vvEPA
United States
Environmental Protection
Agency
Office of
Toxic Substances
Washington DC 20460
EPA-560/13-89-011
April 1980
Toxic Substances
Materials Balance
2 - Nitropropane
Level I Preliminary
Review
Copy
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FINAL REPORT
LEVEL I MATERIALS BALANCE
2-NITROPROPANE
Prepared for:
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF PESTICIDES AND TOXIC SUBSTANCES
SURVEY AND ANALYSIS DIVISION
Task Order No. 19
Contract No. 68-01-5793
Michael A. Callahan - Project Officer
Karen Hammerstrom - Task Manager
Prepared by:
JRB ASSOCIATES, INC.
8400 Westpark Drive
McLean, Virginia 22102
Project Manager: Robert Hall
Task Leader: Phuoc T. Le
Contributing Writers: Eliot Harrison
Terry Shannon
Submitted: December 8, 1980
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DISCLAIMER
This is a report on a Level I Materials Balance on 2-nitropropane.
As such it is presented as a focus of discussion and as a basis
for future materials balance studies: it is not meant to be a
definitive study. The results reported were based on a 1,000-
hour 10-week analysis of information gathered by JRB staff.
This document has been reviewed and approved for publication by
the Office of Testing and Evaluation, Office of Pesticides and
Toxic Substances, U.S. Environmental Protection Agency. Approval
does not signify that the contents necessarily reflect the views
and policies of the Environmental Protection Agency, nor does the
mention of trade names or commercial products constitute endorse-
ment or recommendation for use.
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TABLE OF CONTENTS
Page
EXECUTIVE SUMMARY i
1.0 INTRODUCTION 1-1
2.0 ENVIRONMENTAL RELEASE ASSOCIATED WITH PRODUCTION
OF 2-NITROPROPANE 2-1
2.1 ENVIRONMENTAL RELEASE ASSOCIATED WITH
DIRECT PRODUCTION 2-1
2.1.1 Release of 2-Nitropropane to the Air
from Process Vents 2-4
2.1.2 Emissions of 2-Nitropropane to Air from
Product Storage Tanks (Stream I) 2-6
2.1.3 Emissions of 2-Nitropropane to Air from
Fugitive Sources 2-8
2.1.4 Release of 2-Nitropropane to Air and Water
During Waste Water Treatment 2-8
2.1.5 Emission of 2-Nitropropane to Air During
Heavy-End Waste Disposal 2-10
2.1.6 Emissions of 2-Nitropropane During Loading
and Shipping 2-10
2.2 RELEASES OF 2-NITROPROPANE ASSOCIATED WITH
INADVERTENT PRODUCTION 2-11
2.3 RELEASE OF 2-NITROPROPANE ASSOCIATED WITH NATURAL
PRODUCTION SOURCES 2-11
2.4 IMPORTS 2-13
3.0 ENVIRONMENTAL RELEASE DURING THE USES OF 2-NITROPROPANE 3-1
3.1 RELEASE OF 2-NITROPROPANE ASSOCIATED WITH THE
PRODUCTION OF CHEMICALS 3-1
3.1.1 Release of 2-Nitropropane Associated with
Production of 2-Nitro-2-Methyl-l-Propanol 3-1
3.1.2 Release of 2-Nitropropane During the Uses
of 2-Nitro-2-Methyl-l-Propanol 3-3
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TABLE OF CONTENTS (Continued)
Page
3.1.3 Release of 2-Nitropropane During Formulation
and Uses of Aminohydroxyalcohol Compounds 3-4
3.2 RELEASE OF 2-NITROPROPANE ASSOCIATED WITH NON-
CONSUMPTIVE USES 3-4
3.2.1 Printing Inks 3-5
3.2.2 Surface Coatings 3-12
3.2.3 Miscellaneous Uses 3-20
3.2.4 Exports 3-25
4.0 RELEASE OF 2-NITROPROPANE FROM NITROMETHANE, NITRO-
ETHANE, AND 1-NITROPROPANE USES 4-1
5.0 RELEASE SOURCE EVALUATION 5-1
6.0 SUMMARY OF DISPOSAL AND DESTRUCTION OF WASTES 6-1
7.0 DATA GAPS AND RECOMMENDATIONS 7-1
8.0 REFERENCES 8-1
APPENDIX A A-l
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LIST OF FIGURES
Figure Page
1. Environmental Materials Balance for 2-Nitro-
propane iii
2.1 Location of Producer of 2-Nitropropane 2-2
2.2 Flow Diagram of the Production of 2-Nitropropane
by the Direct Nitration Process 2-3
2.3 Environmental Releases of 2-Nitropropane During
its Production . 2-12
3.1 Flow Diagram for the Production of 2-Nitro-2-Methyl-
1-Propanol and 2-Amino-2-Methyl-l-Propanol 3-2
3.2 Types of Ink-mixing Plants 3-7
3.3 Ink Distribution System for Flexography 3-10
3.4 Rotogravure Ink System 3-11
3.5 Flow Diagram of Environmental Releases of
2-Nitropropane During the Production and Uses
of Printing Ink 3-13
3.6 Usage of 2-Nitropropane and Other Solvents
in the Surface Coating Industry 3-17
3.7 Flow Chart for the Mixing of Surface Coatings 3-18
3.8 Environmental Release Flow Diagram of 2-Nitro-
propane During the Production and Uses of Surface
Coatings 3-21
4.1 Flow Diagram of Manufacture of Hydroxylammonium
Sulfate 4-3
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LIST OF TABLES
Table Page
3.1 Waste Water Disposal Methods for Printing Ink
Manufacture 3-9
5.1 Summary of Environmental Releases of 2-Nitro-
propane, 1979 5-2
5.2 Categorization of 2-Nitropropane Environmental
Releases 5-3
6.1 Releases from Disposal/Destruction of 2-Nitro-
propane-containing Wastes 6-2
7.1 Data Gaps and Recommendations 7-2
A.I Properties of 2-Nitropropane A-2
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EXECUTIVE SUMMARY
2-Nitropropane is a clear, colorless liquid that is slightly soluble
in water. It is manufactured via the direct nitration of propane by the
International Mineral and Chemical Group (IMC) at Sterlington, LA.
2-Nitropropane exists in tautomeric equilibrium with its "aci" or nitronic
acid forms as shown below.
CH ,0 CH3 -0
CH--C N-. -* - *~ CH,
3 3
3
-C=*<
\
^
H
2-Nitropropane 2-Propane nitronic acid
The physical properties of 2-nitropropane are represented in the
Append ix .
It is estimated that the total consumption of 2-nitropropane in 1979
was approximately 14,000 kkg. Of this amount, about 50 percent was con-
sumed captively to produce 2-nitro-2-methyl-l-propanol , 2-amino-2-methyl-
1-propanol, and other aminohydroxy compounds. The remainder was used
nonconsumptively , mainly as a solvent. Imports of 2-nitropropane are
believed to be negligible «0.5 kkg per year). Exports of 2-nitropropane
amounted to 1,400 kkg in 1979.
An estimated 19 percent (2,700 kkg) of 2-nitropropane is used as a
feedstock for the production of 2-nitro-2-methyl-l-propanol , while 31
percent (4,300 kkg) is used as a feedstock in the production of amino-
hydroxy compounds. Approximately 21 percent (2,900 kkg) of 2-nitropropane
is used as a solvent in printing inks; 12 percent (1,600 kkg) is used as a
solvent in surface coating production; and 7 percent (1,100 kkg) of
2-nitropropane is used in miscellaneous uses, including: explosives and
propellants, adhesives, dyes, smoke reducers, rubber, and as a solvent
and/or extraction agent in various chemical reactions.
The materials balance for 2-nitropropane is shown in Figure 1. This
diagram illustrates the flow of 2-nitropropane in the environment and
sources of its release to various media.
Of the estimated 14,000 kkg of 2-nitropropane produced in the United
States in 1979, a total of 5,715 kkg (41 percent) is estimated to have been
released to the environment. Of these releases, 99.99 percent (5,714 kkg)
went to the atmosphere; a negligible amount (1 kkg) went to water. There
were no releases to land. An additional 1.6 percent (230 kkg) was
destroyed by incineration and waste treatment. These estimates are based
on available information and should be verified in later studies.
Most of the releases of 2-nitropropane to air (78 percent or
4,450 kkg) occurred during its use as a solvent in printing inks and
surface coatings. The direct production of 2-nitropropane accounts for
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only 0.3 percent (21 kkg) of the total releases. No information was
available on releases from consumptive uses.
Several major data gaps were encountered during the preparation of
this report. Data were lacking on releases from production processes and
consumptive and nonconsumptive uses. Another major area where data were
lacking was the quantity of 2-nitropropane contaminant in products derived
from 2-nitropropane. Finally, there was insufficient information on
various minor uses of 2-nitropropane. Resolution of these data gaps would
provide a better basis on which to estimate releases of 2-nitropropane.
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Production
Quantities
(kkg)
Consumptive Non-Consumpttve
Uses Uses
(kkg) (kkg) Secondary
Products
(kkg)
Totals:
14,557
8/00
(0)
(0)
These quantities include the amount of 2-nitropropane degraded during waste water
treatment and destroyed during incineration
Figure 1 Flow Diagram of the Materials Balance of 2-Nitropropane
(1979)
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1.0 INTRODUCTION
This report presents the results of a Level I Materials Balance for 2-
nitropropane. This study was conducted for the Survey and Analysis
Division of the United States Environmental Protection Agency, Office of
Pesticides and Toxic Substances (OPTS). The primary objective of this
study was to determine, within the constraints of time and information
availability, the quantity of 2-nitropropane released to the environment
annually, the sources and locations of these releases and the form in which
2-nitropropane is released.
The information used to prepare this Level I materials balance was
gathered by telephone inquiries and literature searches conducted by JRB
staff personnel.
Many assumptions and estimations were made to account for all releases
of 2-nitropropane to the environment. Assumptions for estimates are
clearly stated and the results represent the best analysis of the currently
available data.
The sources of 2-nitropropane and their associated releases are dis-
cussed in Section 2.0. Consumptive, nonconsumptive and miscellaneous uses
and exports are discussed in Section 3.0. Releases of 2-nitropropane from
the uses of nitromethane, nitroethane, and 1-nitropropane are discussed in
Section 4.0. A summary of environmental releases of 2-nitropropane is
presented in Section 5.0. Section 6.0 summarizes the releases that occur
from the disposal and destruction of wastes containing 2-nitropropane, and
Section 7.0 of the report identifies gaps in the available data.
1-1
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2.0 ENVIRONMENTAL RELEASE ASSOCIATED WITH PRODUCTION OF 2-NITROPROPANE
During the manufacturing and processing of nitroparaffin, 2-nitropro-
pane is released directly to the environment from various points in the
production process. Natural production sources are not identifiable, and
indirect sources do not contribute significantly to the total production.
Imports of 2-nitropropane are believed to be less than 0.5 kkg per year.
2.1 Environmental Release Associated with Direct Production
IMC Chemical Groups, Inc. of the International Minerals and Chemical
Corporation is the sole producer of 2-nitropropane in the United States.
The annual production is estimated at 30 million pounds or 14,000 kkg
(NIOSH 1977a). According to IMC, the actual production quantity of 2-
nitropropane in 1979 was approximately equal to the estimated figure.*
U.S. International Trade Commission (1979) also listed IMC as the only
producer of 2-nitropropane.
The 2-nitropropane production process is based on the vapor-phase
nitration of propane with nitric acid (Shreve and Brink 1977). The main
reaction involved in this process can be expressed as follows:
CH3CH2CH3 (excess) + HN03-»CH3CH2CH2N02 + CH-jCHNO^H-j + CH3CH2N02 +
(25%) a (40%) a (10%) a
CH3N02 + C02 + H20 + NO
(25%)3
a
Percent by weight
2-Nitropropane and other nitroparaffins and derivatives are produced
at Sterlington, Louisiana. Figure 2.1 shows the location of the producer
of 2-nitropropane.
The production process of 2-nitropropane and other nitroparaffins
involves the following steps: (1) vapor-phase nitration, (2) product
recovery, (3) reactant recovery, (4) product purification, and (5) product
separation (Reidel 1956). A simplified flow diagram of the production
process is illustrated in Figure 2.2.
The vapor-phase nitration step consists of reacting propane gas with
nitric acid at 400 F and 100 pisa in an adiabatic reactor employing nitric
acid sprays. The gaseous products are then cooled, condensed, and
*G. Hess, IMC: personal communication with P. Le, JRB Associates, January
1980.
2-1
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(1) IMC Group
Sterlington, LA
Figure 2.1 Location of Producer of 2-Nitropropane
2-2
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I
OJ
KITRIC ACID
MAKEUP
2-1P
COLUTI
HP
COLlltl
©
PKOOXT S1UR/AE
C'ihMICAL TREATMENT
TANK
WASTE WATER TREATMENT
Source: Reidel 1956
Figure 2.2 Flow Diagram of the Production of 2-Nitropropane by the Direct Nitration Process
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recovered in the second step. Cooled products, which consist of nitro-
paraffins, water, excess propane, and nitrogen oxide, are separated by
absorption and stripping. Excess propane and nitrogen oxide are scrubbed
out by absorption and are sent to the reactant recovery section. The
absorbed nitroparaffins are then stripped. The stripped paraffins may
contain a small amount of low-boiling oxidation products such as ketones
and aldehydes; these substances are then removed from the nitroparaffin
stream as head products in the heads column (Reidel 1956).
In the product purification step, the nitroparaffins are chemically
treated and then washed with water. Chemical treatment of the nitro-
paraffins is necessary since a small amount of impurities contained in the
nitroparaffins makes them corrosive for ordinary carbon steel and unstable
(Reidel 1956).
In the last step, products are separated by distillation. Here, the
water-washed nitroparaffin products are first dried in a drying column.
Then nitromethane, nitroethane, 2-nitropropane, and 1-nitropropane are
successively recovered from the product stream by fractionation (Reidel
1956).
The following sections will discuss the environmental releases of
2-nitropropane from the production process.
2.1.1 Release of 2-Nitropropane to the Air from Process Vents
As shown in Figure 2.2, 2-nitropropane emissions to the air can occur
from:
The condenser for the nitrification process
The stripper vent (Stream A)
The light-end column vent (Stream B)
The nitromethane distillation column vent (Stream C)
The nitroethane distillation column vent (Stream D)
The 2-nitropropane distillation column vent (Stream E)
The 1-nitropropane distillation column vent (Stream F).
(1) Condenser for the nitrification process. There is no information
on the emission of 2-nitropropane from the condenser. This source is not
believed to have a significant emission rate, since the condenser is only
used as a container of the cooled product from the reactor. The only
opening on a condenser is a safety valve which is only used in case of
emergency. Thus the emission from the source does not greatly contribute
to the total emission from process vents.
(2) Stripper vent (Stream A). There is no information on the
emission rate of 2-nitropropane from the stripper vent during direct nitra-
tion. Judging from engineering knowledge about this type of vent, we
estimate that the typical emission rate of a stripper vent is 0.0005
kkg/kkg of product. The products generated from the stripper include
2-4
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nitromethane, nitroethane, 2-nitropropane, and 1-nitropropane. We assume
that only 1 percent of the total emission from the stripper vent is com-
posed of 2-nitropropane because of the low volatility of this chemical. As
shown in Section 2.1, 2-nitropropane product (14,000 kkg) represents 40
percent of the total nitroparaffins produced. Thus, the total quantity of
nitroparaffins produced is 35,000 kkg. The uncontrolled emission of
2-nitropropane from Stream A can be calculated from the total production of
nitroparaffins, the emission rate, and the fraction of 2-nitropropane in
emissions as 0.18 kkg.
(3) Light-end column (Stream B). Information on the quantity of
2-nitropropane released from the light-end column vent during direct nitra-
tion was not found in the literature. To complete the materials balance we
estimated an emission rate from this source. The typical emission rate of
a light-end column can vary from 0.0005 to 0.0015 kkg/kkg of product.
Therefore, a typical emission rate of the light-end column vent would be
approximately 0.001 kkg/kkg of product. The products produced from the
distillation column are nitroparaffins. We also assume that 2-nitropropane
is present at only 10 ppm, since this stream consists mainly of light-end
materials such as aldehydes and ketones. The uncontrolled emission of
2-nitropropane from light-end column vents can be calculated from the total
production of nitroparaffins, the emission rate, and the level of contami-
nation as 3.5 x 10 kkg.
(4) Nitromethane distillation column vent (Stream C). Nitromethane
is separated from the mixed nitroparaffin crude stream by fractional dis-
tillation. We estimate the typical emission rate of a distillation vent at
0.001 kkg/kkg of nitromethane produced. As shown in Section 2.1, nitro-
methane constitutes 25 percent of the total quantity of nitroparaffins
produced, or an estimated 8,750 kkg for 1979. This stream consists mostly
of inert gas such as nitrogen and other volatile organic components (VOC).
We assume that it is composed of 80 percent inert gas and 20 percent VOC
because the main purpose of the distillation column vent is to release
inert gases such as nitrogen and oxygen and to prevent internal pressure
build-up. We estimate that only 0.1 percent of the total VOC is 2-nitro-
propane due to the low volatility of this compound. Therefore, the pro-
portion of 2-nitropropane in the gas stream released from the distillation
column vent is 0.02 percent. Based on these assumptions, the uncontrolled
emission of 2-nitropropane from this source can be estimated at 1.8 x
10'-3 kkg.
(5) Nitroethane distillation column vent (Stream D). In the product
separation unit shown in Figure 2.2, nitroethane is also removed from the
crude nitroparaffin stream by fractional distillation. Information on the
amount of 2-nitropropane emitted from the nitroethane distillation column
was not found in the literature. As discussed in Section (4) above, we
estimate that the typical release rate of a distillation column vent is
approximately 0.001 kkg/kkg of nitroethane. Nitroethane comprises about
10 percent of nitroparaffins produced (Section 2.1), or 3,500 kkg in 1979.
We also assume that the fraction of VOC in the released gas stream is
about 20 percent. Of the total VOC, we estimate that 3 percent is
2-nitropropane. This percentage is based on the fact that nitroethane
cannot be effectively separated from 2-nitropropane since the boiling
2-5
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temperature difference between these two compounds is rather small (6°C);
the nitroethane product contains 3 to 4 percent 2-nitropropane by weight
(Riddick and Bunger 1970). Therefore, the concentration of 2-nitropropane
in the released gas stream is estimated at 0.6 percent. Based on the above
information, the uncontrolled emission of 2-nitropropane from this source
is estimated as 2.1 x 10 kkg.
(6) 2-Nitropropane distillation column vent (Stream E). 2-Nitropro-
pane is removed from the crude nitroparaffin as an overhead product of the
2-nitropropane distillation column. Again, there is no information on the
amount of 2-nitropropane released from the distillation vent. We assume
again that the typical emission rate of a distillation column vent, 0.001
kkg/kkg of product, can be applied to this vent. We also estimate that VOC
comprise 20 percent of the released gas stream. We speculate that 2-nitro-
propane constitutes 90 percent of the total VOC since this vent is located
on the overhead stream of the 2-nitropropane distillation column. 2-Nitro-
propane therefore represents 18 percent of the constituents in the released
gas stream. The uncontrolled emission of 2-nitropropane from the 2-nitro-
propane distillation column vent can then be estimated at 2.5 kkg.
(7) 1-Nitropropane distillation column vent (Stream F). As shown in
Figure 2.2, 1-nitropropane is the last compound removed from the crude
nitroparaffin stream. In the absence of specific information, we assume
that the gas stream released from the distillation column vent is approxi-
mately 0.001 kkg/kkg of 1-nitropropane. About 25 percent of nitroparaffin
production is 1-nitropropane (Section 2.1); this amounts to 8,750 kkg for
1979. We also assume that VOC comprise 20 percent of the released gas
stream. We estimate that 2-nitropropane constitutes 3 percent of the total
VOC, since 2-nitropropane comprises 3 to 4 percent (by weight) of 1-nitro-
propane product (Riddick and Bunger 1970). Therefore, 2-nitropropane
constitutes 0.6 percent of the released gas stream from this source. From
these values, an uncontrolled emission figure of 5.3 x 10 kkg can be
estimated.
(8) Total uncontrolled and controlled releases. The total quantity
of 2-nitropropane released directly to the air from all vents shown in
Figure 2.2 is the sum of all uncontrolled emissions from these sources, or
2.8 kkg. According to IMC (Purdy 1977), all waste gases generated by the
production process are controlled by incineration and according to IMC
(1979), a properly designed incinerator could achieve a destruction
efficiency of 90 percent or more. Therefore, the controlled emissions of
2-nitropropane from the production process vents is 0.3 kkg.
2.1.2 Emissions of 2-Nitropropane to Air from Product Storage Tanks
(Stream I)
There are two kinds of emissions from storage tanks: loss due to tank
breathing, and working loss or loss due to tank cleaning and filling.
Emission factors for 2-nitropropane from "old" fixed roof tanks can be
calculated as described in the AP-42 report (DSEPA 1977b). The following
sections discuss the emissions from storage tanks. The calculations are
presented in the Appendix.
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(1) Tank breathing. Tank breathing losses are defined by the USEPA
as losses resulting because of the thermal expansion of existing vapors,
vapor expansion as a result of barometric pressure changes, or added
vaporization in the absence of a liquid-level drainage (USEPA 1977b).
The emission factor for 2-nitropropane lost from storage tanks due to
tank breathing can be estimated using the method outlined in USEPA (1977b) .
The calculations associated with this estimate are shown in the Appendix.
The following assumptions were made to estimate the emission of 2-nitro-
propane due to tank breathing:
2-Nitropropane is stored in fixed roof tanks, and the tank is in
"worn" condition
All 2-nitropropane is stored for at least 1 day before it is dis-
tributed for other uses
There are 300 working days in a year
The ambient temperature is 20 C
The tank volume is 15,000 gallons, the average tank height is 10
feet, and the diameter is 16 feet
» The production site has two similar tanks painted either white or
aluminum
Ambient temperature change from day to night is 15 F
The liquid level inside the tank is half the average height of the
tank.
Based on the above assumptions, the calculated emission factor is 6>.7 x
10 kkg/day (see Appendix). The annual uncontrolled emission from product
storage due to tank breathing can be estimatetd at 4.0 x 10 kkg/year.
We then assume that emission of 2-nitropropane due to tank breathing
is controlled by a refrigerated system. The typical efficiency range of
such recovery systems is 65 to 95 percent. Therefore, the estimated
release rate^is 20 percent. The controlled emission can then be estimated
at 8.0 x 10"^ kkg.
(2) Tank handling and cleaning. Environmental losses to air due to
tank handling and cleaning are defined as working loss. The AP-42 report
(USEPA 1977b) has also outlined the method for estimating working loss.
The following assumptions are applicable for these calculations:
The ambient temperature is 20 C
The storage tank capacity is 15,000 gal
The crude oil factor is 1 (USEPA 1977b)
The production site has two storage tanks (15,000 gal).
2-7
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The emission factor for working loss can then be estimated at 9.5 x 10
kkg/10 gal. The calculations associated with this estimate are presented
in the Appendix. Based on an annual throughput volume of 2-nitropropane of
3.7 x 10 gal and the above emission factor, the uncontrolled emission of
2-nitropropane due to working loss is estimated as 7.0 x 10 kkg.
Assuming that working losses of 2-nitropropane from product storage can be
controlled by a vapor recovery system with a 20 percent release rate, then
the controlled emissions are estimated at 1.4 x 10
2.1.3 Emissions of 2-Nitropropane to Air from Fugitive Sources
Sources of fugitive emissions within the production plant include
process pumps, compressors, process valves, and pressure relief devices.
According to Hobbs and Stuewe (1979a), a plant that produces about 50,000
kkg of products per year typically has about 20 pumps, 400 valves, 2 com-
pressors, and 15 pressure relief valves . Typical uncontrolled emission
factors are 1.5 kg/day per pump seal; 0.068 kg/day per valve; 3.9 kg/day
per compressor seal; and 1.1 kg/day per relief valve (Hobbs and Stuewe
1979b) . The reported leakage frequency for pumps, compressors, and valves
averages 10 percent per year (Hobbs and Stuewe 1979a) . Assuming that there
are 300 working days per year, the leakage frequency is 30 days per year.
From this value and those for equipment numbers and release factors given
above, the uncontrolled emissions from fugitive sources can be estimated as
follows:
Pump seal leaking: 9.0 x 10 kkg
Valve leaking: 8.2 x 10"1 kkg
Compressor seal leaking: 2.3 x 10 kkg
Pressure relief valve leaking: 5.0 x 10 kkg.
The total amount of nitroparaffins in uncontrolled fugitive emissions
is estimated at 2.5 kkg. Assuming that 40 percent of the nitroparaffins
released to air is 2-nitropropane, then 1 kkg of 2-nitropropane is released
uncontrolled as fugitive emissions. If 90 percent of fugitive emission
sources can be controlled by regular maintenance procedures and quick
response to and repair of leaks, then the controlled emissions of 2-nitro-
propane from fugitive sources are estimated at 0.1 kkg.
2.1.4 Release of 2-Nitropropane to Air and Water During Waste Water
Treatment
There is no information on the quantity of 2-nitropropane released to
water from the direct nitration process. As shown in Figure 2.2, potential
sources of waste water containing 2-nitropropane are the decanter and the
water wash unit (streams H and J) . Calculation of a waste water emission
factor for 2-nitropropane is based on the following assumptions:
The average density of the mixed nitroparaffin stream is estimated
at 1 . 1 kg/S, .
2-8
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The volume of water used to wash the chemically treated nitro-
paraffin is equal to the volume of nitroparaffins produced.
» The drying column can separate out all the water in the wet nitro-
paraffin stream, and the separated water stream is recycled to the
water wash unit for further use .
Of the recycled water stream from the drying column, 10 percent is
reintroduced to the drying column as reflux stream, and the rest is
recycled to the water wash unit.
e Of the remaining 90 percent of the recycled water stream, 80
percent is reused as process water and 20 percent is discarded as
waste water; thus, the amount discarded is 18 percent of the total
water used.
Maximum solubility of 2-nitropropane in water occurs during the
wash phase (1.7 ml/100 ml at 20 c) .
» A negligible amount of 2-nitropropane is lost from the decanter.
« There is no recovery of the nitroparaffins discharged to water from
the wash unit .
As calculated in Section 2.1.1, the total quantity of nitroparaffins
produced in 1979 is estimated at 35,000 kkg; thus, the total volume of
nitroparaffins produced is 3.2 x 10 7&. The total volume of water used in
the water wash unit is also 3.2 x 10 £, and the volume of water discharged
to waste water treatment is 5.8 x 10 £ or 18 percent of the total volume
of water used. The amount of_2-nitropropane in the discharged waste water
is then estimated at 9.9 x 10 m?,, or 9.9 x 10 H. From the density of
2-nitropropane (0.992 kg/J,) the total quantity of 2-nitropropane emitted to
waste water treatment is calculated as 9.8 x 10 kg, or 98 kkg.
2-Nitropropane is degraded by microbial action during waste water
treatment. The enzymatic reactions responsible for degradation are
believed to be similar to those studied in higher organisms. Little (1957)
demonstrated the degradation of 2-nitropropane by extracts of Neurospora
crassa and pea seedlings. The enzymatic reaction is an oxidative denitri-
fication yielding nitrite and carbonyl compounds; nitrite is further
metabolized to ammonia via other reactions. The oxidative degradation of
2-nitropropane can be represented by the following reaction:
2 CH3CH(N02)CH3
Kido et al . (1976) identified the enzyme responsible for catalyzing this
reaction as a dioxygenase. Dioxygenases are defined as enzymes catalyzing
reactions in which both atoms of the oxygen molecule are incorporated into
the substrates. Kido suggested that the oxidative degradation of
2-nitropropane is very rapid under conditions of maximal temperature (20
o
to 40 c) and pH (6.8 to 7.0).
2-9
-------
We assume that 90 percent of the 2-nitropropane in waste water is
biodegraded during the waste water treatment cycle. Because aeration of
the waste water is part of the treatment process, loss of 2-nitropropane to
air can be anticipated; we assume that this emission constitutes 9 percent
of the 2-nitropropane present in the influent of treatment facilities. The
remaining 1 percent is assumed to remain in the treated water effluent.
(These percentages are only estimates and should be verified in later
studies.) From these percentages, we estimate that in 1979, 9 kkg of
2-nitropropane were lost to air, 88 kkg were biodegraded, and 1 kkg was
retained in the water effluent. According to IMC (Purdy 1977), the waste
water containing nitrate and acids is then discharged by deep-well injec-
tion.
2.1.5 Emission of 2-Nitropropane to Air During Heavy-End Waste Disposal
Heavy-end wastes containing 2-nitropropane can be generated from the
1-nitropropane distillation column. These are typically disposed of
through incineration. There is no information on the quantity of 2-nitro-
propane released in this manner. We estimated the quantity of 2-nitro-
propane generated by use of the following assumptions:
The emission factor for this process is the typical factor for
heavy-end waste from a distillation column, 0.1 kkg/kkg of product.
2-Nitropropane comprises 10 percent of the heavy-end waste stream
since the overhead product (mainly 1-nitropropane) is 3 to 4
percent 2-nitropropane by weight.
Therefore, the emission factor for 2-nitropropane in the heavy-end waste is
0.01 kkg/kkg of 1-nitropropane produced. The quantity of 1-nitropropane
produced in 1979 is estimated at 8,750 kkg. Thus, the quantity of 2-nitro-
propane contained in heavy-end wastes is estimated at 87.5 kkg.
Heavy-end wastes may contain toxic substances, and current methods of
hazardous waste disposal usually require incineration. Thus, we assume
that the heavy-end waste generated from this source is incinerated. We
also assume that the incinerator used to dispose of heavy-end wastes can
achieve a 90 percent efficiency. Then the amount of 2-nitropropane
released to air from the incinerator can be estimated at 8.8 kkg. The
quantity of 2-nitropropane remaining in the ash discharged by the incin-
erator is estimated to be negligible.
2.1.6 Emissions of 2-Nitropropane During Loading and Shipping
According to NIOSH (1977), 96 to 98 percent of 2-nitropropane is
shipped by tank cars and trucks. It is assumed that this percentage
applies to the portion of 2-nitropropane production that is used noncon-
sumptively, 5,600 kkg and to exports, 1,400 kkg.
According to USEPA (1977b), there are two kinds of emissions during
shipping of liquid products: loading and transit losses. The principal
methods of loading cargo carriers are the splash loading method, in which
the fill pipe dispensing the liquid product is only partially lowered into
2-10
-------
the tank, and the submerged loading method, in which the fill pipe is
lowered almost to the bottom of the tank or enters the tank from the
bottom. Either type of loading results in high levels of vapor generation
and loss.
Transit losses are much smaller than those during loading. Small
quantities of vapor are lost due to temperature and barometric pressure
changes during transportation.
Releases of 2-nitropropane during loading and shipping in 1979 were
estimated as 0.8 kkg. The calculations are shown in Appendix B.
Other processes during which fugitive releases could occur include
taking quality control samples, drumming, and spills during loading (NIOSH
1977). JRB concluded that releases from these sources are insignificant
compared to those from other sources.
Figure 2.3 is a flow diagram showing a summary of environmental
releases of 2-nitropropane from the direct nitration process.
2.2 Releases of 2-Nitropropane Associated with Inadvertent Production
Sources
Information on the indirect production of 2-nitropropane from other
chemical production processes was not found in the literature. It seems
unlikely that 2-nitropropane can be produced indirectly because the
chemical can only be formed under the following conditions:
» The presence of a source of propane, or at least a source of
hydrocarbons
The presence of a source of nitric acid
A reaction temperature of approximately 400 F
A reaction pressure of approximately 100 psia
* Vapor-phase reaction conditions.
In our literature search we did not find many chemical production
processes that use both propane and nitric acid as materials and also
operate at high temperature and pressure. Some chemical reactions, such as
that of silver nitrite with an alkyl halide (Riddick and Bunger 1970), can
produce 2-nitropropane inadvertently as a by-product, but we believe that
these reactions do not occur in sufficient quantity to merit further
consideration as a potential source of 2-nitropropane production. There-
fore, as judged from the information available, we believe that inadvertent
production sources do not significantly contribute to the total production
of 2-nitropropane.
2.3 Release of 2-Nitropropane Associated with Natural Production Sources
During the course of data gathering and analysis, no information
was found on the formation of 2-nitropropane from natural sources. We
2-11
-------
NJ
I
NJ
6.4
Air (uncontrolled)
Process vents
2.8
Product storage
- Tank breathing
0.4
- Working loss
0.7
Fugitive releases
2.5
Production of
2-nitropropane
14,193
I
87.5
Heavy-end
wastes
87.5
Incinerators
78.7
Emission
control
devices
5.8
Air (controlled)
Process vents
0.3
Product storage
Tank breathing
0.08
- Working loss
0.14
Fugitive releases
0.1
Transportation loss
to Air
0.8
14,000
Consumption of
2-nitropropane
14.000
Air
8.8
J
Waste water
98
98
Waste water
treatment
sys
:ems
Air
9
Water
1
Biodegradation
Figure 2.3 Environmental Releases of 2-Nitropropane During its Production (kkg)
-------
concluded that 2-nitropropane cannot be produced naturally, since the
critical conditions for formation, such as temperature, pressure, and the
coexistence of propane and nitric acid, are not met concurrently.
2.4 Imports
According to information provided by the Chemical Information
Division, USEPA, 2-nitropropane is probably imported by Thorson Chemical
Corporation, New York, in quantities of less than 0.5 kkg per year (USEPA
1979b).
2-13
-------
3.0 ENVIRONMENTAL RELEASE DURING THE USES OF 2-NITROPROPANE
The annual consumption of 2-nitropropane is estimated at 14,000 kkg
(NIOSH 1977). Of this amount, 7,000 kkg are believed to be used by the
producer for the production of other chemicals, 5,600 kkg are sold domes-
tically (NIOSH 1977), and 1,400 kkg are exported.*
3.1 Release of 2-Nitropropane Associated with the Production of Chemicals
The following chemicals are synthesized from 2-nitropropane: 2-nitro
2-methyl-l-propanol; 2-amino-2-methyl-l-propanol; 2-amino-2-ethyl-
1 ,3-propanediol; 2-amino-2-methyl-l,3-propanediol; and 2-amino-2-hydroxy-
methyl-l,3-propanediol (USITC 1978).
3.1.1 Release of 2-Nitropropane Associated with Production of 2-Nitro-2-
Methyl-1-Propanol
2-Nitro-2-methyl-l-propanol can be produced by the reaction of 2-
nitropropane with formaldehyde, as follows:
CH,
H20 | 3
CH.CHCH, + CH.O - »-CH,-C-CH0-OH
J|3 2 ^ * *. 3(2
I catalyst I
2-nitropropane formaldehyde 2-nitro-2-methyl-l-propanol
Figure 3.1 is a flow diagram showing the process for preparation of
2-nitro-2-methyl-l-propanol and 2-amino-2-methyl-l-propanol.
According to IMC, the quantity of 2-nitropropane used in the pro-
duction of 2-nitro-2-methyl-l-propanol is approximately 20,000 Ib/day (or
9.1 kkg/day) (Purdy 1977). The typical number of working days per year for
a chemical plant is about 300, but actual working days can fluctuate from
260 to 350. Assuming that the IMC production plant operates 300 days per
year, the total quantity of 2-nitropropane consumed in the production of
2-nitro-2-methyl-l-propanol can be calculated at 2,700 kkg.
To calculate the quantity of 2-nitro-2-methyl-l-propanol produced from
the reaction of 2-nitropropane with formaldehyde, we assume that the over-
all yield of this reaction is 80 mole percent. This assumption is based on
the reaction yield range of 70 to 90 percent necessary if an industrial
chemical process is to be economically feasible. The estimated amount of
2-nitro-2-methyl-l-propanol produced in 1979 was 2,900 kkg.
(1) Release of 2-nitropropane to air from process vents. As shown in
Figure 3.1, a possible source of air emission is the concentration still
*G. Hess, IMC: personal communication with P. Le, JRB Associates, January
1980.
3-1
-------
2-AHUO-2-METHYL-1-PROPA1IOL
DRYING
STILL
W-P
STILL
HIGH BOILERS
STILL
2-NITRO-2 HETWL-1-PROPAUOL
2-NP
HCHO
CATALYST
CHjOH
H20
CENTRIFUGE
CATALYST
cctif.:.SATict:
REACTOR
:RYSTAU_INE
2-NITR072-
MhTHYL-i-
PKOPANOL
NITRCME1WLPROPAHOL CONCENTRATE
CONCENTRATION STILL
CRYSTALLIZER
HIGH EOILING
AH I MO -
ALCOHOLS
RES I CUE
Figure 3.1 Flow Diagram for the Production of 2-Nitro-2-Methyl-l-Propanol and 2-Amino-2-
Methyl-1-Propanol
Source: Reidel 1956
-------
vent (stream A). Since there is no information on environmental emissions
of 2-nitropropane from this production process, we estimate that the
emission rate from this vent is 0.001 kkg/kkg of product, a rate typical
for a distillation column. Since most 2-nitropropane is reacted to produce
2-nitro-2-methyl-l-propanol, 2-nitropropane would occur only as an impurity
in the emission stream. The level of 2-nitropropane contamination in this
stream is estimated at 50 ppm with a range of 100 to 1 ppm. Based on these
assumptions, the quantity of 2-nitropropane released to air uncontrolled
from this source is estimated at 1.5 x 10 kkg.
Assuming that this emission source can be controlled by incineration
at 90 percent efficiency, then the controlled emission of 2-nitropropane
from the concentration still vent can be calculated as 1.5 x 10 kkg.
(2) Emission to water. Information on the waterborne emission of
2-nitropropane from production of 2-nitro-2-methyl-l-propanol was not found
in the literature. An analysis of the production process did not reveal
any possible source of emission to water. Therefore, we assume that during
the formulation of 2-nitro-2-methyl-l-propanol, emission of 2-nitropropane
to water is insignificant.
(3) Emission to land. Again, there is no information available on
land-destined emissions from the production process of 2-nitro-2-methyl-l-
propanol. After examination of the manufacturing process, we conclude that
the only possible source of emission to land occurs in the catalyst removal
section of the process. There is no information on the type and amount of
catalyst used in this process, but we believe that either potassium hydrox-
ide or manganese bromide is used.
The common practice for disposal of spent catalysts is to store the
waste in 55-gallon drums that are disposed in landfills. Since we have no
information on the type or amount of catalyst used, we cannot quantify the
2-nitropropane released from the land-destined wasted catalyst.
3.1.2 Release of 2-Nitropropane During the Uses of 2-Nitro-2-Methyl-
1-Propanol
As discussed in Section 3.1.1, the quantity of 2-nitro-2-methyl-
1-propanol produced is estimated at 2,900 kkg. The level of 2-nitropropane
contamination in 2-nitro-2-methyl-l-propanol is estimated at 50 ppm. Thus
the total quantity of 2-nitropropane present in 2-nitro-2-methyl-l-propanol
is estimated at 0.15 kkg.
2-Nitro-2-methyl-l-propanol is chiefly used to produce 2-amino-2-
methyl-1-propanol. Other uses of 2-nitro-2-methyl-l-propanol are unknown.
According to Reidel (1956), the 2-nitro-2-methyl-l-propanol final product
is in crystalline form; thus, any contamination by 2-nitropropane is con-
sidered negligible. The rationale for this assumption is that during
further purification of 2-nitro-2-methyl-l-propanol by the crystallization
method, any liquid contaminant such as 2-nitropropane is efficiently
removed from the final product.
3-3
-------
The production process for 2-amino-2-methyl-l-propanol from 2-nitro-
2-methyl-l-propanol was shown in Figure 3.1. 2-Aniino-2-methyl-l-propanol
can be used in the synthesis of surface agents, vulcanization accelerators,
and pharmaceutical products. It can also be used as an emulsifying agent
for cosmetic creams and lotions, mineral oil and paraffin waxes, leather
dressings, textile specialties, polishes, and cleaning compounds (Merck
1976).
Assuming that 90 percent of 2-nitro-2-methyl-l-propanol is used for
the production of 2-amino-2-methyl-l-propanol, then the quantity of
2-nitropropane introduced into the amino alcohol production is 0.13 kkg.
We assumed that during this production process, 99 percent of contaminant
2-nitropropane (0.13 kkg) is removed from the product; the remaining 0.001
kkg is assumed to be contained in the product. We think that this level of
contamination is not high enough to justify further consideration.
3.1.3 Release of 2-Nitropropane During Formulation and Uses of Aminohy-
droxy Compounds
As mentioned in Section 3.1, 2-nitropropane is used to produce amino-
hydroxy compounds in addition to 2-nitro-2-methyl-l-propanol. The uses of
some major aminohydroxy compounds potentially derived from 2-nitropropane
were listed in the Merck Index (1976). 2-Amino-2-ethyl-l,3-propanediol and
2-amino-2-methyl-l,3-propanediol can be used in the synthesis of surface-
active agents, vulcanization accelerators, and Pharmaceuticals, as emul-
sifying agents, and as absorbents for acidic gases such as carbon dioxide
or hydrogen sulfide. Information pertaining to the production of these
compounds was not found in the literature.
According to IMC,* the total quantity of 2-nitropropane consumed
captively in-plant is estimated at 7,000 kkg, which includes 2,700 kkg used
for the production of 2-nitro-2-methyl-l-propanol. Therefore, 4,300 kkg of
2-nitropropane were consumed in the production of other aminohydroxy com-
pounds. We have no information on the production processes of these amino-
hydroxy compounds; therefore, we cannot quantify any releases of 2-nitro-
propane from their production or use. We believe that the level of con-
tamination of 2-nitropropane in the aminohydroxy compounds is so low that
it does not contribute significantly to the total release of 2-nitropropane
to the environment.
3.2 Release of 2-Nitropropane Associated with Nonconsumptive Uses
Of the 14,000 kkg of 2-nitropropane produced in the United States in
1977, nonconsumptive uses accounted for 5,600 kkg of the total amount
produced. The major nonconsumptive uses were determined to be printing
inks and surface coatings. Minor uses of 2-nitropropane were for explo-
sives, rocket propellants, adhesives, gasoline additives, dyes, pesticides,
rubber, and chemical reactions.
*G. Hess, IMC: personal communication with P. Le, JRB Associates, January
1980.
3-4
-------
The following sections detail the amounts of 2-nitropropane used in
each area identified, and the amounts of multimedia emissions (to air,
water, and land) associated with each.
3.2.1 Printing Inks
A major use for 2-nitropropane is as a solvent in printing inks (NIOSH
1977). Printing inks can be classified into four categories: letterpress,
lithographic, flexographic, and gravure. Letterpress and lithographic
printing inks are viscous, tacky pastes with low solvent concentrations.
Flexographic and gravure printing inks have low viscosity and high solvent
concentrations. 2-Nitropropane cannot be used in letterpress and litho-
graphic printing inks, but it can be used in flexographic and gravure
printing inks.*
Even though 2-nitropropane is reported to be used in flexographic and
gravure printing inks, the literature contains scant information on the
quantities of 2-nitropropane utilized for this purpose. The IMC Company,
sole producer of 2-nitropropane, refused to disclose any information.
Therefore, JRB obtained data through telephone inquiries to trade associ-
ations, printing ink distributors, and manufacturers on use of 2-nitro-
propane in printing inks and the associated environmental releases.
The quantity of 2-nitropropane sold domestically for all uses in 1979
was estimated at 5,600 kkg. According to an industrial source, the
quantity of 2-nitropropane used in printing ink is estimated at 50 percent
of total usage, or 2,800 kkg.
The amounts of flexographic and gravure printing inks produced in 1979
were 70,000 and 143,000 kkg, respectively. A number of solvents are used
in these inks. Telephone inquiries to printing ink distributors and manu-
facturers revealed that 15 percent of the. flexographic and gravure printing
inks contain 2-nitropropane as a solvent.7 Furthermore, a typical batch of
flexographic printing ink containing 2-nitropropane as a solvent was esti-
mated to contain 2 to 4 percent (by weight) of 2-nitropropane. From this
information, the quantity of 2-nitropropane used in flexographic printing
ink in 1979 was estimated at 210 to 420 kkg. 2-Nitropropane was also
estimated to comprise less than 0.5 percent of the total quantity of flexo-
graphic ink produced. This estimate yields a value of 350 kkg of 2-nitro-
propane in flexographic ink. JRB has used this figure as its estimated of
2-nitropropane used in flexographic printing ink.
A typical batch of gravure printing ink using 2-nitropropane as
solvent contains approximately 10 to 15 percent (by weight) of 2-nitro-
propane .i" Thus, 2-nitropropane content in gravure printing inks is
*D. Tuttie, consultant, Cranford, N.J.: personal communication with P. Le,
JRB Associates, September 1980.
TImport Chemical Co., General Printing Ink Co., CPW Printing Co., Croda Ink
Co., Converters Ink Co.: personal communications with E. Harrison, JRB
Associates, January 1980.
§T. Bart, Inmont Corp.: personal communication with P. Le, JRB Associates,
September 1980.
3-5
-------
estimated at 2,150 to 3,220 kkg (average 2,680 kkg). Therefore, a second
estimate for the total quantity of 2-nitropropane used in flexographic and
gravure inks is calculated at 3,030 kkg. The average of the two estimates
for 2-nitropropane used as a solvent in flexographic and gravure printing
inks is 2,900 kkg.
(1) Releases of 2-nitropropane during formulation of printing inks.
The manufacture of most kinds of printing ink can be resolved into two
different stages: mixing and milling. In the mixing stage, the pigment,
the vehicle, and dryers are mixed together thoroughly until the pigment is
no longer discernible as a dry powder (Bowles 1961). In some cases, the
mixture is heated to facilitate mixing. This is accomplished by use of
high-speed mixers or ball mills (USEPA 1979c). Most inks are made in a
batch process in tubs ranging in capacity from 5 to 1,000 gallons (USEPA
1979c). Figure 3.2 shows typical mixing machines used by the printing ink
industry.
For low viscosity mixing, which includes preparation of gravure and
flexographic printing inks, the mixing mechanism can be an impeller
rotating at high speed or rotating blades sweeping the whole area of the
mixer (Bowles 1961). When volatile liquids are used as solvents, covers
are required through which the components can be added. Part (a) of Figure
3.3 shows a typical machine used for mixing flexographic and gravure
printing ink.
To meet the required specifications, many inks may need additional
dispersion through further milling processes. Milling can be accomplished
with three-roll mills, sand mills, or ball mills.
(a) Releases of 2-nitropropane to air. Solvents used in printing
ink, such as 2-nitropropane, can be released to air during the heating and
mixing process. According to USEPA (1977b), the typical release rate for
general organic solvents during the manufacture of printing ink is 60
kg/kkg of product. The amount of flexographic printing ink containing
2-nitropropane is estimated at 10,500 kkg. The percentage of 2-nitro-
propane used in flexographic ink is low: about 3 percent (by weight) of
ink, or 5 percent (by weight) of solvents used. The latter value is calcu-
lated by assuming that solvents comprise 70 to 75 percent of solvent-based
flexographic ink (Bowles 1961). We then assume that 2-nitropropane
accounts for 5 percent of emitted solvents. Therefore, the calculated
release rate for 2-nitropropane during the manufacture of flexographic
printing ink is 3 kg/kkg of product; this gives an estimated release of
32 kkg to air from this manufacturing process in 1979.
The amount of gravure printing ink containing 2-nitropropane as
solvent is 21,500 kkg (15 percent of the total quantity produced). These
inks contain an average of 12.5 percent of 2-nitropropane (by weight).
According to Bowles (1961), gravure inks consist of 50 to 60 percent
solvents. Therefore, 2-nitropropane comprises 23 percent of total solvents
in these inks. The release rate for 2-nitropropane is calculated as
23 percent of the solvent release rate of 60 kg/kkg reported by USEPA
(1977b), or 13.8 kg/kkg of product. Therefore, the quantity of
2-nitropropane released to air during the production of gravure printing
ink in 1979 was 296 kkg.
3-6
-------
OJ
-L,
Figure 3.2 Types of Ink-Mixing Plants
Source: Bowles 1961
-------
The total quantity of 2-nitropropane released to air during the manu-
facture of printing ink in 1979 is estimated as 330 kkg, or 11 percent of
thp 2 ni frnnrnnanp nsorl in nri nf-i na -ink
the 2-nitropropane used in printing ink.
(b) Releases of 2-nitropropane to water. During the production of
printing ink, the major source of water release of 2-nitropropane may come
from the cleaning of mixing tubs. The ink industry commonly uses solvent,
caustic, or water washes to clean ink tubs (USEPA 1979c).
The solvent wash technique is used extensively in cleaning tubs used
to mix solvent-based and oil-based inks. In this process, there is
virtually no discharge of waste water, since most solvents are recycled and
recovered (USEPA 1979c). Caustic wash followed by water wash can sometimes
be used to clean tubs from solvent-based inks.
According to USEPA (1979c), about 38 percent of the ink industry uses
solvent wash techniques, 12 percent uses caustic wash techniques, and about
38 percent uses techniques that results in waste water discharge. For
production of solvent-based printing inks, JRB estimated that about 56
percent of the plants use cleaning techniques that have no waste water
discharge and 44 percent use cleaning methods that results in waste water
releases (USEPA 1979c).
To calculate the amount of 2-nitropropane released to waste water
during the production of printing ink, we assume that only 1 percent of the
ink remains in the tub for cleaning. Using this assumption, the amount of
2-nitropropane lost during cleaning is estimated at 29 kkg. Of this
amount, we assume that 56 percent (or 16 kkg) is not discharged to waste
water, and the remaining 13 kkg is discharged to waste water.
The methods of waste water disposal for printing ink plants are
reported by USEPA (1979c) and are presented in Table 3.1. According to
this table, the amount of 2-nitropropane discharged is as follows: 4 kkg
to POTWs, 1.7 kkg reused, 0.5 kkg landfilled, 3.5 kkg disposed by con-
tractors, and 3.3 kkg disposed by other methods.
Of the quantity discharged to POTWs, we assume that 100 percent is
destroyed by the slow process of biodegradation using activated sludge.
(2) Releases of 2-nitropropane resulting from its use as a printing
ink solvent. The total amount of 2-nitropropane remaining in printing inks
as solvent is 2,540 kkg. Flexographic and gravure printing applications
fall into three major categories: publications, packaging, and special-
ties. In flexographic printing, the image areas are raised above the
nonimage surface. A feed cylinder rotates in a trough of ink and delivers
ink to the plate cylinder through a distribution roll (Vincent and Vatavuk
1978). Figure 3.3 shows a typical ink distribution system for flexography.
With the gravure printing method, image areas are recessed relative
to nonimage areas. The gravure cylinder rotates in an ink trough, and
excess ink is removed by a steel doctor blade. The ink in the cells is
then transferred to the web when it is pressed against the cylinder by a
rubber-covered impression roll, as shown in Figure 3.4 (Vincent and Vatavuk
3-8
-------
Table 3.1 Waste Water Disposal Methods for Printing Ink Manufacture
Disposal method*
Complete reuse
Partial reuse
Evaporation
Discharge to city
sewer
Discharge to storm
sewer
Discharge to receiving
stream
Impoundment on plant
property
Incineration
Contract hauling
Land filled
Well or septic tank
All
Number of
plants
14
45
34
138
13
4
14
2
123
18
1
plants
Percent of
total
3.0
9.8
7.4
30.0
2.8
0.9
3.0
0.4
26.7
3.9
0.2
Plants using
Number of
plants
9
18
9
75
5
2
10
1
61
10
water rinse
Percent of
total
5.7
11.4
5.7
47.5
3.2
1.3
6.3
0.6
97.0
6.3
0
Source: USEPA 1979c
3-9
-------
Plate
Cylinder
Impression
Cylinder
Distributio
Rollers
Ink Fountain
\f
Figure 3.3 Ink Distribution System for Flexography
Source: Vincent and Vatavuk 1978
3-10
-------
(A) Etched cylinder
(B) Impression cylinder
Figure 3.4 Rotogravure Ink System
Source: Vincent and Vatavuk, 1978
3-11
-------
1978). According to Carpenter et al. (1975), about 90 percent of the
applied solvent is believed to be driven out by evaporation during or after
printing. The remaining 10 percent of the original solvent evaporates
slowly from the solidified vehicle resins on the cool web.
Using the above data, JRB assumes that 100 percent (or 2,540 kkg) of
the 2-nitropropane used in printing ink is released to air during the
printing process.
To control the releases of hazardous chemicals used as solvents in
printing ink, the printing industry uses vapor control techniques such as
an activated carbon absorption system (Carpenter et al. 1975), and
scrubbers. Assuming that these various control techniques can achieve a
90 percent efficiency, the remaining 2-nitropropane (254 kkg) is released
to the air from use of printing inks containing 2-nitropropane.
If scrubbers are used to control the evaporation of 2-nitropropane
during application of printing inks, JRB assumes that the scrubbing solu-
tion containing the 2-nitropropane will be discharged to a waste water
treatment system where the 2-nitropropane can be biodegraded slowly. If an
activated carbon system is used to control the emissions of vapor from the
printing process, 2-nitropropane and other solvents will be recovered after
the exhausted activated carbon is regenerated. The recovered product
usually will be hauled for final disposal by contractors.
Figure 3.5 is a flow diagram of the environmental releases of 2-nitro-
propane during the production and uses of printing ink.
3.2.2 Surface Coatings
Coatings are used to protect and decorate various surfaces. Most
coatings are composed of three ingredients: a binder, the pigment, and a
volatile thinner or solvent. Binders are usually organic polymers that
form a film which adheres to the substance being coated and binds the
pigment particles. Pigments give color, opacity, and various other proper-
ties to the film. Thinners or solvents, which evaporate after application,
make it possible to apply the coating. Because of its solubility in
alcohol, the wide range of resins which it dissolves, and the low viscosity
and evaporation rates of the resulting solutions, 2-nitropropane is used as
a solvent in the formulation of vinyl, epoxy, cellulose, and other surface
coatings (Kirk-Othmer 1964).
About 1,600 kkg of 2-nitropropane were in surface coatings in 1977;
this estimate is derived in part (2) of this section. Almost all of this
material, about 1,584 kkg, is believed to be released to air; this consti-
tutes one of the largest estimated environmental releases of 2-nitro-
propane .
(1) Types of surface coatings.
(a) Vinyl. Vinyl surface coatings contain a vinyl resin as the basis
of the coating binder. The resins are produced by emulsion, solution,
suspension, or bulk polymerization techniques. They are used for their
3-12
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Air
254
OJ
I
Emission control
equipment
J 2,200
Destroyed or
to waste
disposal
To air
I
1,540
2,900
2,540
Applications
of printing
ink
Air
330
Production
of
printing ink
0.5
29
13
Waste
water
5.0
| Landfills |
|To water") "-{waste disposal]
Other methods
of disposal
POTW |( Destroyed ]
3.5
(Waste disposal [
Figure 3.5 Flow Diagram of Environmental Release of 2-Nitropropane During the Production
and Uses of Printing Ink
-------
chemical resistance, water resistance, durability, fire retardant proper-
ties, lack of odor or taste, low cost, and versatility (SRI 1977).
Although these vinyl resins are not very soluble in 2-nitropropane or
hydrocarbons alone, they are readily soluble in latent solvent systems such
as a combined 2-nitropropane-hydrocarbon solvent (Bennett 1979). These
combined solvent systems also form azeotropic mixtures which enhance sol-
vent release (evaporation) during application, thus producing a higher
density film and improved adhesion. Such solvent-based coatings, formu-
lated with a solvent instead of a water base, are known as lacquers.
Polyvinyl acetate (PVAc), derivatives of PVAc, and polyvinyl chloride (PVC)
are the major types of vinyl resins produced. Major applications for these
vinyl surface coatings include latex house paints, flat wall paints, and
industrial finishes such as metal container coatings. Approximately 1,500
paint companies are capable of producing vinyl surface coatings (SRI 1977).
(b) Epoxy. 2-Nitropropane is also used in epoxy surface coatings.
These chemically resistant and electrical-grade coatings account for a
substantial portion of the production volume of solid and liquid epoxy
resins. They are primarily used for coating laboratory furniture, lawn
furniture, appliances, hardware, magnetic wire, can and drum linings,
military aircraft, and marine environments (docks, boats), and for floor
coatings, masonry coatings, and swimming pool paints. Specialized formu-
lations for automobile primers constitute the largest single market for
epoxy resin coatings. Their advantages are superior heat resistance,
toughness, and abrasion resistance. Disadvantages include high cost, poor
color stability when exposed to ultraviolet radiation, and chalkiness after
exposure to weathering (Mark and Gaylord 1969).
2-Nitropropane is probably used as a diluent during the formulation of
epoxy surface coatings. The use of pine oil to reduce the viscosity of
many epoxy resins has been documented (Mark and Gaylord 1969). Because
pine oil is used in the same applications as 2-nitropropane, it is likely
that 2-nitropropane is also used to reduce the viscosity of various epoxy
resins. 2-Nitropropane may also be used in epoxy surface coating formu-
lations (IMC 1979; NIOSH 1977) in azeotropic combination with hydrocarbons
(such as butyl alcohol or toluene) which promote good solvent release and
higher density epoxy coating (Bennett 1979).
(c) Cellulose. The use of 2-nitropropane in cellulose surface
coatings was also studied. Either an organic or inorganic cellulose ester
forms the base of these coatings. Nitroparaffins are used for dissolving
commercial organic cellulose esters. Also, as with vinyl and epoxy
coatings, 2-nitropropane may be used as an azeotrope to minimize the for-
mation of moisture during the formulation and application of various
lacquer surface coatings, especially plastic surface coatings. Of the
three primary organic cellulose esters produced, cellulose acetate and
cellulose acetate propionate are soluble or partially soluble in 2-nitro-
propane. Lacquers made from these cellulose esters serve as suitable
protective coatings for wood furniture, paper, metal, glass, fabrics, and
other plastics. They also serve as flexible substrates for foil, cello-
phane, and other packaging materials. Such lacquer surface coatings form
by evaporative drying of organic solvents, as contrasted with polymeri-
zation of resin components or evaporation of water. Their primary
3-14
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advantages are fast drying time and rapid hardening (Mark and Gaylord
1969). Major suppliers of cellulose lacquers for wood furniture include:
Reliance Universal, Inc., Lilly Industrial Coatings, Inc., Guardsmen
Chemicals, Inc., The Sherwin-Williams Co., Mobil Chemical Co./Chemical
Coatings Division, and Inmont Corporation/Finishes Division, a major
supplier of coatings for packaging materials (SRI 1977). Lacquers supplied
by these companies may contain 2-nitropropane.
Use of 2-nitropropane in surface coatings made from inorganic cellu-
lose ester (cellulose nitrate or nitrocellulose) has also been documented.
Because of the solubility, viscosity in solution, compatibility with
modifiers, and other physical properties of cellulose nitrate, its single
largest use is as a surface coating. These coatings have a high film
strength and rapidly release the solvent constituent. The solvent provides
a means of dispersing and uniformly mixing the film components (SRI 1977).
Nitrocellulose lacquers have many possible applications which include:
topcoats for household and industrial furniture, radio and television
cabinets, flooring, interior wood paneling, doors, bowling pins and alleys,
broom handles, caskets, pencils, musical instruments, shoe heels, and toys
and sporting goods; coatings for cellophane book covers, wallpaper, labels,
menus, playing cards, and aluminum foil; primers and topcoats for aircraft,
buses, house trailers, trucks, brass fixtures, and machine tools; leather
finishes for shoes, table tops, luggage, and upholstery; fingernail
polishes; household adhesives; and traffic paints (Kirk-Othmer 1964).
(d) Paints. To ascertain whether 2-nitropropane is used in paints
and, if possible, to quantify this usage, JRB contacted a number of
companies from a list of probable 2-nitropropane users (NIOSH 1979). These
companies included: Baltimore Copper and Paint Company, Baltimore, Mary-
land; El Paco Paint Company, Elkhart, Indiana; Dexter Corporation, Louis-
ville, Kentucky; and the Porter Paint Company, Louisville, Kentucky. All
of these companies stated that they do not use 2-nitropropane in paints.
JRB assumes that the companies contacted reflect an accurate picture of the
industry and concludes that 2-nitropropane has minimal, if any, use in
nonlatex paints.
(e) Chlorinated rubber surface coatings. No indication that 2-nitro-
propane is a raw material for the formulation of chlorinated rubber surface
coatings was found in a review of available literature (Kirk-Othmer 1964,
Mark and Gaylord 1969) or in telephone conversations with industry
officials.* Therefore, despite the statement that 2-nitropropane can be
used as a solvent in the formulation of chlorinated rubber coatings (IMC
1980), it was assumed that 2-nitropropane is used in insignificant amounts
for this purpose, if at all.
(f) Other surface coatings. IMC literature (1979) reports many other
potential uses of 2-nitropropane in manufacture of surface coatings,
including elastomeric polyurethane, polystyrene, phenoxy resin, thermo-
plastic acrylic, alkyd resin, and thermoplastic polyamide systems.
*K. Western, DuPont: personal communication with T. Shannon, JRB
Associates, 1980.
3-15
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However, during the course of literature investigations and telephone
conversations about the surface coatings industry, we were unable to
document the use of 2-nitropropane in the formulation of the above surface
coatings. When we talked by phone with representatives of firms manu-
facturing 2-nitropropane-containing products, as listed in a NISOH (1979)
data base, many contacts stated that the firms had either abandoned
production of the product containing 2-nitropropane, or had stopped using
2-nitropropane in the product's manufacture. One industry official stated
that, due to the possible carcinogenicity of 2-nitropropane, the product
that required it has been taken off the market.* Therefore, we assumed
that the use of 2-nitropropane during recent years in the formulation of
the various surface coatings discussed above was insignificant.
(2) Amount of use. Because of its chemical properties, 2-nitro-
propane is probably used in the formulation of cellulose, vinyl, and epoxy
surface coatings. The present, industrial trend towards replacement of
chlorinated solvents is another factor that could add to the demand for
2-nitropropane. However, conversations with trade association represen-
tatives and industry officials did not yield any information on the amounts
of 2-nitropropane used or its emissions to the environment.
An estimated 9,100 kkg of nitroparaffins, turpentine, arid pine oil,
the major solvents for surface coating formulation, were used in this
industry in 1973. Due to the shift from solvent- to water-based coatings,
no increase in the use of solvent-based coatings is expected through 1982
(SRI 1977). Therefore, it is assumed that 1979 total consumption of nitro-
paraf fins, turpentine, and pine oil remained at 9,100 kkg. JRB has no data
on the relative amounts of these solvents consumed in recent years. How-
ever, due to their low cost and ready availability, it is assumed that
turpentine and pine oil constitute 75 percent of the 9,100 kkg consumed, or
6,800 kkg. The remaining 25 percent, or 2,300 kkg, is assumed to be nitro-
paraf fins. About 70 percent of the total amount of nitroparaffins used in
the surface coatings industry is believed to be 2-nitropropane. The amount
of 2-nitropropane used by the industry is therefore estimated to be 1,600
kkg. The amounts of major solvents used in the surface coatings industry
are summarized in Figure 3.6.
(3) Environmental releases of 2-nitropropane during the production of
surface coating products. The manufacturing process for surface coating
products generally consists of five steps: weighing, mixing, grinding,
tinting and thinning, and packaging. There are no chemical reactions in
these processes. A flow diagram of the surface coating manufacturing
process is shown in Figure 3.7.
Weighing, assembling, and mixing of pigments and vehicles are the
first steps in producing paint. The major ingredients such as resins,
oils, and pigments are introduced into a feed tank in which they are
weighed and then introduced into a mixer where they are thoroughly mixed.
A conventional mixer is similar to a large dough kneader with a sawtooth
*Mr. Young, Jones-Blair Co.: personal communication with T. Shannon, JRB
Associates, 1980.
3-16
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9,100 kkg
Nitroparaffins, turpentine,
and pine oil
Turpentine and
pine oil
6,800 kkgb
Nitroparaffins
2,300
Nitromethane,
nitroethane, and
1-nitropropane
700 kkg b
2-Nitropropane
1600 kkg b
Source: SRI 1977
Source: JRB estimates
Figure 3.6 Usage of 2-Nitropropane and Other Solvents in the
Surface Coating Industry
3-17
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I
I-1
CD
Tints and
thinners
Resins
Oils
Pigments
1
| Feed tank j
\
Weigh tank
Platform
scale
Mixer
Grinding
mills
linting &
thinning
tank
Labeling
machine
Filling machine
]nn
TOPI
nnnnnnnn
Belt conveyor
Carton
packaging
Shipping
Figure 3..7 Flow Chart for the Mixing of Surface Coatings
-------
blade. The batch is then ground and further mixed. Next, the paint is
transferred to another section of the plant and thinned, generally with
organic solvents, and tinted in agitator tanks. The paint is then trans-
ferred to the hopper of the filling machine and poured into cans (Shreve
and Brink 1977; Handbook of Industrial Chemistry 1974; USEPA 1979c).
JRB believes that 2-nitropropane is probably used as a solvent for
viscosity adjustment during the production of surface coatings. Therefore,
it is probably added to the production process during the tinting and
thinning phase.
The loss of organic solvents is usually estimated at 1 or 2 percent
even under well-controlled conditions (USEPA 1977b). The total quantity of
2-nitropropane used for surface coating products is 1,600 kkg. By using an
average loss factor of 1.5 percent, the 2-nitropropane lost to the air is
estimated at 24 kkg.
As discussed in previous sections, 2-nitropropane is believed to be
used mostly in the production of solvent-based surface coating products.
The major source of solvent discharge into waste water (either treated or
untreated) results from tank cleaning (USEPA 1979d). For most tanks used
for formulating solvent-based surface coatings, solvent wash is a common
method of cleaning. The caustic-wash technique also is used in some pro-
duction plants (USEPA 1979d).
No direct discharges to waste water streams are believed to result
from the solvent-wash cleaning technique. The solvents used for washing
are usually recycled, reclaimed, reused, or sent to contractors for proper
disposal (USEPA 1979d).
In plants using a caustic rinse system, the caustic residue is usually
rinsed with water. In most caustic-wash systems, the caustic solution is
recycled and reused. When the caustic solution is exhausted, it is
properly stored in drums and sent to contractors for proper disposal (USEPA
1979d). The water used for rinsing off caustic residues is usually dis-
posed as follows:
Recycled into the caustic solution
Drummed for hauling by contractors
Discharged to either treated or untreated waste water streams.
According to USEPA (1979d), 60 percent of those plants specializing in
solvent-based paints discharge no waste water; the remaining 40 percent are
assumed to have direct waste water discharge. Because of this distribu-
tion, we assume that 40 percent of 2-nitropropane in residue cleaned from
tanks is discharged in waste water.
During the production of surface coating products, 1 percent of the
formulated products is assumed to remain in the tank before it is cleaned.
For 1979, this quantity was 16 kkg. Of this residue, 40 percent (6.4 kkg)
3-19
-------
is believed to be discharged to waste water treatment facilities, and the
rest (9.6 kkg) is thought to be reused or drummed for contract hauling.
The amount of 2-nitropropane remaining in the surface coating is 1,560 kkg.
According to IMC (1979), 2-nitropropane is biodegradable. Numerous
organisms found in soil and in activated sludge slowly decompose it to
carbon dioxide, nitrogen, and water. Therefore, the 2-nitropropane dis-
charged to waste water is assumed to be totally biodegraded.
(4) Environmental releases of 2-nitropropane associated with the
application of surface coating products. Surface coating can be applied
in a variety of ways. Although architectural paints usually are applied by
brush or roller, many applications are now done with spray equipment such
as electrostatic spraying, hot spraying, steam spraying, two-component
spraying, and aerosol spraying (Handbook of Industrial Chemistry 1974).
Other application techniques include dipping, electrodeposition, flow
coating, and powder coating. In dip application, objects to be coated are
suspended and dipped into a large container of paint. Electrodeposition
can be achieved by depositing coatings on a conductive surface from a water
bath containing the paint (Handbook of Industrial Chemistry 1974) . Some of
the industries with surface coating operations are automobile assemblies,
aircraft companies, container manufacturers, and furniture manufacturers
(USEPA 1977b).
Releases of organic chemicals can occur during the application of
surface coating products because of evaporation of the thinner and solvents
used in formulating these coatings. Most of the solvents used in these
products are emitted to the air during the application and drying of the
coating. We thus assume that the total amount of 2-nitropropane in these
products, 1,560 kkg, is released to the air after their application.
Figure 3.8 presents a flow diagram of the environmental releases of
2-nitropropane during the production and uses of surface coatings con-
taining 2-nitropropane as solvent.
3.2.3 Miscellaneous Uses
(1) Adhesives. Until recently, adhesives were often selected
arbitrarily. Wider use of adhesives in the last 30 years has prompted
developments in the science of adhesives. Today, adhesives are an
essential element in the manufacturing of many products, including building
and household goods, shoe and leather products, automobiles, plywood,
pressure-sensitive tapes, and corrugated cartons (Mark and Gaylord 1969).
Although JRB was unable to confirm the use of 2-nitropropane in
adhesives,* the use of nitroethane and nitromethane, two other nitro-
paraffins, is documented. Organic solvents serve as good carriers and
viscosity reducers for adhesive compositions. Contact cements and pres-
sure-sensitive tapes are examples of cements utilizing organic solvents.
*C. Witzman, National Starch Co.: personal communication with T. Shannon,
JRB Associates, January 1980.
3-20
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Air
24
1,600
Air
1,560
Production of
surface
coatings
1,560
Applications
of surface
coatings
16
I To water
6.4
Waste water
treatment
6.4
Destroyed or
reused
9.6
{Waste disposal]
Figure 3.8 Environmental Release Flow Diagram of 2-Nitropropane During the
Production and Uses of Surface Coatings
-------
Simple polymer-containing and monomer-containing solvents are used in
cements. Simple solvents, or blends of solvents, are selected for the
bonding of a specific plastic. Solvency must be adequate to ensure suf-
ficient flow during application, drying must complete without bloom, and a
minimum of high-boiling residues must remain. The requirement for a sol-
vent of lower boiling point would seem to indicate the use of nitroparaf-
fins, which possess moderate boiling points. For bonding cellulose
acetate, nitroethane is recommended, while nitromethane is recommended for
the bonding of cellulose acetate butyrate and propionate (Mark and Gaylord
1969).
Although no quantitative data were obtained on use of 2-nitropropane
in the adhesives industry, we believe that the use of 2-nitropropane in
1979 in this application could have been significant. Because of the
extensive use of adhesives and the suitability of 2-nitropropane as a
solvent in the industry, the extent of its use should be studied further.
(2) Explosives and rocket propellants. Use of 2-nitropropane in the
explosives industry has been reported by an industry representative.* It is
used in "prilling" formulations, in which 2-nitropropane and a 12 to 16
percent alcohol are mixed, yielding a high density, high energy-yielding
explosive. Such a prill can be substituted for the traditional mixture of
crushed ammonium nitrate, 6 percent fuel oil, and alcohol. The advantages
of the 2-nitropropane prill are ease of formulation, good priming charac-
terisitics, and high detonation conduction. Disadvantages are its poor
storage characteristics and higher cost. The market at present is not well
established. Trojan, Inc., Philadelphia, was identified as a distributor,
but this information could not be verified.
A representative of the Bureau of Explosives verified the use of
2-nitropropane in the explosives industry.t It is reportedly used as a
prill, solely by IMC, Inc. Vulcan Materials, Inc. was suggested as a
marketing agent for explosives containing 2-nitropropane. However, con-
versations with officials of both the Birmingham, Alabama, and Wichita,
Kansas plants of Vulcan Materials, Inc., did not corroborate this con-
tention. Neither plant was reportedly involved in the distribution of any
explosives, but explosives containing 2-nitropropane for rock quarrying may
be used by the Wichita facility.§
A review of available literature did not yield significant information
on use of 2-nitropropane in the explosives industry. Data on its presence
in air, water, or land emissions were not found. Detailed studies of the
manufacturing processes, chemical formulation, production centers, and the
consumption of explosives did not address the use of 2-nitropropane (USEPA
1975, 1976, 1977c).
*M.Irving, DuPont de Nemours, Inc.: personal communication with T.
Shannon, JRB Associates, January 1980.
tDr. Chang, Bureau of Explosives: personal communication with T. Shannon,
JRB Associates, 1980.
§R. McKee, Vulcan: personal communication with T. Shannon, JRB Associates,
January 1980.
3-22
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Use of 2-nitropropane as a rocket propellant was also explored. A
review of available literature did not yield any significant information on
its use in this industry. A NASA in-house review, conducted upon request
by JRB, did not reveal any awareness of the use of 2-nitropropane as a
rocket propellant.* A member of the Aerospace Industrial Association of
America, although familiar with use of 2-nitropropane as a rocket propel-
lant, did not believe its use was widespread. He characterized it as a
high-energy, unstable chemical propellant.''' An official of the Chemical
Propulsion Information Agency stated that the use of 2-nitropropane as a
rocket propellant is very limited. He reported that probably the agency
did not possess information that would be useful in quantitative use of
2-nitropropane.§
Attempts to estimate the amounts of use and emissions of 2-nitropro-
pane by the explosives and rocket propellant industry were hindered by
substantial data gaps. Although it is likely that 2-nitropropane is used
as a blasting agent in the explosives industry, quantitative data to corro-
borate this fact were unavailable. It is likely that 2-nitropropane is
being marketed as a blasting agent in the form of a prill, although it
presently has a restricted market. Also, it is probably used as a volatile
solvent in the casting-powder process of some double base propeHants.
(3) Dyes. According to IMC, 2-nitropropane can be used to dissolve
many types of dyes, such as nigrosine and induline dyes. However, its use
in this capacity could not be documented in our literature search or
industry contacts. According to an official of Atlantic Chemical, 2-nitro-
propane is not widely used in the dye business because this chemical is
under consideration for classification as a carcinogen.11 A representative
of American Cyanamid, a U.S. producer of nigrosine and induline dyes,
reported that 2-nitropropane is not used in the manufacture of either dye
or during their application by the user. This is because the chemical is
expensive and "may be" a carcinogen.** We conclude that there is no
evidence of 2-nitropropane usage in dye manufacturing and application.
(4) Gasoline additives. When nitroparaffins, including 2-nitro-
propane, are substituted for hydrocarbon fuels, power output of Otto cycle
(gasoline) engines is increased 6 percent because more fuel is burned per
unit of air. Smoke generation is reduced 50 percent. Various nitro-
paraf fins, including 2-nitropropane, have also been used as fuel additives
in model engines and racing cars for short distances (Kirk-Othmer 1964).
*F. Stephenson, NASA: personal communication with T. Shannon, JRB
Associates, January 1980.
M. Snodgrass, AIAA: personal communication with T. Shannon, JRB
Associates, January 1980.
R. Brown, CPIA: personal communication with T. Shannon, JRB Associates,
January 1980.
^B. Bochnar, Atlantic Chemical Corp.: personal communication with P. Le.,
JRB Associates, January 1980.
**S. Greber, American Cyanamid: personal communication with P. Le, JRB
Associates, January 1980.
3-23
-------
However, investigations by JRB did not reveal any use of 2-nitro-
propane as a fuel additive. A laboratory official at Gulf Oil, Phila-
delphia, had not encountered the use of 2-nitropropane as either a com-
mercial gasoline and diesel fuel additive or as a racing car fuel
additive.* The director of the racing fuel formulation laboratory of Sun
Oil's Marcus Hook refinery also reported that 2-nitropropane is not used as
an additive in either their commercial gasoline or diesel fuels or racing
fuel formulations.''" A representative of the American Petroleum Institute
also could not confirm the use of 2-nitropropane as a fuel additive.§ We
conclude that there are no significant emissions of 2-nitropropane as a
result of its use as a fuel additive.
(5) Other uses. Other possible nonconsumptive uses of 2-nitropropane
include pesticides, rubber, model cars, smoke reducers, and as a solvent
and stabilizer.
Chloropicrin, and old industrial chemical and military gas, is used
extensively today as an insecticide, fungicide, soil sterilizer, and
fumigant. One relatively outdated source (Kirk-Othmer 1964) reported that
the pesticide is composed of a mixture which includes 2-nitropropane.
However, review of USEPA/OPTS 1979 Pesticide Product Information files
indicates that none of the 195 products containing chloropicrin as an
active ingredient include 2-nitropropane in their formulation (USEPA
1979a). Rather, it is possible that chloropicrin (or trichloronitro-
methane) contains 2-nitropropane residual impurities, since the base chemi-
cal, nitromethane, is produced in the same process that yields 2-nitro-
propane and other nitroparaffins. However, residual 2-nitropropane would
comprise much less than 0.1 percent of pesticide formulations containing
chloropicrin, because nitromethane itself contains no more than 0.1 percent
nitropropane. We therefore believe that pesticide formulation and usage
represent an insignificant source of 2-nitropropane releases.
The rubber industry has a wide range of processes requiring solvents
which could possibly include 2-nitropropane. However, no information was
found on the use of 2-nitropropane in any rubber formulation processes.
2-Nitropropane has also been identified as being used in model car fuels
and as a solvent and stabilizer for a wide range of chemical reactions. As
with rubber, significant information detailing the use of 2-nitropropane in
such applications was unavailable. Based on the chemical and physical
properties of 2-nitropropane, JRB believes that it may be used as a solvent
in the above areas.
(6) Releases from miscellaneous uses. The total amount of 2-nitro-
propane used in all the miscellaneous applications discussed above can be
estimated by determining all 2-nitropropane unaccounted for based on the
*Mr. Bower, Gulf Oil: personal communication with T. Shannon, JRB
Associates, January 1980.
1"B. Burtder, Sun Oil: personal communication with T. Shannon, JRB
Associates, January 1980.
§M. Tiffany, API: personal communication with T. Shannon, JRB Associates,
January 1980.
3-24
-------
1977 production total of 14,000 kkg. After summing total quantities
exported (1,400 kkg), consumptively used (7,000 kkg), used in printing inks
(2,900 kkg) and surface coating formulations (1,600 kkg), there are 1,100
kkg of the compound still unaccounted for. We assume that this total is
divided among uses in adhesives, explosives, propellants, dyes, and other
miscellaneous applications.
Because 2-nitropropane is assumed to be used principally as a solvent
in the miscellaneous applications discussed above, the distribution of
environmental emissions was assumed to be similar to that from the surface
coatings industry, where 2-nitropropane is also used primarily as a sol-
vent. Of 2-nitropropane used by the surface coatings industry, 1 percent
is destroyed, 99 percent is emitted to air, and a negligible amount is
released to waste water; there were no land emissions.
Applying these percentages to the 1,100 kkg of 2-nitropropane used by
various miscellaneous uses, the emissions are as follows:
Destruction: 11 kkg
Air: 1,089 kkg
Water: neg
Land: 0 kkg
3.2.4 Exports
In 1979, approximately 10 percent of the total production of 2-nitro-
propane (or 1,400 kkg) were exported. Most of the exports were to the IMC
plant in West Germany.* Releases of 2-nitropropane during transportation,
storage, and handling during export are considered to be negligible.
*G. Hess, IMC: personal communication with P. Le, JRB Associates, January
1980.
3-25
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4.0 RELEASE OF 2-NITROPROPANE FROM NITROMETHANE, NITROETHANE, AND
1-NITROPROPANE USES
The amount of 2-nitropropane present in nitromethane products is less
than 0.1 percent by weight (Riddick and Bunger 1970). From this percentage
and the amount of nitromethane produced (8,750 kkg), the total quantity of
2-nitropropane is estimated as less than 8.8 kkg.
Nitromethane is used as a rocket fuel, and as a solvent in the sur-
face-coating industry (Merck 1976). By assuming that use as a solvent is
the predominant use, we conclude that all 2-nitropropane (8.8 kkg) present
as contaminant in nitromethane in 1979 was released to the environment.
Nitroethane production in 1979 was estimated at 1,400 kkg. The level
of 2-nitropropane contamination of nitroethane is reported at 3 to 4
percent (Riddick and Bunger 1970). Thus the quantity of 2-nitropropane
contained in nitroethane in 1979 was estimated at 42 to 56 kkg, with an
average of 50 kkg.
According to the Merck Index (1976), nitroethane is mainly used as a
solvent in the synthesis of organic chemicals. It is also used experi-
mentally as a liquid propellant. Because nitroethane is used principally
as a solvent, we assume that all of the 2-nitropropane contained in nitro-
ethane is released to the environment through volatilization.
The level of 2-nitropropane contamination in 1-nitropropane is
estimated at 3 to 4 percent by weight (3.5 percent) (Riddick and Bunger
1970). The production of 1-nitropropane in 1979 was estimated at 8,750
kkg. Therefore, 1-nitropropane manufactured in 1979 was calculated to
contain 305 kkg of 2-nitropropane.
The uses of 1-nitropropane are the same as those for 2-nitropropane
(Merck 1976). The information on the quantity of consumptive and noncon-
sumptive uses of 1-nitropropane does not exist in the literature. There-
fore, to quantify the amount of 2-nitropropane in each type of 1-nitro-
propane use, we assume that the usage percentages are the same as those
presented in Chapter 3 for nonconsumptive and consumptive uses of 2-nitro-
propane: 40 percent and 60 percent, respectively. By using these percen-
tages, we therefore can estimate the amount of 2-nitropropane present in
consumptive and nonconsumptive uses of 1-nitropropane at 185 kkg and 120
kkg, respectively.
1-Nitropropane can be used captively in the production of hydroxyl-
ammonium sulfate and other derivatives. Hydroxylamine salts can be
prepared by the hydrolysis of 1-nitropropane with acid and water. The
reaction of 1-nitropropane with KUSO, and water produces hydroxylammonium
acid sulfate. This reaction can be accomplished in a glass-lined, agitated
reactor. The product of this reaction is then reacted with an aqueous 85
percent methanol solution in another glass-lined reactor to produce
crystalline hydroxylammonium sulfate. Propionic acid is a by-product
4-1
-------
(Reidel 1956). Figure 4.1 presents a flow diagram of the production of
hydroxylammonium sulfate.
During the production of 1-nitropropane derivatives, we can assume
that most of the 2-nitropropane contaminant is destroyed or reacted with
other chemicals. Thus, the final 1-nitropropane derivative products would
probably contain a minimal amount of 2-nitropropane. Assuming that 99.9
percent of the 2-nitropropane contaminant is destroyed or chemically
changed during the production and processing of these derivatives, then the
amount of 2-nitropropane remaining in the final products is 0.20 kkg.
The nonconsumptive uses of 1-nitropropane are reported to be the same
as those for 2-nitropropane (Merck 1976). Thus, we can assume that the
fate of the 2-nitropropane contaminant going to these nonconsumptive uses
is as follows: 99 percent is released to the air, and 1 percent is
destroyed. Using these percentages, we estimated that in 1979, of the
total amount of the 2-nitropropane contaminant in 1-nitropropane used
nonconsumptively (120 kkg), 119 kkg were released to the air and 1 kkg was
destroyed. (These values are only estimates and should be verified in
further studies.)
4-2
-------
1-NP
Hydroxylammonium sulfate
Reactor
Crystallizer
Propionic
acid
Solvent Extractor
Mother
liquor to
recovery
Dryer
Crystalline
hydroxylammon-
ium sulfate
Raffinate
Decanter
Crude propionic acid containing
H20, 1-NP, etc.
SO,
'
Prop ionic
acid
Propionic
acid still
Figure 4.1 Flow Diagram of Manufacture of Hydroxylairanonium Sulfate
-------
5.0 RELEASE SOURCE EVALUATION
The total environmental releases of 2-nitropropane in 1979 are
estimated to be 5,715 kkg. Table 5.1 summarizes the releases by the source
of emission, quantity released, and destination (air or water); these
quantities have been determined previously in the report. Table 5.2 cate-
gorizes these emissions by usage and geographic location.
The majority of 2-nitropropane emissions (78 percent or 4,450 kkg)
come from the use of 2-nitropropane as a solvent in printing inks and
surface coatings. The remaining 22 percent of the releases (1,265 kkg)
result from the direct production of 2-nitropropane, miscellaneous uses of
2-nitropropane, and uses of other nitroparaffin products.
Most 2-nitropropane releases (5,714 kkg) are to the atmosphere. Water
releases are negligible compared to the total releases. There are no land
releases. The largest source of air releases is in the use of 2-nitro-
propane as a solvent in printing inks.
5-1
-------
Table 5.1 Summary of Environmental Releases of 2-Nitropropane, 1979
Ol
Is)
Sources
of releases
Direct production
Uses
Contaminants of
other nitro-
paraffin products
Totals
Total
releases
(kkg)
20
5,543
178
5,741
Air
(kkg) (
19
5,543
178
5,740
releases Land releases
[% of total) (% of total)
0.3
96.6
3.1
100
Water releases
(kkg)
1
0
0
1
(% of total)
100
0
0
100
-------
Table 5.2 Categorization of 2-Nitropropane Environmental Releases
Total environmental releases
Geographic
Source location
Direct
production 1 plant in LA
Consumptive
uses 1 plant in LA
Printing
inks All over U.S.
Surface
coatings All over U.S.
Miscellaneous
uses
Contaminants
of NM, NE,
1-NP All over U.S.
Air
(kkg)
19
Neg
2,870
1,584
1,089
178
Water
(kkg)
1.0
Neg
Neg
Neg
Neg
Neg
Land
(kkg)
5-3
-------
6.0 SUMMARY OF DISPOSAL AND DESTRUCTION OF WASTES
This chapter summarizes the amount of 2-nitropropane released to the
environment during the destruction and disposal of wastes containing
2-nitropropane; these releases have been discussed previously in the
report. Table 6.1 summarizes the amount of waste, type of waste, and area
of release.
2-Nitropropane wastes are produced during the nitration of propane,
formulation and use of surface coatings, and the formulation of printing
inks. The total amount of 2-nitropropane in solid and liquid waste is
estimated to be 231 kkg.
Incineration and biodegradation destroy 92 percent (212 kkg) of this
waste, the remaining quantity (18 kkg) is either released to air or water.
6-1
-------
Table 6.1 Releases from Disposal/Destruction of 2-Nitropropane-Containing Wastes
(liquid and solid wastes)
NJ
Waste
Process (kkg)
Nitration of
propane 186
Formulation of
printing inks 29
Formulation of
surface
coatings 16
Total 231
Destroyed by
incinerat ion/
waste treatment
(kkg)
167
29
16
212
Released to air Released to water
after control after control
(kkg) (kkg)
18 1
neg neg
neg neg
18 1
-------
7.0 DATA GAPS AND RECOMMENDATIONS
Numerous data gaps were encountered during the preparation of this
report. These data gaps were due to incomplete literature on pertinent
subjects, the confidentiality of much industrial information, the lack of
research in various areas, and the lack of monitoring data within the
industrial facilities.
The most important area for which data were lacking was the process
descriptions and associated emission factors for 2-nitropropane manufacture
as well as for its primary and secondary uses. The emissions can be better
estimated when data are available on the emission factors for each process,
waste treatment methods used by the manufacturers, and the quantity of
2-nitropropane present in the product.
With regard to the uses of 2-nitropropane, there were serious infor-
mation gaps, both qualitative and quantitative, on primary and secondary
products. Basic information was unavailable for the major primary uses
(such as quantity of 2-nitropropane used, manufacturers, and locations).
For the minor primary uses, data on the amount of 2-nitropropane used were
lacking. Other data gaps included percentage breakdowns for each primary
use, the rate of degradation of 2-nitropropane-containing products, site of
manufacture, and site of use of manufactured products.
The materials balance for 2-nitropropane contains data gaps that could
be resolved primarily with monitoring, sampling, and additional information
detailing the amounts of 2-nitropropane used by various industries. Table
7.1 lists the major data gaps for 2-nitropropane and recommendations of
methods for their solution.
7-1
-------
Table 7.1 Data Gaps and Recommendations
Data Gaps
Recommendations
A. Production
1. Description of current processes
and associated emissions
2. Quantity of each form of
nitroparaffins produced
3. Amount of 2-nitropropane
present as impurity in each
form
4. Waste Incineration
a. Whether 2-nitropropane is
inadvertently produced
during incineration
b. Type of emission contfol
system and associated
releases
B. Exports
1. Quantity exported
Chemical engineering literature; contact IMC;
Manufacturing Chemists Association
Contact IMC; Manufacturing Chemists Association;
extensive literature search
Contact IMC; extensive literature search; Manu-
facturing Chemists Association; laboratory
analyses
Literature search; contact with municipal incin-
eration plants
Contact with incineration plants; contact IMC
Bureau of Census; export agents; contact with
manufacturers
-------
Table 7.1 Data Gaps and Recommendations (continued)
OJ
Data Gaps
Recommendations
2. Storage, handling, transpor-
tation releases
3. Ports of exit
C. Uses
1. Consumptive uses
a. 2-Nitro-2-methyl-l-propanol
1. Production capacity
2. Current process descrip-
tion and associated releases
3. Amount of 2-nitropro-
pane used
4. Secondary products -
production processes
and associated 2-nitro-
propane releases
b. Aminohydroxy compounds
1. Production capacity
Department of Transportation; port authorities;
contact with manufacturers
Contact with manufacturers; Bureau of Census;
export agents
Contact manufacturer
Contact manufacturer; chemical engineering
literature; monitoring
Contact manufacturer; extensive literature
search; Manufacturing Chemists Association;
laboratory analysis
Contact manufacturer; extensive literature
search
Contact manufacturer
-------
Table 7.1 Data Gaps and Recommendations (continued)
Data Gaps
Recommendations
2. Process description and
associated releases
3. Impurity level of 2-
nitropropane
4. Secondary products -
production processes
and associated releases
2. Nonconsumptive Uses
a. Surface coatings
1. Cellulose coatings
a. Quantity of 2-nitropro-
pane used
b. Identification of
products
c. Manufacturers and
locations
Chemical engineering literature; contact
manufacturer; monitoring
Contact manufacturer; extensive literature
search; Manufacturing Chemists Association;
laboratory analysis
Contact manufacturer; extensive literature
search
Contact IMC; contact cellulose coatings
manufacturers
Manufacturing Chemists Association; contact
cellulose coatings manufacturers; contact
cellulose resin manufacturers
Contact IMC
-------
Table 7.1 Data Gaps and Recommendations (continued)
Data Gaps
Recommendations
Description of produc-
tion process and asso-
ciated emissions
Manufacturers, locations,
and plant capacities
2. Vinyl coatings
a. Capacity of producers
b. Description of produc-
tion process and asso-
ciated emissions
c. Amount of 2-nitropropane
used
d. Process descriptions and
associated emissions for
secondary products and
uses
e. Manufacturers, locations,
and plant capacities
Chemical engineering literature; contact
manufacturers; monitoring
Contact IMC; Chemical Economics Handbook;
Manufacturing Chemists Association; contact
manufacturers
Contact manufacturers
Chemical engineering literature; contact manufac-
turers ; monitoring
Extensive literature search; contact with manu-
facturers; laboratory analysis
Extensive literature search; contact with manu-
facturers; Manufacturing Chemists Association
Contact IMC; Chemical Economics Handbook;
Manufacturing Chemists Association; contact
manufacturers
-------
Table 7.1 Data Gaps and Recommendations (continued)
Data Gaps
Recommendations
3. Epoxy Coatings
a. Capacity of producers
b. Description of production
processes and associated
emissions
c. Identification of pro-
ducts
d. Manufacturers and loca-
tions
e. Description of produc-
tion process and asso-
ciated emissions
4. Other Miscellaneous Coatings
a. Capacity of producers
b. Description of produc-
tion process and asso-
ciated emissions
c. Amount of 2-nitropropane
used
Contact manufacturers
Chemical engineering literature; contact manu-
facturers ; monitoring
Manufacturing Chemists Association; contact IMC;
contact coating manufacturers
Contact IMC
Chemical engineering literature; contact manu-
facturers; monitoring
Contact manufacturers
Chemical engineering literature; contact manu-
facturers; monitoring
Extensive literature search; contact with manu-
facturers; laboratory analysis
-------
Table 7.1 Data Gaps and Recommendations (continued)
Data Gaps
Recommendations
Process descriptions and
associated emissions for
secondary products and
uses
Manufacturers, locations
of plants and capacities
b. Printing Inks
1. Capacity of producers
2. Description of production
processes and associated
emissions
3. Amount of 2-nitropropane
used
4. Process descriptions and
associated emissions for
secondary products and uses
5. Manufacturers, location of
plants, capacities
Extensive literature search; contact with manu-
facturers; Manufacturing Chemists Association
Contact IMC; Chemical Economics Handbook; Manu-
facturing Chemists Association; contact manu-
facturers
Contact manufacturers
Chemical engineering literature; contact manu-
facturers; monitoring
Extensive literature search; contact with manu-
facturers; laboratory analysis
Extensive literature search; contact with manu-
facturers; Manufacturing Chemists Association
Contact IMC; Chemical Economics Handbook; Manu-
facturing Chemists Association; contact manu-
facturers; USEPA Effluent Guidelines Divison.
-------
Table 7.1 Data Gaps and Recommendations (continued)
00
Data Gaps
Recommendations
c. Adhesives
1. Amount of 2-nitropropane
used
2. Description of process and
emissions of 2-nitropropane
3. Destruction of wastes
4. Amount of 2-nitropropane
retained as impurity
5. Percentage breakdown of uses
6. Process descriptions for uses
and associated emission
factors
7. Breakdown products
8. End products of each use
9. Manufacturers, location of
plants, capacities
Contact manufacturers; contact IMC
Chemical engineering literature; contact manu-
facturers; monitoring
Contact manufacturers
Chemistry literature; contact manufacturers
Extensive literature search; Chemical Economics
Handbook; contact manufacturers; Manufacturing
Chemists Association
Chemical engineering literature; contact manu-
facturers and users
Chemistry literature; contact manufacturers
Extensive literature search; contact users;
Consumer Product Safety Commission
Contact IMC; Chemical Economics Handbook; Manu-
facturing Chemists Association; contact manu-
facturers
-------
Table 7.1 Data Gaps and Recommendations (continued)
Data Gaps
Recommendations
d. Explosives
1. Amount of 2-nitropropane used
2. Quantity produced
3. Description of production
process and emissions of
2-nitropropane
4. Destruction of wastes
5. Amount of 2-nitropropane
retained as an impurity
6. Percentage breakdown of
uses
7. Manufacturers, location of
plants, capacities
e. Dyes
1. Amount of 2-nitropropane used
Contact manufacturers; contact IMC
Chemical Economics Handbook; contact IMC; USITC
Chemical engineering literature; contact
manufacturers; monitoring
Contact manufacturers
Chemistry literature; contact manufacturers
Literature search; Chemical Economics Handbook;
contact manufacturers; Manufacturing Chemists
Association
Contact IMC; Chemical Economics Handbook; Manu-
facturing Chemists Association; contact manu-
facturers
Contact manufacturers; contact IMC
-------
Table 7.1 Data Gaps and Recommendations (continued)
Data Gaps
Recommendations
5. Amount of 2-nitropropane
retained as an impurity
6. Percentage breakdown of uses
7. Manufacturers, location of
plants, capacities
g. Contaminants in nitroethane (NE),
nitromethane (NM), and 1-nitro-
propane (1-NP)
1. Percentage breakdown of uses
of NE, NM, and 1-NP
Locations of consumers of
NE, NM, and 1-NP
Releases of 2-nitropropane
associated with production
and use of NE, NM, and 1-NP
Chemistry literature; contact manufacturers
Literature search; Chemical Economics Handbook;
contact manufacturers; Manufacturing Chemists
Association
Contact IMC; Chemical Economics Handbook; Manu-
facturing Chemists Association; contact manu-
facturers
Literature search; Chemical Economics Handbook;
contact manufacturers; Manufacturing Chemists
Association
Literature search; Chemical Economics Handbook;
contact manufacturers; Manufacturing Chemists
Association
Contact IMC; contact manufacturers
-------
Table 7.1 Data Gaps and Recommendations (continued)
I
o
Data Gaps
Recommendations
2. Quantity produced
3. Description of production
process and emissions of
2-nitropropane
4. Destruction of wastes
5. Amount of 2-nitropropane
retained as an impurity
6. Percentage breakdown of
uses
f. Other Miscellaneous Uses
1. Amount of 2-nitropropane
used
2. Quantity produced
3. Description of production
process and emissions of
2-nitropropane
4. Destruction of wastes
Chemical Economics Handbook; contact IMC; USITC
Chemical engineering literature; contact
manufacturers; monitoring
Contact manufacturers
Chemistry literature; contact manufacturers
Literature search; Chemical Economics Handbook;
contact manufacturers; Manufacturing Chemists
Association
Contact manufacturers; contact IMC
Chemical Economics Handbook; contact IMC; USITC
Chemical engineering literature; contact with
manufacturers; monitoring
Contact manufacturers
-------
8.0 REFERENCES
Bennett R. 1979. Nitropropane as an aid to solvent balance control.
Pigment and Resin Technology. 5-9; January.
Bowles RF, ed. 1961. Printing ink manual. Cambridge, England: W. Heffer
and Sons LTD.
y Brown D, Dobbin R. 1977. Industrial hygiene survey report: 2-nitro-
propane at International Minerals and Chemicals Corp., Sterlington, LA.
Washington, D.C.: National Institute of Occupational Safety and Health.
Carpenter BH, Hilliard GK. 1976. Overview of printing processes and
chemicals used. From: Environmental aspects of chemical use in printing
operations. Washington, D.C.: Office of Toxic Substances, U.S. Environ-
mental Protection Agency. EPA-560/1-75-005.
Handbook of Industrial Chemistry (Reigel's), seventh edition. 1974. Kent
JA, ed. New York: Van Nostrand Reinhold Co.
Hobbs F, Stuewe C. Hydroscience. 1979a. Emission control options for the
synthetic organic chemicals industry: carbon tetrachloride and perchloro-
ethylene. Draft. Research Triangle Park, NC: U.S. Environmental Pro-
tection Agency. Contract no. 68-02-2577.
Hobbs F, Stuewe C. Hydroscience. 1979b. Emission control options for the
synthetic organic chemicals manufacturing industry: fugitive emissions
report. Draft report. Research Triangle Park, NC: U.S. Environmental
Protection Agency. Contract no. 68-02-2577.
IMC Chemical Group, Inc. 1979. For high-performance solvent blends in
compliance with air pollution regulations depend on NiPar S-30 and NiPar
S-20. Hillside, IL: International Mineral and Chemical Corporation. NP
Division Technical bulletin series no. 36; The nitroparaffins. Hillside,
IL: International Minerals and Chemical Corporation. NP Division
Technical Data Sheet No. 1.
IMC Chemical Group, Inc. 1980. The storage and handling of nitropropane
solvents. Hillside, IL: International Minerals and Chemical Corporation.
NP Division Technical Data Sheet no. 20.
Kido T, Soda K, Suzuki T, Asada K. 1976. A new oxygenase, 2-nitropropane
dioxygenase of Hansenula mrakii. Journal of Biological Chemistry.
251(22); November 25.
y Kirk-Othmer Encyclopedia of Chemical Technology. 1964. New York: John
Wiley and Sons.
Kirk-Othmer Encyclopedia of Chemical Technology. 1977. New York: John
Wiley and Sons, Inc.
8-1
-------
Little H. 1957. The oxidation of 2-nitropropane by extract of pea plants.
Amherst, MA: Department of Chemistry, Univeristy of Massachusetts.
Mark H, Gaylord N, eds. 1969. Encyclopedia of polymer science and tech-
nology, vol. 3. New York: John Wiley and Sons, Inc.
McGurdy P, ed. 1978. Chemical week buyer's guide issue. New York:
McGraw-Hill. October 25.
Merck Index, The, 9th ed. 1976. Windholz M, ed. Rahway, NJ: Merck and
Co., Inc.
NIOSH. 1977. National Institute of Occupational Safety and Health.
Current intelligence bulletin 17: 2-nitropropane. Washington, D.C.:
National Institute of Occupational Safety and Health.
NIOSH. 1979. National Institute of Occupational Safety and Health. NIOSH
trade name ingredient data base: 2-nitropropane. Washington, D.C.:
National Institute of Occupational Safety and Health.
Purdy A. 1977. Memo on meeting between NIOSH and International Minerals
and Chemical Corporation (IMC). Washington, D.C.: National Institute of
Occupational Safety and Health.
Reidel JC. 1956. Propane to nitroparaffins. Vapor-phase nitration used
by C.S.C. Oil and Gas Journal. 110-114; January 9.
Riddick J, Bunger W. 1970 Techniques of chemistry, vol. II: organic
solvents, 3rd ed. New York: Interscience Publishers.
Shreve RN, Brink JA, Jr. 1977. Chemical process industries, fourth
edition. New York: McGraw-Hill Book Company.
SRI. 1977. Stanford Research Institute. Chemical economics handbook.
Menlo Park, CA: Stanford Research Institute.
USEPA. 1975. U.S. Environmental Protection Agency. Office of Research
and Development. State-of-the-art for the inorganic chemicals industry:
commercial explosives. Washington, D.C.: U.S. Environmental Protection
Agency. EPA-600/2-74/009b.
USEPA. 1976. U.S. Environmental Protection Agency. Effluent Guidelines
Division. Development document for interim-final effluent limitations
guidelines and proposed new source performance standards for the explosives
manufacturing point source category. Washington, D.C.: U.S. Environmental
Protection Agency. EPA-440/1-76-060J.
USEPA. 1977a. U.S. Environmental Protection Agency. Chemical hazard
information profile: 2-nitropropane. Washington, D.C.: Office of
Chemical Substances, U.S. Environmental Protection Agency.
8-2
-------
USEPA. 1977b. U.S. Environmental Protection Agency. Compilation of air
pollution emission factors, 3rd ed. Research Triangle Park, NC: Office of
Air Quality Planning and Standards, U.S. Environmental Protection Agency.
AP-42. Parts A and B.
USEPA. 1977c. U.S. Environmental Protection Agency. Industrial process
profiles for environmental use. Chapter 12: the explosives industry.
Cincinnati, OH: Industrial Environmental Research Laboratory, U.S.
Environmental Protection Agency. EPA-600/2-77-023b.
USEPA. 1979a. U.S. Environmental Protection Agency. Office of
Pesticides and Toxic Substances. Pesticide registration files.
Washington, D.C.: U.S. Environmental Protection Agency.
USEPA. 1979b. U.S. Environmental Protection Agency. Inventory search:
2-Nitropropane. Washington, D.C.: Office of Pesticides and Toxic Sub-
stances, Chemical Information Division, U.S. Environmental Protection
Agency.
USEPA. 1979c. U.S. Environmental Protection Agency. Development document
for effluent limitations guidelines and standards for the ink formulating
industry point source category. Washington, D.C.: Office of Water and
Waste Management, U.S. Environmental Protection Agency. EPA-440/l-79-090b.
USEPA. 1979d. U.S. Environmental Protection Agency. Development document
for effluent limitations guidelines and standards for the paint formulating
a point source category. Washington, B.C.: U.S. Environmental Protection
Agency. EPA-440/l-79-049b.
USITC. 1978. U.S. International Trade Commission. Synthetic organic
chemicals: U.S. production and sales, 1977. Washington, D.C.: U.S.
Government Printing Office.
USITC. 1979. U.S. International Trade Commission. Synthetic organic
chemicals: U.S. production and sales, 1978. Washington, D.C.: U.S.
Government Printing Office.
Vincent EJ, Vatavuk WM. 1978. Control of volatile organic emissions from
existing stationary sources. Vol. Ill: graphic arts - rotogravure and
flexography. Research Triangle Park, NC: Office of Air Quality Planning
and Standards, U.S. Environmental Protection Agency. EPA-450/2-78-033.
Weast RC, ed. 1973. Handbook of Chemistry and Physics, 53rd ed.
Cleveland, OH: CRC Press.
8-3
-------
APPENDIX A
PROPERTIES OF 2-NITROPROPANE
A-l
-------
Table A.I Properties of 2-Nitropropane
Synonyms
Molecular Formula
Molecular Weight
Physical State
Vapor Pressure
Boiling Point
Melting Point
Water Solubility
Dimethylnitromethane
Isonitropropane
89.09
Colorless liquid
20 mm Hg at 25°C
120°C
-93°C
Slightly soluble
Source: USEPA, 1977a
A-2
-------
A-l RELEASE OF 2-NITROPROPANE TO AIR FROM PRODUCT STORAGE TANKS
There are two kinds of releases from storage tanks: loss due to
tank breathing, and working loss or loss due to tank cleaning and
filling.
According to the AP-42 report(USEPA 1977b), emission factors of
2-nitropropane from "old" fixed roof tanks can be calculated. The following
sections discuss in detail methods of estimating the emission of
2-nitropropane from product storage tanks.
(a) Emission of 2-Nitropropane to Air Because of. Tank Breathing
Tank breathing losses are defined by the AP-42 report as losses
resulting from a tank because of the thermal expansion of existing
vapors, vapor expansions as a result of barometric pressure changes,
and/or an increase in the amount of vapor because of added vaporization
'in the absence of a liquid-level change (USEPA 1977b) .
The emission factor for 2-nitropropane from a storage tank due to
tank breathing can be calculated by means of an equation obtained from
the AP-42 report (US EPA, 1977b).
= (2.21 x 10-4)M r^WT'68 D^V^VT)0-5 F.CK (1)
where:
L^ = Fixed roof breathing loss (Ib/day)
M = Molecular weight of vapor in storage tank (Ib/lb-mole)
P = True vapor pressure at bulk liquid conditions (psia)
D = Tank diameter (ft)
H = Average vapor space height, including roof volume correction (ft)
AT = Average ambient temperature change from day to night ( F)
F = Paint factor (dimensionless)
P
C = Adjustment factor for small diameter tanks (dimensionless)
K« = Crude oil factor (dimensionless)
A-3
-------
To calculate the amount of 2-nitropropane lost to the air because
of tank breathing, we make the following assumptions:
2-Nitropropane is stored in fixed roof tanks, and the tank is in
"worn" condition
» All 2-nitropropane is stored for at least one day before it is
distributed for other uses
0 There are 300 working days in a year
0" The ambient temperature is 20°C (68°F)
The tank volume is 15,000 gallons, the average tank height is
10 feet, the diameter is 16 feet, and the site has 2 tanks
0 The tank is painted either white or aluminum
0 The liquid level inside the tank is half the average height of
the tank
o Ambient temperature change from day to night is 15 F.
Based on the above assumptions, the variables presented in equation
(1) can be evaluated as follows:
M = 89 Ib/lb mole
D = 16 ft
H = 5 ft
AT = 15 °F
F =1.14 (USEPA 1977b)
P
C = 1
KC-= l
The value of the vapor pressure for bulk liquid conditions (20 C) can
be calculated by means of the Antoine's equation as follows:
T _ -0.2185A , v ,0.
Log1Q P = + B (2)
where:
P = pressure (mm Hg)
K = temperature (degrees Kelvin)
A = 9,476.9 for 2-nitropropane (Weast 1973)
B = 8.164069 for 2-nitropropane (Weast 1973)
A-4
-------
By applying these obtained variables to equation (2) , the true vapor
pressure of 2-nitropropane at 20 C (
follows: f (-0.2185)(9. 476. 9)
-
pressure of 2-nitropropane at 20 C (or 293.15 K) can be estimated as
4= 12.6 mm Hg or 0.24 psia
The emission factor of 2-nitropropane associated with tank breath-
ing loss can then be calculated by inserting the determined values for
variables in equation (1). The emission factor is estimated as follows:
n 11 in~S (w\f °-24 *V-68 1.73 0.51 0.5
LB u-^i x iu ; ^y; \i4.7-0.24j (16) (5) (15) (1.14) (1) (1) =
1.47 Ib/day or 6.1 x 10~4kkg/day/tank
Assuming that there are 300 working days in a year, the annual uncon-
trolled emissions from product storage due to tank breathing are:
f 2 "\ r Emission Factor \f \
yTanksy Vfor Tank Breathing) Working Days)
Uncontrolled Losses
(2) (6.7 x 10~\kg/day)(300 days/year) = 4.0 x 10 l kkg/year
We assume that the emission of 2-nitropropane due to tank breathing
can be controlled by a refrigerated system that can achieve an 80 percent
control efficiency. The typical efficiency range of such recovery system
is from 65 to 95 percent. Therefore the estimated release rate is 20
percent. The controlled emissions can be calculated as follows:
(
Uncontrolled ~\ /Inefficiency "N n j *, j i
Emission of ) ( Factor of V (C°T^ed Emission)
2-Nitropropaney Control Device/ ^f 2-Nitropropane J
(4.0 x lO'^kg) (0.2) = 8.0 x 10~2 kkg
(b) Emission of 2-Nitropropane to Air During Tank Handling and
Tank Cleaning
Environmental loss to air due to tank handling and tank cleaning is
defined as working loss. Using the equation given by the AP-42 report,
the emission factor for working loss can be estimated (USEPA 1977b) . The
equation is as follows :
A-5
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(2.4 x 10 2) MPK (3)
where :
2
L^ = Fixed roof tank working loss (lb/10 gal)
M = Molecular weight of vapor in storage tank (Ib/lb mole)
P = True vapor pressure at bulk liquid conditions (psia)
K^ = Turnover factor
K = Crude oil factor
L*
The following assumptions are made to determine the value of each
variable stated above:
The density of 2-nitropropane at 20°C is 0.9876 kg/£
(Weast 1973)
The vapor pressure of 2-nitropropane at 20 C is estimated
at 0.24 psia (see (a) above)
The storage tank capacity is 15,000 gal (see (a) above)
The crude oil factor is 1 (USEPA 1977b)
The production site has 2 storage tanks (15,000 gal)
Based on the above assumptions, the turnover factor K^ is estimated
at 0.41 (USEPA 1977b) . The emission factor for working loss can also
be calculated by using the above factors in equation (3) .
Ly= (2.4 x 10~2) (89) (0.24) (0.41) (1) = 2.1 x lO'1 lb/103gal or
9.5 x 10~5 kkg/103 gal (+10%)
The annual throughput volume of 2-nitropropane is calculated as
follows:
(Production of\ I Density of \ , - _ , ,
I 0 . . I 1 1 M . ^ I = Annual Throughput Volume
V 2-Nitropropane/ y2-Nitropropane J ° *
(14,000 kkg)/(0.9876 kkg/103 X,)'1 = 14 x 106 t or 3.7 x 106 gal
The quantity of 2-nitropropane lost in uncontrolled emissions to
the air because of working loss can then be estimated as follows :
~>'^nnual ~\ Emission FactorA Uncontrolled Emission of
f 2\
( . J (Throughput J I for Working J= 2-Nitropropane Due to
V J \ Volume ~s ^^, Loss -^ Working Loss
ranks) (3.7 x 106gal)(9.5 x 10 5 kkg/103 gal/tank)- 7.0 x 10-1 kkg
A-6
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Assuming that the working losses of 2-nitropropane from product storage
can be controlled by a vapor recovery system with 20 percent release rate
(Typical range of efficiency of the vapor recovery system is from 65 to 95
percent), then the controlled emissions can be calculated as follows:
I Uncontrolled A f Inefficiency A
{ Emission Due J I Factor of } = Controlled Emissions
Vto Working Loss J \Control Device J
(7.0 x 10"1 kkg) (0.2) = 1.4 x lO"1 kkg
A-7
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A-2 RELEASE OF 2-NITROPROPANE DURING LOADING AND TRANSPORTATION
Loading losses from tank car and tank truck operations are major sources
of emission. Loading losses occur as vapors residing in empty cargo tanks are
displaced to the atmosphere by the liquid being added into the tank (USEPA
1977b).
The emission factor for loading tank cars and trucks is given as follows
(USEPA 1977b):
2
where: L. = Loading loss (lb/10 gal of liquid loaded)
M = Molecular weight of vapors (Ib/lb mole)
T = Bulk temperature of liquid loaded (°R)
P = True vapor pressure of the liquid loading (psia)
S = Saturation factor.
To calculate the emission factor for loading operations, the following
conditions and properties are used:
1. The only quantity that is shipped is the amount used for
nonconsumptive uses and export (7,000 kkg)
2. The density of 2-nitropropane is 0.988 g/ml
3. The bulk temperature of the liquid loading is 25°C (or 77°F or 537CR)
4. From USEPA 1977b, the S factor is 0.6, assuming that the operation is
accomplished through submerged loading with normal dedicated service.
5. The vapor pressure of 2-nitropropane at 25°C is 0.32 psia
6. The molecular weight of 2-nitropropane is 89 Ib/lb-mole
Using this factor, the loading loss can be calculated as follows:
T _ 12.46 (0.6)(0.32_X89_1 Q>4 lb/1Q3 gal
A-8
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The total amount of 2-nitropropane shipped is 7,000 kkg (7.1 x 10 & or
1.9 x 10 gal). Therefore, the total quantity of 2-nitropropane lost during
loading is (0.4 lb/103 gal)(1.9 x 106 gal) = 760 Ib or 0.3 kkg. Assuming that
the unloading loss is equal to the loading loss, the amount of 2-nitropropane
released during unloading in the United Stated is:
(0.4 lb/103 gal)(5,600 kkg) 103 A A/gal = 600 Ib or 0.3 kkg
.988 kkg 3.785S-
During the transportation of volatile liquids, small quantities of vapor
are expelled from the tank due to temperature and barometric changes. The
loss during transportation can be estimated using the following equation
(USEPA 1977b):
LT = O.IPW
where:
LT = Transit loss (lb/week-10 gal transported)
P = True vapor pressure of the transported liquid (psia)
W = Density of the condensed vapors (Ib/gal)
If the density of the condensed vapor of 2-nitropropane is equal to
the liquid density (as is true for most pure compounds), then W is equal to
0.988 g/ml or 8.18 Ib/gal. The true vapor pressure was given previously as
0.32 psia. Therefore the transit loss can be estimated as follows:
LT = (0.1)(0.32)(8.18) - 0.26 lb/103gal-week.
If we assume that the total amount of liquid transported is 1.5 x 10 gal
(see calculations in the previous section) and residence time of the
transported material is 1 week, then
f0.26 Ib \ (1 week),. ,. In6 .x " 390 Ib or 0.18 kkg
_ 1 vi.j x lu g&ij
^10 gal-weekl
Therefore the total amount of 2-nitropropane released to the air during
all phases of loading and transportation is 0.18 kkg + 0.6 kkg = 0.8 kkg.
A-9
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-560/13-89-011
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Materials Balance for 2-Nitropropane:
Level I - Preliminary
5. REPORT DATE
April 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Phuoc T. Le, Eliot Harrison, Terry Shannon, and
Robert L. Hall
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
JRB Associates, Inc.
8400 Westpark Drive
McLean, VA 22102
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-5793
12. SPONSORING AGENCY NAME AND ADDRESS
Survey and Analysis Division (TS-793)
Office of Pesticides and Toxic Substances
U.S. Environmental Protection Agency
Washington, DC 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
Project Officer - Michael Callahan
16. ABSTRACT
A Level I materials balance was performed for 2-nitropropane for the year 1979.
Releases to the respective environmental media were estimated for the processes in
which 2-nitropropane is produced, consumed, used nonconsumptively, destroyed, or
carried over into products. Of the estimated 1979 production of 14,000 kkg,. 5,715
kkg (41 percent) were estimated to have been released to the environment. The major
contributor to this release estimate was evaporation of 2-nitropropane used as a
solvent in printing ink and surface coatings (4,450 kkg; 78 percent of releases).
Atmospheric emissions accounted for essentially all 2-nitropropane released. The
report describes the estimation methods used, and characterizes the reliabilities of
the estimated values. Data gaps are discussed and suggestions are made for obtaining
the information required.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report}
Unclassified
21. NO. OF PAGES
79
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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