
Granule (10%):
Basic Producer: Stauffer Chemical Co.
4. Amiben
Chemical Name: 3-Amino-2,5-dichlorobenzoic acid
COOH
Cl
Use: Pre-emergent weed control
Formulation: Granular and liquid (2 Ib/gal)
Basic Producer: Amchem Products, Inc.
41
-------
Table V-6. Chemistry of Alternative Products for Naptalam Applications (Spencer,
1968; Anon., 1974 a; Agway, 1975; Woolfolk Chemical Works, Inc., 1976)
(Cont'd)
5. Trifluralin (Treflari^)
Chemical Name: a,a,ot-Trifluoro-2,6-dinitro-N,N-dipropyl-p_-toluidine
Manufacture: Reaction of 4-trifluorodinitrochlorobenzene with dipropylamine
Use: Weed control. Application made after thinning or blocking and
must be incorporated in top 2 to. 4 inches of soil immediately.
Will not control established weeds.
Formulation: Emulsifiable concentrate (4 Ib/gal);
Granular 5%
Basic Producer: Elanco Products Co., division of Eli Lilly and Co.
42
-------
Table V-7. Alternative Herbicide Products—Comparative Cost and Persistence
Current Retail
Selling Price/Unit
Approximate
Cost to Farmer
o
Per Acre Use'1
Persistence Time in
Months for 75-100%
Disappearance
4
Naptalam
Linuron
Alachlor
Vernolate
Amiben
Trifluralin
uyanap
Ancrak
$8.40/gal
$3.70/lb
$15.00/gal
$17.95/gal
$11.10/gal
$31.20/gal
$7.65/gal
$7.65/gal
$4-$5
$Us-$2l5
$4-$5
$7-$8
$5-$6
$5-$6
$3-$4
$3-$4
1-3
3-10
1-3
1-3
1-3
1-3
1-3
1-3
Agway (1975); Woolfolk Chemical Works, Inc. (1976)
Calculated from data from U. S. Department of Agriculture (1974); Agway (1975);
and Woodfolk Chemical Works, Inc. (1976)
Von Rumker et al. (1974)
Current price for Alanap
43
-------
]}. Dyes
1. Processing Sites
a-Naphthylamine-derived dye processing sites are listed in
Table V-8 by company, products, and estimated annual production.
2. Process Description
The general method for dye production incorporating a-naphthylamine
is illustrated in Figure V-4.
The diazotization reaction occurs in a batch reactor made of
either wood or coated metal. The most convenient solvent for the diazotization
is water, which is used whenever possible (Donaldson, 1958), as is the case
with a-naphthylamine.
The initial amine chemical intermediate (usually not a-naphthyl-
amine) is dissolved in water, usually as the hydrochloride, and introduced into
the reactor where it is cooled to 0°C by addition of crushed ice while hydro-
chloric acid is slowly added. To the resulting solution or suspension, a solu-
tion of sodium nitrite is rapidly injected under the surface and reacts with a
portion of the hydrochloric acid to form nitrous acid:
slow
HC1 + NaN02 , >- NaCl + HONO > NO
The nitrous acid diazotizes the initial chemical intermediate
by the following proposed mechanism (March, 1968):
1. Ar — NH,, + NO >• Ar-—NH^—N= 0 + NO,,
-
2. Ar — NH2-N=0 - - - >• Ar — NH— N=rO
3. Ar — N — N = 0 - ,. Ar — N=N — OH
I-
H
A. Ar — N=N —OH >- [Ar — N=N]C1 + HO
-------
Table V-8. Processing Sites for a-Naphthylamine Dyes
Company
1. American Color & Chemical Co.
2. Crompton & Knowles Corp.
3. GAF Corp.
4. Harshaw Chemical Co.,
Div. of Kewanee Oil Co.
Site Products
Reading, PA Acid Orange 116
Acid Blue 113
Acid Black 24
Direct Blue 71
Direct Blue 78
Disperse Black 1
Gibraltar, PA Acid Blue 113
Direct Blue 78
Disperse Black 1
Others (Classified
Structures)
Rensselaer, NY Acid Orange 116
Acid Blue 113
Acid Black 24
Disperse Black 1
Louisville , . KY Pigment Red 54
Lowell, NC Direct Blue 126
2
Estimated Annual
Dye Production,
Active Ingredients Capacities
<2 Million Ibs N.A.
<2 Million Ibs N.A.
-------
a -NAPHTHYLAMINE
HYDROCHLORIC
ACID
SOLUTION
STEP 2
HCI t NO2
ICE
STEP 4
Na2CO3
STEPb
NaCI
CHEMICAL
INTERMEDIATES
(AROMATIC AMINE)
WASTE
DISPOSAL
Na2SO4
NON-DUSTING AGENTS
SURFACTANTS
DFXTRINS
Figure V-4. Dye Process Schematic (adapted from information from Donaldson, 1958; various personal
communications)
-------
Sufficient hydrochloric acid has been previously added to insure formation of
+
the diazonium chloride (Ar-N N Cl). Tests are conducted to make sure diazoti-
zation is completed.
The a-naphthylamine is converted to the more water soluble hydro-
chloride salt prior to addition to the reactor by dissolving it in boiling water
containing hydrochloric acid. This solution is allowed to cool to 50°C and is
then charged into the reactor at a rate determined by previous experience.
Crushed ice is periodically added to maintain a temperature range of 0°-5°C
in the reactor to prevent decomposition of the diazonium chloride. When the
coupling reaction is complete, the diazonium chloride and a-naphthylamine will
form a monoazo-dye. If another chemical intermediate is to be coupled to this
monoazo-dye, which is usually the case, hydrochloric acid and sodium nitrite are
added to diazotize the monoazo-dye, and the process proceeds as previously de-
scribed. The entire process may take several days to complete (Allied Chemical
Corp. , 1975).
As an example, consider Acid Blue 113, which is the largest
volume a-naphthylamine-derived dye produced in the United States:
Step //I; Diazotization of metanilic acid
HC1
HONO
-H20
•N=N Cl
Step #2; Addition of a-naphthylamine (hydrochloride) to form
monoazo-dye
47
-------
HO S
J
Step #3; Diazotization of monoazo-dye
HONO
N sN 01
Step /M; Addition of N-phenyl Peri acid and neutralization
to form Acid Blue 113
= N Cl +
Na2C°3
-HC1
NaO S
(Acid Blue 113)
Sodium carbonate is added to the reactor to neutralize any excess
acid. The dye, which is water soluble, is now "salted-out" (precipitated-out)
of solution by addition of sodium chloride. This "mother liquor" is now trans-
ferred from the reactor to filter presses to remove the excess water and to
collect the solid dye. The excess water goes to waste disposal while the
"filter cakes" (the solid dyes) are thoroughly dried in ovens and then granu-
lated by mechanical means to the required mesh sizes.
48
-------
The granulated dye is taken to the packaging department and
"cut" to commercial strength by additions of sodium sulfate, non-dusting agents,
surfactants, dextrins, and other inert ingredients. The actual dye content of
the final product may be as low as 25% (Rounds, 1975).
The commercial strength dye is packaged into common fiberboard
drums for shipment to customers. There are no shipping regulations or required
safety precautions during shipment of any a-naphthylamine-derived dyes.
3. Environmental Management
Effluents from a-naphthylamine dye production that need to be
dispoised of originate at the filter pressing stage as shown in Figure V-4.
At this stage, the "mother liquor" is forced against filter cloth which sepa-
rates the dye solids from the excess liquid. This excess liquid will mainly
be a saline solution, but it will also contain small amounts of dye, unreacted
intermediates, and possibly some excess acid. After adjusting the pH, the
excess liquid is released to city or county sewage systems or to the ocean.
Disposal methods used by the current manufacturers are listed in Table V-9.
The disposed dye and unreacted intermediates will be discussed in Section VI-C
(Material Balance - Exposure to the Environment).
4. Use
Table V-10 lists the quantities of a-naphthylamine used for
domestic dye production for 1964-1973. The production quantities and prices
of the individual a-naphthylamine derived dyes for 1964-1973 are listed in
Table V-ll. Table V-12 lists the companies and the a-naphthylamine dyes they
produced from 1964-1973.
49
-------
Table V-9. Disposal of Dye Wastes
Ul
o
Manufacturer
1. American Color & Chemical Co.
2. GAF Corp.
3. Crompton & Knowles Corp.
4. Harshaw Chemical Co.
Div. of Kewanee Oil Co.
Site
Reading, PA
Rensselaer, NY
Gibraltar, PA
Louisville, KY
Lowell, NC
EPA Region Disposal
III City or county, sewage system
II City or county sewage system
III To the ocean
IV City or county sewage system
IV City or county sewage system
Alternative disposal methods are being evaluated (Horning, 1975)
-------
Table V-10. Annual Consumption of a-Naphthylamine Used in Dye Production
Year Quantity (1Q3 Ib)1
1973 840
1972 930
1971 840
1970 690
1969 720
1968 690
1967 450
1966 570
1965 620
1964 610
SRC Estimation
51
-------
Table V-ll. Dyes Made Directly from a-Naphthylamine (U.S. International Trade Commission, 1960-1973)
Acid Orange 116
Acid Red 17
Acid Blue 113
Acid Blue 1.20
Acid Black 2k
Acid Black 26B
Azoic Coupling C. 4
Direct Blue 71
t_n
|O Direct Blue 78
Direct Blue 81
Direct Blue 126
Disperse Black 1
Solvent Black 3
Pigment Red 54
1974*
531(2., '9)
523(2.59)
(3.71)
(4.29)
(2.31)
L973
iM(2.46)
34 —
841(2.42)
--
--
-
--
131(3.68)
105(3.44)
93(3.33)
— (1.92)
-
76(2.58)
Production Quantities in LO Ibs; Prices in Pricc/lh (in Pjrontheses)
1972
799(2.29)
—
842(2.52)
34 —
54(2.07)
~
-
118(3.12)
133(3.26)
144(3.21)
335(1.70)
—
78(2.57)
I97l_
746(2.27)
832(2.31)
— (2.111
— (2.07)
—
--
— (3.14)
141(3.20)
203(3.36)
— (1.89)
"
1970
•546(2.20)
„
623(2.09)
-- (1.95)
-- (1.86)
—
23(2.33)
36(3.12)
72(3.24)
142(3.21)
238(1.87)
-
87(2.26)
1969
618(2.21.)
X
681(2.11)
-- (2.05)
89(1.78)
—
16(1.95)
— (2.80)
141(3.24)
155(3.00)
X
—
—
1968 1967
548(2.24)
—
729(1.88)
--
96(1.83)
—
23(2.20)
50(2.84)
120(2.98)
-- (2.81)
188(1.76)
--
71(2.28)
282(2.24)
--
532(1.76)
-
61(1.74)
-'-
8(2.00)
35(2.60)
118(2.93)
X
130(2.81)
102(1.43)
—
72(2.31)
1966 •
297(2.17)
—
564(1.45)
—
129(1.67)
-
39(2.11)
—
129(2.77)
X
292(2.97)
156(1.76)
~
59(2.28)
1965
X
357(1.51)
—
101(J .75)
—
53(2.00)
80(2.93)
124(2.81)
142(2.64)
344(1.22)
—
69(2.21)
1964
--
345(1.39)
--
92(1.78)
—
-- (2.14)
62(2.59)
83(2.82)
X
185(2.47)
342(1.18)
-
—
* Preliminary figures
— Produced hut production and sales data were unavailable.
X Not produced
-------
Table V-12. a-Naphthylamine Dye Producers and Products, 1964-1973
(U.S. International Trade Commission, 1960-1973; Anon., 1974 b)
Note: Parenthesized years indicate production years; all = 1964-1973.
5.
6.
7.
8.
Note: Parenthesized years indicate production years; all
* Indicates no longer manufacturing a-naphthylamine.dyes.
'''Allied Chemical—Specialty Chemicals Div. ; Buffalo, NY
Acid Orange
Acid Blue
Acid Blue
Acid Black
Acid Red
116 (all)
113 (1966-1973)
120 (all)
24 (all)
17 (all)
Direct Blue
Direct Blue
Direct Blue
Solvent Black
71 (all)
78 (all)
126 (1964-1967)
3 (all)
American Color & Chemical Corp.; Lock Haven, PA
(American Aniline Products)
Disperse Black 1 (all)
^Atlantic Chemical Corp.; Nutley, NJ
Acid Orange
Acid Blue
Acid Blue
Acid Black
Acid Red
116 (1965, 69, 73)
113 (1966-1973)
120 (1969-1973)
26B (1970-1973)
17 (all)
Direct Blue
Direct Blue
Direct Blue
Direct Blue
Direct Red
71
78
81
126
7
Azoic Coupling Component 4 (1964, 64, 67, 69-73)
*Baychem Corp.; Bayonne, NJ
Acid Orange 116 (1972)
Direct Blue 71 (1971)
Direct Blue 126 (all)
*Benzenoid Organics, Inc.; Bellingham, MA
Acid Blue 113 (1965-1973)
*Bernscolors-Poughkeepsie Inc.; Poughkeepsie, NY
Acid Blue 113 (1969-1973)
*Blackman-Uhler Chemical Co.; Spartanburg, SC
Azoic Coupling Component 4 (all)
Crompton & Knowles Corp.; Gibraltar, PA
Acid Orange 116 (1965-1973)
Acid Blue 113 (1967-1973)
9. *E. I. duPont; Deepwater Point, NJ
Acid Blue 113 (all)
Acid Black 24 (all)
Acid Black 26B (all)
Disperse Black 1 (all)
Direct Blue
Direct Blue
Direct Blue
71
78
126
(1964, 65, 69-73)
(all)
(all)
(1969-1973)
(1966-1973)
(1964-1968)
(all)
(1964-1968)
53
-------
Table V-12. a-Naphthylamine Dye Producers and Products, 1964-1973
(U.S. International Trade Commission, 1960-1973; Anon., 1974 b)
(Cont'd)
.1.0. '''Fabricolor Inc.
Acid Orange
Acid Blue
Paterson, NJ
116 (1968-1973)
113 (1968-1973)
11. GAP Corp.; Rensselaer, NY
Acid Orange
Acid Blue
Acid Blue
Acid Black
Acid Black
.116
113
120
24
(1966-1973)
(all)
(all)
(all)
Direct Blue
Direct Blue
Direct Blue
Disperse Black
71
78
126
1
(all)
(1964-1967)
(1968-1968)
(all)
26B (1973)
12,
Azoic Coupling Component 4 (1964-1972)
Harshaw Chemical Co.; Louisville, KY
Pigment Red 54 (all)
13. *Hercules, Inc.; Glens Falls, NY
Pigment Red 54 (all)
14. *Max Marx Color & Chemical Co.; Irvington, NJ
Pigment Red 54 (1964-1967)
15. *Nyanza Inc.; Ashland, MA
Acid Orange 116 (1972-1973)
Acid Blue 113 (all)
Acid Black
Direct Blue
24 (1964-1971)
78 (all)
16. *Pfister Chemical Inc.; Charlotte, NC
Azoic Coupling Component- 4 (1965-1970)
17. *Sterling Drug, Inc. (Hilton-Davis Chemical); Cincinnati, OH
Pigment Red 54 (all)
18. *Tenneco Inc.; Reading, PA
' Acid Orange 116 (1964, 66-71, 73)
Acid Blue 1.13 (1965-1973)
Acid Blue 120 (1964)
19. *Toms River Chemical Corp.; Toms River,
Acid Orange 116 (all)
Acid Blue 113 (1.967-1973)
Acid Black 26B (1964-1972)
Acid Red 17 (all)
NJ
Direct Blue 71
Direct Blue 78
Direct Blue 126
Disperse Black 1
(all)
(all)
(all)
(all)
20. *J. S. Young (Young's Aniline Works); Baltimore, MD
Acid Orange 116 (1969-1973)
Acid Blue 113 (1970-1973)
Acid Red 17 (1964-1969)
54
-------
Table V-12. a-Naphthylamine Dye Producers and Products, 1964-1973
(U.S. International Trade Commission, 1960-1973; Anon., 1974 b)
(Cont'd)
21. *John Campbell & Co.; Perkasie, PA
Acid Blue 113 (to 1973)
Acid Black 24 (to 1973)
Acid Red 17 (to 1973)
22. "Sandoz-Wander, Inc.; Hanover, NJ
Acid Orange 116 (to 1973)
Acid Blue 113 (to 1973)
Acid Red 17 (to 1973)
Acid Blue 120 (to 1973)
Direct Blue
Direct Blue
Acid Black
Direct Blue
Direct Blue
Direct Blue
71
78
(to 1973)
(to 1973)
26A (to 1973)
71 (to 1973)
78 (to 1973)
126 (to 1973)
23. *0rganic Chemical Corp.; E. Providence, RI
Acid Blue 113 (to 1973)
24. *ICI America, Inc; Dighton, MA
Acid Blue 113 (to 1973)
55
-------
Table V-13 contains information on the individual ot-naphthyla-
mine-derived dyes such as estimated current annual production, chemical formula,
raw materials and synthesis approaches, and current producers.
5. Economics
The following is a rough estimation of the material costs.of
the major intermediates used in a-naphthylamine-derived dye production (Chemical
Marketing Reporter, 1976; various personal communications):
a-Naphthylamine (flaked) $1.45/lb
Metanilic Acid' $1.35/lb
N-Phenyl-Peri Acid $1.35/lb
_p_-Cresol $0.72/lb
5-Amino-l-Naphthalenesulfonic Acid $0.87/lb
1,7-Cleve's Acid $2.42/lb
J Acid (6-Amino-l-naphthol-3-sulfonic acid) $4.72/lb
N-Phenyl-J Acid $4.72/lb
_p_-Nitroaniline $0.84/lb
l-Naphtho.l-5-Sulfonic Acid $2.25/lb
Sodium Nitrite $0.19/lb
Hydrochloric Acid $0.22/lb
Consider Acid Blue 113 (Metanilic Acid *• a-Naph thy la-
mine >• N-Phenyl-Peri Acid). The raw material costs amount to approxi-
mately $2.70 per pound of Acid Blue 113. However, the 100% strength dye is
"cut" to commercial strength by addition of inert ingredients such as sodium
sulfate and dextrins. This enables the dye purchasers to more accurately
weigh-out a specific strength of dyes, and at the same time, aid the dyeing
56
-------
Table V-13. Dyes Manufactured from a-Naphthylamine (Anon., 1974 b; Colour
Index; various personal communications)
1. Acid Orange 116
Estimated Annual Production:
Chemical Formula:
<1 million pounds
OH
N=N
Raw Materials: Metanilic Acid
CH,
a-Naph thylamine
Current Producers and Tradenames:
GAP Corp. - Nyliton Fast Orange DNL
American Color & Chemical Co. - Duronyl Fast Orange LSF
jg-Cresol
2. Acid Blue 113
Estimated Annual Production: <1 million pounds
Chemical Formula:
NaO S
£
•
Raw Materials: Metanilic Acid
a-Naphthylamine
Current Producers and Tradenames:
Crompton & Knowles Corp. - Intrazone Blue 5R
GAF Corp. - Sulpho Cyanine 5RA or Fenazo Blue 5RA
American Color & Chemical Co. - Amacid Cyanine 5RA
N-Phenyl Peri Acid
57
-------
Table V-13. Dyes Manufactured from a-Naphthylamine (Anon., 1974 b; Colour
Index; various personal communications) (Cont'd)
3. Acid Black 24
Estimated Annual Production: <100,000 pounds
Chemical Formula:
Raw Materials: 5-Amino-l-Naphthalenesulfonic Acid
N-Phenyl Peri Acid
a-Naph thylamine
Current Producers and Tradenames:
GAF Corp. - Sulphon Cyanine Black BA
American Color & Chemical Co. - Durosol Milling Black B
4. Acid Black 26A
Chemical Formula:
CH
Raw Materials: 5-Amino-2-(o-toluido)-benzenesulfonic Acid -»•
a-Naphthylamine »• 2-Hydroxy-6-naphthalenesulfonic Acid
(Schaeffer's Acid)
Current Producers: None
58
-------
Table V-13. Dyes Manufactured from a-Naphthylamine (Anon., 1974 b; Colour
Index; various personal communications) (Cont'd)
5. Acid Blue 120
Chemical Formula:
NaO S
Raw Materials: Metanilic Acid
N-_p_-Tolyl Peri Acid
Current Producers: None
•*• a-Naphthylamine
6. Acid Red 17
Chemical Formula:
HO SC- Na
J
Raw Materials: a-Naphthylamine
Acid (R Acid)
Current Producers: None
3-Hydroxy-2,7-Naphthalendisulfonic
59
-------
Table V-13. Dyes Manufactured from a-Naphthylamine (Anon., 1974 b; Colour
Index; various personal communications) (Cont'd)
'7. Direct Blue 71
Estimated Annual Production: Not Available
Chemical Formula:
= N-
e
=. N
Raw Materials: 3-Amino-l,5-Naphthalenedisulfonic Acid
a-Naph thy lamine •»• 1,7-Cleve's Acid -
6-Amino-l-Naphthol-3-Sulfonic Acid (J Acid)
Current Producer and Tradename:
American Color & Chemical Co. - Amanil Fast Blue FFB
8. Direct Blue 78
Estimated Annual Production: Not Available
Chemical Formula:
£>>•=
NaO S
Raw Materials: 2-Amino-p_-Benzenedisulfonic Acid : >•
1,7-Cleve's Acid *• a-Naph thy lamine
N-Phenyl J Acid
Current Producers and Tradenames:
American Color & Chemical Co. - Amanil Fast Blue 4GL
Crompton & Knowles Corp. - Intralite Blue AGL New
60
-------
Table V-13. Dyes Manufactured from a-Naphthylamine (Anon., 1974 b; Colour
Index; various personal communications) (Cont'd)
9. Direct Blue 81
Chemical Formula:
Raw Materials: o-Phenylsulfonyl H Acid >• a-Naphthylamine
1,7-Cleve's Acid >• N-Phenyl j Acid
Current Producers: None
10. Direct Blue 126
Estimated Annual Production:
Chemical Formula:
NaC- S
<100,000 pounds
OCR
N—N
3
NH,
Raw Materials: 3-Amino-l,5-Naphthalenedisulfonic Acid >
a-Naphthylamine >• 1,6-(and l,7)-Cleve's
Acid >• Cresidine
Current Producer and Tradename:
Harshaw Chemical Co. - Belamine Diazo Blue 2RW 200% New
61
-------
Table V-13. Dyes Manufactured from a-Naphthylamine (Anon., 1974 b; Colour
Index; various personal communications) (Cont'd)
11. Disperse Black 1
Estimated Annual Production: Not Available
Chemical Formula:
Raw Materials: £-Nitroaniline (NO- group reduced after diazotization)
a-Naphthylamine
Current Producers and Tradenames:
American Color & Chemical Co. - Amacel Black 4S Ext.
GAF Corp. - Cellitzaol NSD Extra
Crompton & Knowles Corp. - Intrasperse Diazo Black GNSP
12. Pigment Red 54
Estimated Annual Production: <100,000 pounds
Chemical Formula:
\)
8
= N
Raw Materials: a-Naph thy lamine >• l-Naphthol-5-Sulfonic Acid
Current Producer and Tradename:
Harshaw Chemical Co. - Maroon HB Toner 1159
62
-------
Table V-13. Dyes Manufactured from a-Naphthylamine (Anon., 1974 b; Colour
Index; various personal communications) (Cont'd)
13. Solvent Black 3
Chemical Formula:
N— N
Raw Materials: Aniline
-*• a-Naphthylamine
2,3-Dihydr-2 ,2-Dlmethylperimidine.
Current Producers: None
14. Azoic Coupling Component No. 4
Chemical Formula:
Raw Materials: a-Naphthylamine
Current Producers: None
3-Hydroxy-2-Naphthioc Acid
63
-------
process. Addition of these inert ingredients varies from dye to dye and from
manufacturer to manufacturer. The retail selling price of commercial strength
Acid Blue 113 is approximately $3.60/lb (Chemical Marketing Reporter, 1976).
It is impractical to attempt to evaluate costs considering the
unknown additions of inert ingredients. However, in 1973 total sales from
a-naphthylamine-derived dyes amounted to approximately $5 million (calculated
from data from United States International Trade Commission, 1960-1973).
6. Alternative Final Use Products - Dyes
Each organic dye has a different chemical formula and a different
hue. This means that Acid Blue 113, for example, will have a different hue
from all the other Acid Blues. Also, the unique chemical formula of each dye
gives it individual dyeing properties such as fastness, dischargeability, effect
on metal, and fiber suitability.
It may be possible, however, to imitate the hue of a dye by
mixing combinations of other dyes. For example, the hue of Acid Blue 113 may
possibly be obtained by mixing other Acid Blues with other Acid colors. This
mixing technique makes it theoretically possible to obtain any a-naphthylamine
dye hue, regardless if the dye is Acid, Direct, Disperse, or any other dye
grouping. The major problem would be the suitability of the mixed dye. It
may not have the essential properties for coloration inherent in the a-naphthyla-
mine dye. This would have to be ascertained by experimentation.
In general, specific alternatives to a-naphthylamine dyes have
not been developed because the need has never existed. An exception is an
Acid Orange 116 product offered for sale by Nyanza Inc. The Nyanza product
does not use a-naphthylamine. This^will be discussed further in the next
section.
64
-------
7. Alternative Chemicals for Synthesis
A number of dye producers have indicated efforts to synthesize
ct-naphthylamine dye formulas with intermediates other than a-naphthylamine.
All but one dye producer report that the efforts have been unsuccessful as
the new synthesis made a very inferior dye. The exception is Nyanza Inc.
(Leary, 1975). Nyanza has synthesized an Acid Orange 116 without the use of
a-naphthylamine. The process is considered proprietary information and, there-
fore, was not available. It should be noted, however, that Nyanza's Acid Orange
116 is slightly more expensive than the a-naphthylamine Acid Orange 116 and
has some restrictions for use in continuous dyeing operations. However, it
does indicate the possibility of synthesis without a-naphthylamine.
65
-------
C. Discontinued Uses
1. Substituted a-Naphthylamine Derivatives
In the past, a-naphthylamine has been used to synthesize a
number of chemical intermediates. Domestically, however, a-naphthylamine is
no longer used for these synthesis applications. These applications have
either been terminated or replaced with a substitute process which does not
utilize a-naphthylamine.
Table V-14 lists the 1972 production volumes and values of
a-naphthylamine-derived intermediates for DuPont, the only producer in 1972.
Additional information concerning the derived intermediates is given below.
Table V-14. 1972 DuPont Production Quantities and Values for a-Naphthylamine
Derived Intermediates
Intermediates
N-Ethyl-a-Naphthylamine
Sodium Naphthionate
N-Phenyl-a-Naphthylamine
o-Naphthionic Acid
l-Naphthol-4-Sulfonic Acid
3
Production Quantities (10 Ibs)
276
1,100
2,557
15
71
Value (103
290
770
1,740
42
110
$)
(Nevile and Winther's Acid)
66
-------
a. N-Phenyl-a-Naphthylamine
N-Phenyl-a-naphthylamine is still being domestically pro-
duced, but not from a-naphthylamine. The terminated a-naphthylamine process
involved vapor phase condensation of a-naphthylamine with aniline over alumina
gel at 300°C or fractional distillation of heated a-naphthylamine, aniline,
and catalyst (p_-toluenesulfonic acid) (Donaldson, 1958). The production chemis-
try was:
HN-
o
OIOJ * CO
-NH
DIG
This was the method employed by DuPont up through 1973; at that time DuPont
.switched to an alternative method, not using a-naphthylamine. Union Carbide
has also produced N-phenyl-a-naphthylamine (1967, 1968, 1972, 1973) (U.S.
International Trade Commission, 1960-1973), however the Carbide process proba-
bly utilized the Bucherer reaction described below.
In the alternative production method, a-naphthol is re-
acted with aniline. The a-naphthol hydroxyl group is replaced by an amino
group from the aniline (or aniline sulfite can be used) in the presence of
ammonium sulfite catalyst, and is known as the Bucherer reaction (Bent, 1963),
The suggested mechanism is illustrated below:
OH NH,
67
-------
N-Phenyl-a-naphthylamine is used as an antioxidant for
rubber, petroleum, paint, and plastic. The less expensive cost of a-naphthol
($0.75/lb) (Chemical Marketing Reporter, 1975), compared to a-naphthylamine
($1.10/lb), makes the substitute process economically more favorable.
b. N-Ethyl-a-Naphthylamine
N-Ethyl-a-naphthylamine is still being domestically pro-
duced by DuPont, but not using a-naphthylamine. The terminated process in-
volved heating a-naphthylamine with ethyl chloride.
NH,
-HC1
+ C2H5C1
In addition to DuPont, Dye Specialties, Inc. has produced N-ethy1^a-naphthyl-
amine (1964-1965, 1967-1969, 1971-1972) (U.S. International Trade Commission,
1960-1973). The Dye Specialities process method was not available; however,
use was probably captive for dye production. The only major use for N-ethyl-
a-naphthylamine is as a dye intermediate.
A possible alternative production method again involves
the Bucherer reaction of a-napthol and ethylamine in the presence of ammonium
bisulfite.
OK),
HN —
NH.HSCL ""
68
-------
Comparative raw material cost would be as follows (Boyd, 1975-1976; Chemical
Marketing Reporter, 1976):
a-naphthylamine $1.10/lb a-napthol $0.75/lb
ethyl chloride $ .09/lb ethylamine $0.49/lb
tx-Naphthylamine Process: $0.95/lb raw material cost
a-Naphthol Process: $0.78/lb raw material cost
Here again, the substitute process is economically more favorable.
c. Sodium Naphthionate (Naphthionic Acid-Sodium Salt)
Sodium naphthionate or naphthionic acid is no longer made
in the United States. Approximately 2.5 million Ibs of these chemicals are
used annually for dye production (SRC estimation). The only present source
for the dye producers is importation. Past domestic producers of sodium
naphthionate and naphthionic acid, from 1964, include DuPont (1964-1973),
Allied Chemical (1964-1970), and American Cyanamid (1964-1973) (U.S. Inter-
national Trade Commission, 1960-1973).
The naphthionic acid was prepared by sulfonation of
a-naphthylamine. a-Naphthylamine, direct from its purification process, is
run (in molten form) to a reactor containing an equimolar amount of concen-
trated sulfuric acid (Allied Chemical Corp., 1975).
DID,
H..SO,
180 °C
69
-------
Neutralization with caustic soda or soda ash gives the sodium naphthionate.
There is no known practical method for producing naphthionic acid without
using a-naphthylamine. Estimates of historical production quantities for
sodium naphthionate are given in Table V-15, along with the isolated quantities
of naphthionic acid not neutralized to the sodium salt.
d. l-Naphthol-4-Sulfonic Acid (Nevile and Winther's Acid)
l-Naphthol-4-sulfonic acid is no longer made in the United
States. However, it is currently used as a dye intermediate, with annual use
nearing 200,000 Ibs (SRC estimation), all of which is presently imported.
In the past, DuPont (1964-1973) and Allied Chemical (1964-1970) produced the
acid in quantities approaching one-half the total domestic consumption (see
Table V-16 for l-naphthol-4-sulfonic acid production estimates).
l-Naphthol-4-sulfonic acid was prepared by the Bucherer
reaction by heating naphthionic acid with sodium bisulfite liquor at 90-100°C
and treating the resulting intermediate with sodium hydroxide.
OH
NaHSO , NaOH
-NH3
OJO
There is no known practical method for preparing 1-naphthol-
4-sulfonic acid without using a-naphthylamine derivatives. The direct sulfo-
nation of 1-naphthol results in a mixture of the 2- and 4-isomers (Treibl,
1967).
70
-------
Table V-15. Annual Production Quantities of Sodium Naphthionate and Naphthionic
Acid
1 2
Production Quantities of Production Quantities of
Year Sodium Naphthionate (103 Ib) Isolated Naphthionic Acid (103 Ib)
1973 1400
1972 1300
1971 1350
1970 1450
1969 750 178
1968 650 173
1967 1150 141
1966 224
1965 145
1SRC Estimations
2
U.S. International Trade Commission (1960-1973)
Table V-16. Annual Production Quantities of l-Naphthol-4-Sulfonic Acid
Year 103 Ib
1973
1972 71
1971 110
1970 105
1969 90
1968 90
1967 140
SRC Estimations
71
-------
e. o-Naphthionic Acid
c^-Naphthionic acid is no longer produced in the United
States. DuPont was the only domestic producer after 1964; production years
1964-1973 (U.S. International Trade Commission, 1966-1973). o-Naphthionic
acid was used in pigment production. It was manufactured by heating a-naph-
thylamine with sulfuric acid at 180-185°C, or with aminosulfonic acids at
170-190°C (Donaldson, 1958; Treibl, 1967).
170°-190°C
There is no practical method for production without using a-naphthylamine
derivatives.
2. Aldol-a-Naphthylamine Condensate
In 1973, B.F. Goodrich Co., Chemicals Division, Akron, Ohio,
terminated production of a rubber antioxidant called aldol-ot-naphthylamine
condensate. For production, a-naphthylamine was reacted with aldol (3-hydroxy-
butanol); the details of the process were not available. Reaction chemistry
was probably the following:
CH_ — CH — OH
CH,— CH— OH
3 I
CH — CHO
OP
-" 2°
N=CH— CH,
72
-------
Approximately 200,000 Ibs of aldol-a-naphthylamine condensate
were produced in 1972 (SRC estimation).
3. Rodenticide (cx-Naphthylthiourea)
In 1973, S.B. Penick and Co., division of CPC International,
Inc., terminated production of the rodenticide a-naphthylthiourea, tradenamed
ANTU. a-Naphthylthiourea is manufactured by the interaction of a-naphthylamine
and ammonium thiocyanate (Spencer, 1968).
NH,
HN — C — NH,
-NH,
NH.CNS
DJQ
a-Naphthylthiourea is a rat poison specific to the Norway rat
with toxic doses of 6-8 mg/kg. It is less toxic to other species of rat and
is relatively harmless to man and herbivores. It will induce vomiting in
dogs. Formulation consists of baits of 1-3% in suitable protein or carbohy-
drate-rich material. It is chemically stable on exposure to air and sun
(Spencer, 1968).
a-Naphthylthiourea is presently being imported by the Millmaster
Chemical Co. in very small quantities with prices ranging from $').2r>/'ll> to
$3.50/lb (Kaner, 1975). Import history is listed below (U.S. Dept. of Agri-
culture, 1971):
Year Quantity in Pounds
1969
1968
1967
1966
1965
5,676
3,637
2,000
5,000
4,500
73
-------
There is no practical method for producing a-naphthylthiourea
without a-naphthylamine. However, there are excellent alternatives to a-naphthyl-
thiourea use in rodent control, notably, Warfarin.
74
-------
VI. Material Balance - Exposure to the Environment
This section considers the possible release and exposure of a-naphthylamine
to mart and the environment. Occupational exposure to persons involved in the
production and use of a-naphthylamine is regulated by OSHA standards (Appendix A)
as of January 29, 1974, and will not be considered.
A. a-Naphthylamine Manufacture
There appears to be no disposal or loss of a-naphthylamine to the
environment during the manufacturing process used for a-naphthylamine. Any
wastes or by-products generated during the process are collected and incinerated.
Cleaning wastes are also incinerated (Boyd, 1975-1976). After formation, the
chemical is shipped and stored in the molten form. It is possible that small
spills or leaks from the equipment could occur, but OSHA standards and the
manufacturer (Boyd, 1975-1976) suggest that any wastes from the cleanup of
such spills would be incinerated and not be released to the external environ-
ment.
B. Herbicides
There appears to be no disposal or loss of a-naphthylamine to the
environment during the manufacturing process for herbicides. Small quantities
of a-naphthylamine may be released when the reactors are cleaned or pipes and
valves fail, but these quantities are probably insignificant.
The only potential route for significant a-naphthylamine exposure to
the environment from a-naphthylamine-derived herbicides is from the final herbi-
cide products. In the manufacturing process the a-naphthylamine and phthalic
anhydride have been dissolved in the xylene, benzene, or kerosene and react to
form naptalam which precipitates out of solution. The reaction is at least
75
-------
99% complete by the time the naptalam leaves the reactor for separation (Porter,
1975). In order for the unreacted a-naphthylamine to contaminate the final pro-
duct, it must either be extracted by the sodium salt solution or be retained
on the filtered naptalam, depending upon the separation method used.
It appears highly unlikely that the unreacted a-naphthylamine will be
extracted from the benzene or xylene solution into the aqueous sodium hydroxide
solution. a-Naphthylamine is very soluble in xylene or benzene but fairly in-
soluble in water (0.469 g/£). Naptalam is soluble in the basic aqueous solution
because it can form the water-soluble sodium salt of the phthalamic acid. How-
ever, a-naphthylamine is a weak base and therefore would not disassociate
and be extracted into the aqueous sodium hydroxide solution.
If the naptalam is separated from the organic solvent by filtration,
some unreacted a-naphthylamine might remain on the filter cake. Since the
reaction is 99% complete and a-naphthylamine is very soluble in benzene or
xylene, the amount of a-naphthylamine remaining in the naptalam or sodium
naptalam product should be extremely small. No analytical study could be
located which had attempted to measure the concentration of a-naphthylamine in
the naptalam.
Naptalam is susceptible to hydrolysis at pH 9.3 or higher, which
would result in the formation of a-naphthylamine and phthalic acid. However,
the aqueous solutions of the sodium naptalam are very stable, since the pH
is close to neutral.
C. Dyes
The percent yield for the reactions used to produce a-naphthylamine-
derived dyes, like most organic reactions, rarely exceeds 95%. This will vary
from dye to dye. However, it raises the question as to what is and what
76
-------
happens to the non-product material which accounts for the remaining approxi-
mately 5% of the yield.
In the a-naphthylamine dyes currently being produced, the ot-naphthyl-
amine is almost always coupled to an aromatic amine which has been previously
diazotized. The general coupling reaction with a-naphthylamine (or a-naphthyl-
amine hydrochloride) can be depicted as indicated in the following equation:
R— NS NCI
-HC1
chloride may exist in the reactor in uncoupled form. With the exception of
the dye, Disperse Black 1, the batch is diazotized again for additional coupling
of intermediates. This type of diazotization is a very complete reaction, so
• virtually all of the coupled and uncoupled a-naphthylamine will be diazotized
' as follows:
R _ N ~
HONO
HONO
R— N =N
2H 0
77
-------
As described in Section V-B, ice is added to the reactor to maintain
a temperature range of 0°-5°C to prevent decomposition of the diazonium chlo-
rides. After the coupling reaction of the final intermediate, a small percentage
of unreacted diazonium chlorides will still exist, and when they emerge from the
reactor in the "mother liquid," they will warm up and decompose.
Diazonium salts in acid solution decompose smoothly by a unimolecular
reaction with liberation of nitrogen and formation of phenol derivatives.
Small amounts of haloaromatics may also be obtained in the decomposition of
diazonium halides. For a-naphthylamine, the reactions are illustrated below
(Donaldson, 1958):
(1)
= NX
OH + HX + N,
(2)
Therefore, there will be virtually no free a-naphthylamine in the
"mother liquid" after it has emerged from the reactor. The actual quantity
of free a-naphthylamine has been suggested to be in the "parts per billion"
range (Boyd, 1975-1976; Morgan, 1975; Jackobetz, 1975).
78
-------
The water effluent from the dye processes will contain salt (used
for salting-out the dye), some unprecipitated dye, some acid, and very small
amounts of a-naphthylamine and decomposed diazonium chlorides. The effluent
from the dye plants is either released to the city or country sewage system
or to the ocean (see Table V-9). Although very little information is available
on the biodegradability of a-naphthylamine in water treatment plants, Lutin
and coworkers (1975) have suggested that the chemical is either resistant or
an inhibitor to the action of activated sludge.
In summary, the amount of a-naphthylamine released to the environment from
dye manufacturing plants is probably very small. However, if the chemical is
being released, it probably will not be removed by water treatment.
79
-------
VII. Environmental Assessment
a-Naphthylamine is a suspected carcinogen and, therefore, considerable
caution should be exercised so that workers are not exposed to the chemical
or that the chemical is not released to the environment where human contact
may also be possible. Standards established by the Occupational Safety and
Health Administration (see Appendix A) have controlled the occupational ex-
posure to a-naphthylamine and have also had an impact on reducing contamina-
tion of the external environment. For example, the standards state that:
"Any equipment, material, or other item taken into or removed from a regulated
area [any area where a-naphthylamine is manufactured, processed, used, re-
packaged, released, handled, or stored] shall be done so in a manner that does
not cause contamination in nonregulated areas or the external environment"
(Anon,, 1974 c).
As indicated in the previous section, the OSHA regulations, along with
current industry practices, appear to have eliminated the release of a-nap-
thylainine to the external environment. All wastes from the manufacturing
process (3-4 million pounds a year) are incinerated. a-Naphthylamine pro-
duced in the United States is only available in the molten form and can only
be handled in closed systems. Small amounts (0.25-0.50 million pounds a year)
(
of solid flaked a-naphthylamine are imported for use in the dye industry,
but handling of that material must also meet OSHA standards. As described
in detail in the previous section, the use of a-naphthylamine as a chemical
intermediate for the herbicide naptalam (80-90% of the total production)
and for the synthesis of various dyes (10-20% of the total production) does
not appear to result in any release of a-naphthylamine to the environment.
80
-------
However, firm conclusions on the potential release of ct-naphthylamine from
these intermediate uses require effluent monitoring data that is not available
at this time.
All the previous discussions have concentrated on potential sources of
release of a-naphthylamine, since it is the suspected carcinogen. However,
it is possible that an a-naphthylamine-derived compound could be released to
the environment and then degrade to a-naphthylamine. At least two possible
sources of this type of contamination seem possible.
Takemura ej: al. (1965) have detected a-naphthylamine in the Sumida River.
They concluded that the contamination was due to wastes from dye and pigment
factories along the river. However, they suggested that the a-naphthylamine
was not necessarily discharged in the waste, but may have been produced by
reduction of the azo-dyes in the wastes by H~S or SCL in the river. The
authors demonstrated that aromatic amines could be formed by bubbling H_S
through a pure azo-dye solution. Since the water effluents from a-naphthyl-
amine-derived dyes contain some unprecipitated dye and it is unknown if the
treatment process used will remove the dyes, the possibility is quite high
that the dyes may reach rivers or the ocean. However, the water system re-
ceiving the dyes would have to be very polluted so that H S or SCL (or a re-
ducing environment) would be available for conversion of the dye to a-naphthyl-
amine .
The other possible indirect source of a-naphthylamine deserves considerable
evaluation. Naptalam (N-1-Naphthylphthalamic acid) is produced and consumed
in approximately six million pounds annually. It is used as a pre-emergent
herbicide with soybeans and peanuts and thus is widely released into the en-
vironment. The environmental fate of naptalam has not been studied and reported
81
-------
in the open literature, although some information must have been developed for
EPA registration purposes. Naptalam does hydrolyze to naphthylamine at pH 9.5
or above (Smith and Stone, 1953; Spencer, 1968). If all the naptalam hydrolyzed
to a-naphthylamine, the annual use of naptalam would be the source of three
million pounds of a-naphthylamine in the environment.
82
-------
Appendix A
Occupational Safety and Health Standards and Interpretations
1910.1004 ALPHA-NAPHTHYLAMINE
83
-------
§ 1910.93d nlplia-Naplilliylaniine.
(a) Scope and application. (1) This
section applies to any area In which
alpha-Naphthylnmine, Chemical Ab-
stracts Service Registry Number 134327
Is manufactured, processed, repackaged,
released, handled, or stored, but shall
not apply to transshipment in sealed
containers, except for the labeling re-
quirements under paragraphs (e)(2),
(3), and (4) of this section.
(2) This section shall not appjy to
solid or liquid mixtures containing less
than 1.0 percent by weight or volume of
alpha-Naphthylamine.
(3) This section will not apply to oper-
ations Involving the destructive distilla-
tion of carbonaceous materials, such as
occurs in coke ovens.
(b) Definitions. For the purposes of
this section: (1) "Absolute filter" is one
capable of retaining 99.97 percent of a
mono disperse aerosol of 0.3 nm particles.
(2) "Authorized employee" means an
employee whose duties require him to
be in the regulated area and who has
been specifically assigned by the
employer.
(3) "Clean change room" means a
room where employees put on clean
clothing and/or protective equipment in
an environment free of alpha-
Naphthylamine. The clean change room
shall be contiguous to and have an entry
from 61 shower room, when the shower
room facilities are otherwise required in
this section.
(4) "Closed system" means an opera-
tion Involving alpha-NaphthyJamine
where containment prevents the release
of alpha-Naphthylamine into regulated
areas, nonregulated areas, or the ex-
ternal enviroilment.
(5) "Decontamination" means the in-
activation of alpha-Naphthylamine or its
safe disposal.
(6) "Director" means the Director,
National Institute for Occupational
Safety and Health, or any person di-
rected by him or the Secretary of Health,
Education, and Welfare to act for the
Director.
(7) "Disposal" means the safe removal
of alpha-Naphthylamine from the work
environment.
(8) "Emergency" means an unfor-
seen circumstance or set of circum-
stances-resulting in the release of alpha-
Naphthylamine which may result in
exposure to or contact with alpha-
Naphthylarnlne.
(9) "Extertal environment" means
any environment external to regulated
and nonregulated areas.
(10) "Isolated system" means a fully
enclosed structure other than the ve?(;el
of containment of alpha-Naphthylamine,
which Is impervious to the passage of.
alpha-Naphthylamine, and which wo'ild
prevent the entry of alpha-Naphthyla-
mlne into regulate areas, nonregulated
areas, or the external environment,
should leakage or spillage from the ves-
sel of containment occur.
• (11) "Laboratory type hood" is a do-
vlce enclosed on three Sides and the top
and bottom, designed and maintained no
as to draw air inward at an average
linear face velocity of 150 feet per minute
with a minimum of 125 feet per minute;
designed, constructed, and maintained In
such a way that an operation involving
alpha-Naphthylamine within the hood
does not require the insertion of any por-
tion of any employees' body other than
his hands and arms.
(12) "Nonregulated area" means any
area under the control of the employer
where entry and exit is neither restricted
nor controlled.
(13) "Open-vessel system" means on
operation involving alpha-Naphthyla-
mine in an open vessel, which is not In
an Isolated system, a laboratory type
hood, nor in any 'other system affording
equivalent protection against the entry
of alpha-Naphthylamine Into regulated
areas, nonregulated areas, or the external
environment.
(14) "Protective clothing" means
clothing designed to protect an employee
against contact with or exposure to
alpha-Naphthylamine.
(15) "Regulated area" means an arcn
where entry and exit Is restricted and
controlled.
(c) Requirements for areas containing
alpha-Naphthvlamine. A regulated area
shall be established by an employer
where alpha-Naphthylamine is manu-
factured, processed, usi:d. repackaged,
released, handled or stored. All such
areas shall be controlled in accordance
with the requirements for the following
category or categories describing the op-
eration involved: U) Isolated systems.
Employees working with alpha-Naph-
thylamine within an isolated system,
such as a "glove box" shall wash their
hands and arms upon completion of the
assigned task and before engaging in
other activities not associated with the
Isolated system.
(2) Closed system operation. Within
regulated areas where alpha-Naphthyla-
mine Is stored in sealed containers, or
contained hi a closed system, including
piping systems, with any sample port* or
openings closed while alpha-Naphthyla-
mine is contained within: (1) Access shfUl
be restricted to authorized employees
only;
(11) Employees shall be required to
wash hands, foreanns, face and neck
upon each exit from the regulated areas,
close to the point of exit and before en-
gaging In other activities.
(3) Open vessel svstem operations.
Open vessel system operations as defined
in paragraph (b) (13) of this section are
prohibited.
84
-------
(4) Transfer from a closed system,
charging or discharging point operations,
or otherwise opening a closed system. In
operations involving "laboratory type
hoods," or in locations where alpha-
Naphthylamine is contained In an
otherwise "closed system." but is trans-
ferred; charged, or discharged into other
normally cjosed containers, the pro-
visions of this subparagraph shall apply.
(1) Access shall be restricted to author-
ized employees only:
(11) Each operation shall be provided
with continuous local exhaust ventila-
tion so that air movement is always
from ordinary work areas to the opera-
tion. Exhaust air shall not be discharged
to regulated areas, nonregulated areas
or the external environment unless de-
contaminated. Clean makeup air shall be
Introduced In sufficient volume to main-
tain tho correct operation of the local
exhaust system.
(ill) Employees shall be provided with,
and required to wear, clean, full body
protective clothing (smocks, coveralls, or
long-sleeved shirt and pants), and shoe
covers and gloves prior to entering a
regulatod area.
(iv) Employees engaged in alpha-
Naphthylamlne handling operations shall
be provided with and required to wear
and use a half-face, filter-type respira-
tor for dusts, mists, and fumes, In ac-
cordance with 8 1910.134. A respirator
affording higher levels of protection may
be substituted.
(v) Prior to each exit from a regu-
lated area, employees shall be required
to remove and leave protective clothing
and equipment at the point of exit and
at the last exist of the day, to place
vised clothing and equipment In Impervi-
ous containers at the point of exit for
purposes of decontamination or disposal.
The contents of such Impervious con-
tainers shall be Identified, as required
under paragraphs (e)(2), (3), and (4)
of this section.
(vi) Employees shall be required to
wash hands, forearms, face and neck on
each exit from the regulated area, close
to the point of exit, and before engaging
In other activities.
(vli) Employees shall be required to
shower after the last exit of the day.
(vill) Drinking fountains are prohib-
ited in the regulated area.
(5) Maintenance and decontamina-
tion activities. In cleanup of leaks or
spills, .maintenance or repair operations
on contaminated systems or equipment,
or any operations Involving work In an
area where direct contact with alpha-
Naphthylamlne could result, each au-
thorized employee entering that area
shall:
(1) Ete provided with and required to
wear clean, Impervious garments, includ-
ing gloves, boots and continuous-air sup-
plied hood in accordance with {1910.134.
(11) Be decontaminated before remov-
ing the protective garments and hood;
(ill) Be required to shower upon re-
moving the protective garments and
hood.
(6) Laboratory activities. The require-
ments of this subparagraph shall apply
to research and quality control activities"
involving the use of alpha-Naphthyla-
mlne. (i) Mechanical pipetting aids shall
be used for all pipetting procedures.
(11) Experiments, procedures and
equipment which could produce aerosols
shall be confined to laboratory-type
hoods or glove boxes.
(Ill) Surfaces on which alpha-Naph-
thylamlne is handled shall be protected
from contamination.
(iv) Contaminated wastes and animal
carcasses shall be collected in impervi-
ous containers which are closed and de-
contaminated prior to removal from the
work area. Such wastes and carcasses
shall be Incinerated in such a manner
that no carcinogenic products are re-
leased.
(v) All other forms of alpha-Naph-
thylamlne shall be Inactivated prior to
disposal.
(vi) Laboratory vacuum systems shall
be protected with high-efficiency scrub-
bers or with disposable absolute filters.
(vll) Employees engaged In animal
support activities shall be (a) provided
with, and required to wear, a complete
protective clothing change, clean each
day. Including coveralls, or pants and
shirt, foot covers, head covers, gloves,
and appropriate respiratory protective
equipment or devices; and
(b) Prior to each exit from a regulated
area, employees shall be required to re-
move and leave protective clotlilng and
equipment at the point of exit and at the
last exit of the day, to place used clothing
and equipment in impervious containers
at the point of exit for purposes of de-
contamination or disposal. The contents
of such impervious containers shall be
identified as required under paragraph's
(e) (2), (3), and (4) of this section.
-------
(b) Prior to each exit from a regulated
nrea, employees shall be required to re-
move and leave protective clothing and
equipment at the point of exit and at the
last exit of the day, to place used clothing
and equipment in impervious containers
at the point of exit for purposes of de-
contamination or disposal. The contents
of such Impervious containers shall be
identified as required under paragraphs
(e) (2), (3), and (4) of this section.
(c) Required to wash hands, forearms,
face and neck upon each exit from the
regulated area close to the point of exit,
and before engaging In other activities.
througli
(vil).
(iii) Where employees are required by
this section to shower, shower facilities
shall be provided in accordance with
5 1910.141(d)(3>.
(iv) Where employees wear protective
clothing and equipment clean change
rooms shall be provided, in accordance
with 51910.141(e), for the number of
such employees required to change
clothes.
(v) Where toilets are in regulated
areas, such toilets shall be In a separate
room.
(4) Contamination control. (1) Regu-
lated areas, except for outdoor systems,
shall be maintained under pressure nega-
tive with respect to nonregulated areas.
Local exhaust ventilation may be used
to satisfy this requirement. Clean make-
up air in equal volume shall replace air
removed.
(li) Any equipment, material, or other
item taken Into or removed from a regu-
lated area shall be done so in a manner
that does not cause contamination in
nonregulated areas or the external
environment.
(Hi) Decontamination procedures shall
be established and Implemented to re-
move alpha-Naphthylamlne from the
surfaces of materials, equipment and the
decontamination facility.
(iv) Dry sweeping and dry mopping
are prohibited.
(e) Signs, information and training—
(1) Signs. (1) Entrances to regulated
areas shall be posted with signs bearing
the legend:
CANCER-SUSPECT AGENT
AUTHORIZED PERSONNEL ONLY
86
-------
(It) Entrances to regulated areas con-
taining operations covered In paragraph
(c) (5) of this section shall be posted
With signs bearing the legend:
CANCER-SUSPECT AGENT EXPOSED IN Tins
AREA IMPERVIOUS SUIT INCLUDING
GLOVES, BOOTS, AND AIR-SUPPLIED HOOD
REQUIRED AT ALL TIMES AUTHORIZED
PERSONNEL ONLY
(111) Appropriate signs and Instruc-
tions shall be posted at the entrance to,
and exit from, regulated areas, inform-
ing employees of the procedures that
must be followed In entering and leaving
a regulated avea.
(2) Container contents identification.
(1) Containers of alpha-Naphthylamine
•and containers required under para-
graphs (c) (4) (v) and (c) (6) (vil) (b),
and (c) (6) (vlll) (b) of this section
which are accessible only to, and han-
dled only by, authorized employees, or
by other employees trained In accord-
ance with subparagraph (5) of this para-
graph, may have contents Identification
limited to a generic or proprietary name,
or other proprietary Identification, of the
carcinogen and percent.
(ii) Containers of alpha-Naphthyla-
mine ajid containers required under
paragraphs (c) (4) (v), (c) (6) (vli) (b).
and (c) (6> (viiii tb> of tliis section which
are accessible to, or handled by employees
other than authorized employees or em-
ployees trained in accordance with sub-
paragraph (5> of this paragraph shall
have contents identification which in-
cludes the full chemical name and
Chemical Abstracts Service Registry
number as listed in paragraph (a)(l)
of this section.
-------
(2) Incidents. Incidents which result
in the release of a)pha-Naphthylamine
Into any area where employees may be
potentially exposed shall be reported in
accordance with this subparagraph. (i)
A report of the occurrence of the in-
cident and the facts obtainable at that
time including a report on any medical
treatment of affected employees shall
be made within 24 hours to the nearest
OSHA Area Director.
(ii) A written report shall be filed
with the nearest OSHA Area Director
within 15 calendar, days thereafter and
shall include:
(o> A specification of the amount of
material: released, the amount of time
Involved, and an explanation of the pro-
cedure used In determining this figure:
!f>> A description of the area involved.
and the extent of known and possible
employee exposure and area contamina-
tion, and
(r) A report of any medical treatment
of affected employees, and any medical
surveillance program implemented; and
(rt) An analysis of the circumstances
of the incident, and measures taken or
to be taken, with specific completion
dates, to avoid further similar releases
(qt Medical surveillance. At no cost
to the employee, a program of medical
surveillance shall be established and im-
plemented for employees considered for
assignment to enter regulated areas, and
for authorized employees. (1) Examina-
tions. (1) Before an employee Is assigned
to enter a regulated area, a preassign-
ment physical examination by a physioan
shall be provided. The examination shall
include the personal history of the em-
ployee, family and occupational back-
ground, including genetic and environ-
mental factors.
(10 Authorized employees shall be
provided periodic physical examinations.
not less often than annually, following
the preassignmentfcxamlnation.
(till In all physical examinations, the
examining physician shall consider
whether there exist conditions of in-
creased risk, including reduced 1m-
munologlcal competence, those under-
going treatment with steroids or cyto-
toxic agents, pregnancy and cigarette
smoking.
(2) Records. (1) Employers of em-
ployees examined pursuant to this para-
graph shall cause to be maintained com-
jilete and accurate records of all such
medical examinations. Records shall be
maintained for the duration of the em-
ployee's employment. Upon termination
of the employee's employment, including
retirement or death, or in the 'event that
the employer ceases business without a
successor, records, or notarized true
copies thereof, shall be forwarded by
registered mail to the Director.
(it) Records required by this para-
graph shall be provided upon request to
authorized representatives of the Assist-
ant Secretary or the Director; and upon
request of an employee or former em-
ployee, to a physician designated by the
employee or to a new employer.
(ill) Any physician who conducts a
medical examination required by this
paragraph shall furnish to the employer
a statement of the employee's suitability
for employment in the specific exposure.
88
-------
Appendix B
Material Safety Data Sheet for Alpha-Naphthylamine
89
-------
U.S. UtPARlMLNI Of LABUK
OCCUPATIONAL SAFETY & HEALTH ADMINISTRATION
MATERIAL SAFETY DATA SHEET
SECTION 1
MANUFACTURE'S NAM(
E. I, du Pont de Nemourn, Inc.
AOORISS {Numlir, Slufl, Ci'lr. Stall, and i\P Codt)
Tftilri4fttftonf Delaware 19898
CHIMICAL NAME AND SYNONYMS
1— Aminonaph.thalene
CHEMICAL FAMILY FORMULA
Aromatic £mine
EMfRGF.NCV TELEPHONE NO.
(302)-774-7500
TRADE NAME AND SYNONYMS
alDha-Naphthylamine Technical
C10H7NH2
SECTION II HAZARDOUS INGREDIENTS
PAINTS. PRESERVATIVES, & SOLVENTS
PIGMENTS
CATALYST
VEHICLE
SOLVENTS
ADDITIVES
OTHERS
* TLV
* (Unit.)
ALLOYS AND METALLIC COATINGS
BASE METAL
ALLOYS
METALLIC COATINGS
FILLER METAL
PLUS COATING OR CORE FLUX
OTHERS
HAZARDOUS MIXTURES OF OTHER LIQUIDS
, SOLIDS. OR CASES
This section not applicable
alpha-Naphthylamine may contain up to 0.5$ beta-Naphthylainine
(5,000 ppm)
*
»
TLV
(Unit!)
TLV
(Unlit)
SECTION 1 II PHYSICAL DATA
BOILING POINT (*F.|
VAPOR PRESSURE lrr*n Hg.l
VAPOR DENSITY UIR=1|
SOLUBILITY IN WATER
572° F.
1MM/2190
It. 93
slightly
SPECIFIC GRAVITY IHjO-1)
PERCENT VOLATILE ,. , . . , .
BY VOLUME (*i Not applicable
EVAPORATION RATE
• ri| Not applicable
Ap»fA«ANCE AND ODOR Tan to ,br,own flakes tends to darken on storage.
araine odor .
1.2
Characteristic
SECTION IV FIRE AND EXPLOSION HAZARD DATA
FLASH POINT lM«lhod used)
315° F. (O.C.)
EXTINGUISHING MEDIA ,, .
Water, C02, foam
FLAMMABLE LIMITS
Not available
SPECIAL FIRE FIGHTING PROCEDURES
If product is exposed to fire or intense
Lei
Ual
heat toxic fumes
may be generated. If exposure is likely complete body protection may be required
UNUSUAL FIRE AND EXPLOSION HAZARDS
None except fumes
noted above.
NOTICE FROM DU PONT
The data in this Material Safety Data Sheet relates only to the specific material designated herein ond does not
relate to use in combination with any other material or in any process.
90
-------
SECTION V HEALTH HAZARD DATA
THRESHOLD LIMIT VALUE
Not available.
EFFECTS OF OVEREXPOSURE
Because alpha-Naphthylamine may contain the carcinogen beta-Naph-
tnylamine exposure to the commercial productmust be minimized.
exposure may result in bladder tumors. (See below")
Prolonged chronic
EMERGENCY AMD FIRST AID PROCEDURES
Wash exposed parts of body vith soap and vater. Obtain
medical attention for cyanosis. Periodic medical examination of workers vith
potential, exposure to alpha-Naphthylamine should be performed.
SECTION VI REACTIVITY DATA
STABILITY u
1
S
NSTABLE '
TABLE X
:ONDITIONSTO AVOID
INCOMPATABILITY (Uaurialt to avoid) . , . .
Oxidizing agents
HAZARDOUS DECOMPOSITION PRODUCTS
Oxides of nitrogen
HAZARDOUS
POLYMERIZATION
MAY OCCUR
WILL NOT OCCUR
CONDITIONS TO AVOID
X
SECTION VII SPILL OR LEAK PROCEDURES
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED
Use dust respirator if dust is present.
Clean up area followed by washing to remove residual material.
WASTE DISPOSAL METHOD Product may be incinerated.
: ' .
SECTION VIM SPECIAL
PROTECTION INFORMATION
RESPIRATORY PROTECTION (Specify tjft) /gee V,e"low}
VENTILATION
PROTECTIVE GLOVES
LOCAL EXHAUST
A.
MECHANICAL (Central)
Butyl rubber
SPECIAL
OTHER
EVE PROTECTION
Side shield safety glasses
OTHER PROTECTIVE EQUIPMENT Where exposure is likely, complete body protection such as
Hhpm— Prnn-f Rin't." i =; rprmi rf>e\
•
PRECAUTIONS TO BE TAKEN IN HANDLING
Direct body exposure to
SECTION 1
AND STORING
fumes and
X SPECIAL PRECAUTIONS
Store material in well ventilated area.
dust must be prevented.
I OTHER PRECAUTIONS
Exposure to alpha-Naphthylamine may also cause cyanosis.
91
-------
H-
3
OQ
Hi
o
t-t
25
(to
13
3*
rT-
cr
(to
g
H-
3
CD
ro
3
LOT.
PKG..
5-A
OR-'. 01
'3 REV
NAPHTHYLAMINE TECH. 134327
(Contains up to 0.5% beta-Naphthylamine)
CANCER SUSPECT AGENT
WARNING! Harmful Dust and Vapor
Repeated inhalation or Skin Absorption
May Result in Bladder Tumors
Avoid breathing dust or vapor.
Use only with adequate ventilation.
Avoid contact with skin.
Wash thoroughly after handling.
Wear fresh clothing daily. Take a hot shower after work,
using plenty of soap.
Keep container closed.
Store in a cool dry place.
SPILL: Sweep up; remove to chemical waste area.
Before using, read MCA Chemical Safety Data Sheet SD-32. beta-Naphthyla-
mine.
MADE IN U.S.A.
-------
REFERENCES
Agway, Inc. (1975), Personal communication with various personnel, Pesticides
Sales Dept., Dewitt, N.Y., December.
Allied Chemical Corporation (1975), Personal communication with various
personnel, Buffalo, N.Y. and Morristown, N.J., December.
American Cyanamid Company (1975), Personal communication with various
personnel, Bound Brook, N.J., December.
Amitirano, R. (1975), Personal communication, Aceto Chemical Co., Inc.,
Flushing, N.Y.
Anon.. (1973), "Emergency Temporary Standard on Certain Carcinogens," Fed.
Regist., 38(85), 10929-30, May 3, 1973.
Anon.. (1974a), Farm Chemicals Handbook, Meister Publishing Co., Willoughby,
Ohio.
Anon. (1974b), "Products /75," Textile Chem. Colorists, 6/10A).
Anon. (1974c), "Part 1910 Occupational Safety and Helath Standards. Carcinogens.
1910.93d alpha-Naphthylamine," Fed. Regist., 39_(20), 3756-3797.
Bent, R.L. (1963), "Amines." Kirk-Othmer Encycl. Chem. Technol.. 2nd Ed.,
2, 99-116.
Boyd, S.N. (1975-76), Personal communication, Manager of Environmental Affairs,
E.I. duPont de Nemours and Co., Inc., Deepwater Point, N.J., November,
December, January.
Chavkin, R. (1975), Personal communication, Biddle-Sawyer Corp., New York,
N.Y., October.
Chemical Marketing Reporter (1976), "Current Prices of Chemicals and Related
Materials," p. 28-40, January 26.
Colour Index (1956), 2nd Edition, Vol. 1-4, Chorley and Pickersgill Ltd.,
Leeds and Percy Lund, Humphries and Co., Ltd., London.
Donaldson, N. (1958), The Chemistry and Technology of Naphthalene Compounds,
Edward Arnold Ltd., London, England.
Dowling, R.J. (1975), Personal communication, Toxicology Coordinator, Uniroyal
Chemical, Div. of Uniroyal, Inc., Naugatuck, Conn., December.
Fallek Chemical Corp. (1975), Personal communication with various personnel,
New York, N.Y.
93
-------
Fox, D. (1975), Personal communication, Production Dept., Thompson-Hayward
Chemical Co., Kansas City, Kansas, November.
Henke, C.O. and Benner, R.G. (1938), "Hydrogenation of a-Nitronaphthalene,"
U.S. Patent No. 2,105,321, January 11.
Horning, Dr. (1975), Personal communication, Crompton and Knowles Corp.,
Gibraltar, Penn., December.
Jacobetz, J.F. (1975), Personal communication, Safety Director, American
Color and Chemical Co., Lock Haven, Penn., December.
Kaner, J. (1975), Personal communication, Millmaster Chemical Co., New York,
N.Y., December.
Leary, G. (1975), Personal communication, Nyanza, Inc., Ashland, Mass.,
November.
Liggin, S. (1975), Personal communication, Helena Chemical Co., W. Helena,
Ark., December.
Liggin, S. and Holloway, W. (1975), Personal communication, Helena Chemical
Co., W. Helena, Ark., November.
Lutin, P.A., Cibulka, J.J. and Malaney, G.W. (1965), "Oxidation of Selected
Carcinogenic Compounds by Activated Sludge," Purdue Univ. Ext. Ser.,
118, 131-145.
March, J. (1968), Advanced Organic Chemistry: Reactions, Mechanisms, and
Structure, McGraw-Hill, New York.
Milligan, D. (1975), Personal communication, Vice-President of Production,
Crystal Chemical Co., Houston, Texas, November.
Morgan, J. (1975), Personal communication, GAF Corp., Rensselaer, N.Y.,
December.
Muelluer, J. (1975), Personal communication, Orlex Chemical Co., Fair Lawn,
N.J., December.
Nicklaus, J. (1975), Personal communication, Marketing Dept., The Ansul Co.,
Marinette, Wise., November.
OPD Chemical Buyers Directory (1975-76), Schnell Publishing Co., New York, N.Y.
.Porter, D. (1975), Personal communication, Chief Chemist, Uniroyal Chemicals
Div., Gastonia, N.C., November.
Roberts, J.D. and Caserio, M.C. (1964), Basic Principles of Organic Chemistry,
W.A. Benjamin, Inc., New York, N.Y.
94
-------
Rounds, R. (1975), Personal communication, GAF Corp., Rensselaer, N.Y.,
November.
Shreve, N.R. (1963), "Amination By Reduction," Kirk-Othmer Encycl. Chem.
Techno 1., 2nd Ed., _2, 83-84.
Smith, A.E. and Hoffman, O.L. (1950), "Plant Growth Regulants and Phytocides,"
U.S. Patent No. 2,556,644-5, assigned to United States Rubber Co., March 18.
Smith, A.E. and Stone, G.M. (1953), "Microdetermination of N-1-Naphthyl-
phthalamic Acid Residue in Plant Tissues," Anal. Chem., 25, 1397.
Spencer, E.Y. (1968), Guide to the Chemicals Used in Crop Protection, Canadian
Dept. of Agriculture, Publ. 1093, 5th Ed., February.
Takemura, N., Akiyama, T. and Nakahama, C. (1965), "A Survey of the Pollution
of the Sumida River, Especially on the Aromatic Amines in the Water,"
Inter. J. Air Pollut., 9/10), 665-70.
Treibl, H.G. (1967), "Naphthalene Derivatives," Kirk-Othmer Encycl. Chem.
Technol., 2nd Ed., 13, 697-726.
U.S. Department of Agriculture (1974), Farmers' Use of Pesticides in 1971
Quantities, Agriculture Economic Report No. 252, Washington, D.C.
U.S. Department of Agriculture (1971), Pesticide Review 1970, Washington, D.C.
U.S. International Trade Commission (1960-73), Synthetic Organic Chemicals,
United States Production.and Sales, Washington, D.C.
U.S. Tariff Commission (1967-73), Imports of Benzenoid Chemicals and Products,
Washington, D.C.
Von Rumker, R., Meiners, A.F. and Lawless, E.W. (1974), "Production, Distri-
bution, Use, and Environmental Impact Potential of Selected Pesticides,"
U.S. Nat. Tech. Inform. Serv. PB 238-795.
Wherry, C.R. (1968), "Herbicides," in Chemical Economics Handbook, Stanford
Research Institute, Menlo Park, Calif.
Woolfolk Chemical Works, Inc. (1976), Personal communication with various
personnel, Herbicide Dept.-, Fort Valley, Ga.
Wooster, C.B. (1963), "Ammonolysis," Kirk-Othmer Encycl. Chem. Technol., 2nd
Ed., 2, 332-373.
95
-------
TECHNICAL REPORT DATA
(Please read Imuructiomi on llic reverse before completing!
1 REPORT NO.
EPA 560/6-77-002
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Chemical Market Input/Output Analysis of Selected
Chemical Substances to Assess Sources of Environmental
Contamination: Task I. Naphthylamines
5. REPORT DATE
March 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHORIS)
William M. Meylan, Philip H. Howard, Milton Sack
8. PERFORMING ORGANIZATION REPORT NO
TR 76-523
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Center for Chemical Hazard Assessment
Syracuse Research Corporation
Merrill Lane
Syracuse, New York 13210
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA 68-01-3224-Task 1
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Technical Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report considers the sources of environmental contamination from
naphthylamines. Because B-naphthylamine is a proven human carcinogen and there
are other alternatives to its use, it is no longer produced and consumed com-
mercially in the United States. However, ct-naphthylamine, which is a suspected
carcinogen, is still manufactured for use as a chemical intermediate for dyes
and herbicides. Thus, this report concentrates on the commercial production
and use of a-naphthylamine. Standards established by the Occupational Safety
and Health Administration have controlled the occupational exposure to a-naph-
thylamine and have also had an impact on reducing contamination of the external
environment. The OSHA regulations, along with current industry practices, appear
to have eliminated the release of a-naphthylamine to the external environment.
However, firm conclusions on the potential release of a-naphthylamine from its
' uses as a chemical intermediate require effluent monitoring data that is un-
available at this time. Further, it is possible that an a-naphthylamine-derived
compound could be released to the environment and then degrade to a-naphthylamine.
At least two possible sources of this type of contamination seem possible.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATl Held/Group
18. DISTRIBUTION STATEMENT "
Document is available to the public
through the National Technical Informa-
tion Service. Springfield. VA 22151
19. SECURITY CLASS (Tlii.i Report)
21. NO. OP I'AC.t S
102
20. SECURITY CLASS (This pane)
22. PRICK
EPA Form 2220-1 (.9-73)
-------
|