-------
Bibliography
1. American Defense Preparedness Assn. Wastewater Treatment in the Military
Explosives and Propellants Production Industry. 3 Vols. Washington, D.C.,
Oct. 1975.
2. Booz-Allen Applied Research, Inc. A Study of Hazardous Waste Materials,
Hazardous Effects and Disposal Methods. 3 Vols. Vol. II, PB 221-466,
Bethesda, Md., 1973.
3. Bradley, R. F., et al. Classification of Industries. Descriptions and
Product Lists. SRI Project ECD-3423 94025 for U. S. Environmental Pro-
tection Agency. Menlo Park, California, Stanford Research Institute,
Dec. 1974.
4. Davis, Tenney L. The Chemistry of Powder and Explosives. N.Y., Wiley,
1941, 1943.
5. Environmental Protection Agency. Development Document for Interim Final
Effluent Limitations Guidelines and Proposed New Source Performance
Standards for the Explosives Manufacturing Point Source Category. EPA
440/1-76/060-j, Group II, Washington, D.C., March 1976.
6. Environmental Protection Agency, Mid-Atlantic Region, Report on Waste
Disposal Practices, Radford Army Ammunition Plant, Radford, Virginia.
Philadelphia, Pa., May 1973.
7. Explosives. In: Kirk-Othmer Encyclopedia of Chemical Technology.
Vol 8. H. F. Mark, ed. N.Y., Wiley, 1966, pp. 581-718.
8. Hedley, W. H., et al. Potential Pollutants from Petrochemical Processes,
final report. Contract 68-02-0226, Task 9, MRC-DA-406. Dayton, Ohio,
Monsanto Research Corp., Dayton Lab., Dec. 1973.
9. Kent, James A., ed. Reigel's Handbook of Industrial Chemistry. 7th Ed.
N.Y., Van Nostrand Reinhold, 1974.
10. Nelson, T. P. and R. E. Pyle. Screening Study to Determine the Need for
New Source Performance Standards in the Explosives Manufacturing Industry.
Radian Corp. EPA Contract 68-02-1319, Task 50, July 1976.
11. Processes Research, Inc. Air Pollution from Nitration Processes. Contract
No. CPA 70-1, Task 22. Cincinnati, Ohio, March 1972.
12. United Stated International Trade Commission. Synthetic Organic Chemicals,
United States Production and Sales, 1973. ITC Publication 728, Washington,
1975.
13. United States Tariff Commisson. Synthetic Organic Chemicals, United
States Production and Sales, 1972. TC Publication 681, Washington, 1974.
14. United States Tariff Commission. Synthetic Organic Chemicals, United
States Production and Sales, 1971. TC Publication 614, Washington, 1973.
27
-------
15. U. S. Department of Commerce, Social and Economic Statistics Adminis-
tration, Bureau of the Census. 1972 Census of Manufacturers. Industry
Series MC72(2)-28, Misc. Chemical Products, SIC Industry Group 289.
December 1974.
16. U. S. Office of Scientific Research and Development, National Defense
Research Committee, Div. 8. The Preparation and Testing of Explosives.
Summary Technical Report of Division 8, NDRC. Washington, D. C., 1946.
General References
A. Cook, Melvin A., The Science of High Explosives., N.Y. Reinhold, 1958.
B. U. S. Army Material Command, Engineering Design Handbook - Explosive
Trains, AMC Pamphlet AMCP 706-179, January 1974.
C. U. S. Army Material Command, Engineering Design Handbook - Properties
of Explosives of Military Interest, AMC Pamphlet AMCP 706-177,'March 1967
28
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INDUSTRY ANALYSIS
Organic nitration processes leading to the production of explosive
compounds are described in this chapter. Five nitration processes are
described along with the process for manufacture, concentration and recovery
of nitric acid used in the nitration reactions. In several cases, process
descriptions are somewhat generalized in order to encompass minor operational
variations between batch and continuous flow production techniques.
Each operation is represented by a flow chart indicating input materials
(brackets), processes (numbered rectangles), and product or by-product streams
(large circles). Solid, liquid, and gaseous waste streams are indicated
by small squares, triangles and circles, respectively, attached to the numbered
process rectangles. Process descriptions follow the flow charts on which they
are presented.
Data are given in metric units according to the System Internationale
described in the ASTM Metric Practice Guide. Preferred base units and
rules for rounding numbers converted from one system of units to another are
described therein.
The information used to prepare this catalog entry consisted of books,
encyclopedias, results of EPA supported investigations, replies to question-
naires submitted to representatives of commercial and governmental production
facilities and results of field surveys at selected production installations.
Additional sources of information exist, such as patent literature and pub-
lications of Stanford Research Institute's Process Economics Program, which
were not utilized because of the limited resources available for this study.
The reader is advised to consult such additional sources of information on
subjects which were not treated in sufficient depth to meet specific needs.
There are some recognized deficiencies and inconsistencies in the data
used to prepare this report. Many commercial facilities consider data re-
lating to raw materials consumption or production as proprietary information.
Certain governmental (GOCO) production facilities for which information was
gathered and used in the preparation of this study have since reduced pro-
duction, eliminated certain products from their line, or ceased operations
altogether. Others are in the process of modernizing operations, or are
actively engaged in development of pollution abatement programs which were
only in planning stages when source information for this study was generated.
Inconsistencies appear also in lists of commercial producers of organic ni-
tration products. Producer/product data compiled from the 1976 Directory of
Chemical Producers differ somewhat from such data compiled by a telephone survey
of producers listed in an EIS data file. Limited attempts to resolve this
inconsistency were unsuccessful and the data are presented as compiled.
29
-------
Nitric Acid Production Processes
Production of nitrating acids is the largest operation in the explosive
manufacturing system. All military explosives manufacturing plants and most
of the major commercial plants make their own acid. At recent production
rates (1969-1971) the volume of H2S04 manufactured by military explosive
plants was four times the volume of TNT produced and 4 percent of the U.S.
total for all purposes. Nitric acid and oleum production levels were corres-
pondingly high (see Figure 3 ).
The various nitration processes use nitric acid either alone or in con-
junction with sulfuric acid (oleum) or acetic acid to produce the desired
product. Spent acids from nitration are processed to recover unused HN03 as
well as HaSOi, or acetic acid. The recovered acids are then either recycled
or disposed of as by-products.
Within the scope of this study only those processes involving the pro-
duction and recovery of nitric acid are examined. Figure 4 is a flow chart
for the processes described.
The high-pressure ammonium oxidation process described in Process No. 1
is typical of current production methods. The National Emission Data System
shows a Source Classification Code and emission factor for older, low-pressure
process, but sources consulted for this study failed to identify any manu-
facturing facility still producing HN03 by the older method.
Process Nos. 2 and 3 are typical of nitric acid concentration (NAC) and
spent acid recovery (SAR) operations in general. However, for purposes of
establishing Source Classification Codes and emission factors, the National
Emission Data System treats nitric acid concentration (NAC) from TNT spent
acid recovery (SAR) separately from NAC during original production of nitric
acid. In a like manner H2S04 regeneration during TNT-SAR is assigned a
unique SCC and specific emission factors. For the purposes of this study, NAC
and SAR are considered to be processes common to a number of process groups.
Acid production and recovery plants are major contributors to the waste
stream entering the atmosphere from the explosives industry. Emissions from
absorber stacks routinely appear as visible plumes, indicating high N0x or
SOV concentration in the tail gas stream.
30
-------
OLEUM
DILUTE HNO3
CONG. HNO3
CONG. H2SO4
1969-1971 PRODUCTION
CD CAPACITY
I
I
50 100 150
GIGAGRAMS PER MONTH
200
250
FIGURE 3. PRODUCTION OF NITRATION ACIDS
Source: American Defense Preoaredness Assn. Wastewater Treatment in the
Military Explosives and Propellants Production Industry. 3 Vols,
Washington, D.C., Oct. 1975.
31
-------
OQASEOUS EMISSIONS
^LIQUID EMISSIONS
DSOLIO EMISSIONS
LJ>
AMMONIA
OXIDATION
PROCESS
1
f WEAK \
[ HN03
V (60-65%) /
o
NITRIC ACID
CONCENTRATION
4. 7, 9.r\, 141
NITRATION
H2SO<
OR Mg {NO3)2
fH2SO< OR ]
CH3COOH J
SPENT ACID
RECOVERY
CH3COOH
H2S04
TO RECYCLE
A NO/OR
DISPOSAL
FIGURE 4. FLOW CHART FOR NITRIC ACID PRODUCTION
32
-------
NITRIC ACID PRODUCTION PROCESS NO. 1
Ammonia Oxidation Process (AOP)
1. Function - Anhydrous ammonia is vaporized, mixed with preheated air and
combusted under pressure in the presence of a catalyst to produce nitric oxide
(NO) which is further oxidized by the excess air to nitrogen dioxide (N02) and
its dimer (N2O.J. The equilibrium mixture is absorbed in water in a cooled
absorber tower to form weak (60-65%) HN03. The NO formed at the same time is
reoxidized to form additional HN03. These chemical reactions are represented
by the following equations.
12 NH3 + 15 02> 12 NO + 18 H20 (1-1)
12 NO + 6 02 > 12 N02 (1-2)
12 N02 + 4 H20* 8 HN03 + 4 NO (1-3)
2. Input Materials - Anhydrous ammonia gas and preheated air constitute the
feed stream to the catalytic oxidizer. Ammonia consumption is approximately
0.4 kg/kg HN03 produced. Conversion is at least 95 percent of theoretical.
3. Operating Parameters - The ammonia/air mixture passes through a catalyst
bed at a-temperature of 800 to 960ฐC and a pressure of 929 kPa (120 psig).
The reaction air is first compressed and preheated to 260ฐC by hot reaction
gasses from the catalyst bed. Sources consulted indicate platinum-rhubidium
as well as platinum-palladium-mercury may be used to catalyze the reaction.
4. Utilities - Specific data relating to utilities consumption were not found
in the sources consulted for this study. However, one source indicates effective
utilization of heat generated during catalytic oxidation by passing the reaction
gases through heat exchangers to: 1) preheat reaction air, 2) reheat tail gases,
3) produce steam for the compressor turbine and 4) produce steam for export from
the process.
5. Waste Streams - The only source for atmospheric emissions from the AOP is
tail gas from the absorption tower. The National Emission Data System listing
shows emission factors of 26.25 g N0x/kg HN03 for the older (atmospheric pressure
reaction) oxidation process and 2.5 g NO /kg HN03 for the newer (high pressure)
process described here.
A summary of gaseous emissions from AOP at two commercial facilities and
six Army ammunition plants is presented in Table 11. Only three of the AAP's
are currently in operation.
Waste waters from AOP facilities include cooling water and leakage, as well
as water used for cleanup. Because AOP effluents are normally mixed with
large volumes of cooling water and are frequently combined with wastes from NAC
and sulfuric acid processes, it is difficult to specify pollutant discharges
solely associated with AOP. A study of AOP at one military production facility,
Holston Army Ammunition Plant (HAAP), resulted in waste-water data summarized
in Table 12. From this it may be seen that, beyond the expected highly acidic
33
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ph, AOP process effluent will contain appreciable quantities of nitrate and
ammonia nitrogen. Current treatment of waste-waters, where performed, consists
solely of pH adjustment.
6. EPA Source Classification Code -
Ammonia Oxidation Process (old method): 3-01-013-01
Ammonia Oxidation Process (new method): 3-01-013-02
7. References -
1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Expolsives and Propellants Production Industry. 3 Vols.
Washington, D. C., Oct. 1975.
2) Environmental Protection Agency, Mid-Atlantic Region, Report on
Waste Disposal Practices, Radford Army Ammunition Plant, Radford,
Virginia, Philadelphia, Pa., May 1973.
37
-------
NITRIC ACID PRODUCTION PROCESS NO. 2
Nitric Acid Concentration (NAC)
1. Function - The standard nitric acid concentration (NAC) process is a con-
tinuous operation in which weak nitric acid is distilled in the presence of
sulfuric acid. Weak (60-65%) HN03 and concentrated H2SO.t are fed to the dis-
tillation tower along with steam. The sulfuric acid combines with free water
while HN03 vapors (98-99%) form an overhead stream. The nitric acl'd vapors,
contaminated with small amounts of NOX and 02 from HN03 dissociation, pass to
a bleacher and condenser. The HN03 vapors condense as 95-99% HN03, while NOX
and oxygen pass to an absorber column for conversion to and recovery of addi-
tional weak nitric acid. This weak acid is recycled to the dehydrating unit.
The still bottoms, consisting of approximately 68% H2SOm are recovered and
sent to a concentration unit for reprocessing. In an alternate method, used
in one military production plant, weak HN03 from the AOP is mixed with hot
concentrated aqueous magnesium nitrate. The hot mixture is passed through a
stripping column; 99% HN03 is distilled off; and spent magnesium nitrate is
drained off, reconcentrated and recycled.
2. Input Materials - Dilute nitric acid from the AOP (Process No. 1) or SAR
(Process No. 3) constitutes the primary feed stream to this process. Concen-
trated sulfuric acid or magnesium nitrate solution may be used as dehydrating
agents.
3. Operating Parameters - Specific data relating to flow rates, temperatures,
pressures and equipment were not found in sources consulted for this study.
4- Utilities - Data were not available in sources consulted for this study.
5- Waste Streams - Absorber tail gas is the principal source of NOX emissions
from the nitric acid concentration process. In the National Emission Data
System listing, emission factors range from 0.1 to 2.5 g N0x/kg HNOs produced.
The NO content of tail gas is affected by several variables. Elevated NO
emissions may be caused by insufficient air supply or high temperatures inxthe
absorber tower, exceeding design capacities for the system and internal leaks
which permit gases from AOP to enter the tail gas system. A summary of gaseous
emissions data from NAC at three commercial facilities and seven Army ammunition
plants is presented in Table 13. Only three of the AAPs are currently in
operation.
Because of a general lack of data on liquid process effluent from either
AOP or NAC operations, definition of pollutant levels is difficult. Data on
combined flows from several AOP and NAC facilities are available, however, and
are presented in Table 14. The table presents data from commercial as well as
military production plants. The data presented show considerable variability,
due primarily to the extent of dilution of process effluents with non-contact
waters. Nevertheless, it is readily apparent that low pH, high ammonia and
nitrate nitrogen, and high sulfate levels are characteristic of effluents from
NAC facilities. Where employed, treatment consists of acid neutralization and
calcium sulfate sludge removal.
38
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6. EPA Source Classification Code - HNOa Concentrators (TNT process): 3-01-010-02
HMOs Concentration (old method): 3-01-013-03
HN03 Concentration (new method): 3-01-013-04
7. References -
American Defense Preparedness Assn. Wastewater Treatment in the Military
Explosives and Propellants Production Industry. 3 Vols. Washington, D.C.,
Oct. 1975.
42
-------
Nitric Acid Production PROCESS NO. 3
Spent Acid Recovery (SAR)
1. Function - Spent acid from various nitration processes flows into the top
of a denitrating tower. Steam, fed in at the bottom, rises through the tower
stripping HN03 and NOX from the spent acid. During recovery of spent, mixed
acid, the still bottoms which contain diluted sulfuric acid are sent to the
H2S04 concentrator. Sulfuric acid (93%) from the concentrator is a by-product
of most nitration processes. In some cases it can be recycled to oleum pro-
duction or sold; depending on the source of the spent acid (nitration process),
contamination with nitrobodies may limit its marketability.
In the bleacher the nitrogen compounds are further oxidized and/or con-
densed as nitric acid. Reflux of the condensate absorbs more NOX, increasing
the yield of acid which is then withdrawn, concentrated, and recycled to the
nitration process. Uncondensed gaseous materials from the reflux column are
routed through an absorption column where they are scrubbed with dilute HN03.
Further oxidation of NO occurs, generating additional HN03 which is recycled
to the denitrator tower.
2. Input Materials - The main feed stream to the acid recovery process consists
of spent acid from various nitration processes. This spent acid is usually a
mixture of dilute HN03 and HaSO^ and may also contain nitrosylsulfuric acid and
nitrobodies. Steam and air in quantities not specified comprise the other feed
streams to this process.
3. Operating Parameters - Specific data on operational temperatures or pres-
sures have not been found in sources consulted for this study. One source in-
dicates a total process capacity for a typical recovery unit of 0.018 Gg/hour
with a feed input of 0.018 Gg/hour of spent acid.
4. Utilities - No specific data for water or energy consumption were found in
the sources consulted during the study of this process.
5. Waste Streams - Waste waters from SAR units processing spent acid from TNT
production may be considered typical of SAR waste waters in general. Thev are
characterized by high dissolved solids content, on the order of 11 kg/Mg of
TNT production, sulfates (4 kg/Mg TNT) and small quantities of nitrogen salts.
One source indicates that limited observation of one spent acid recovery unit
showed no apparent problems with atmospheric emissions from the denitrating
tower even though the unit has no emission control equipment. However, the
same source states that a dark orange plume is continually emitted from the
stack of nitric acid concentrators indicating a high concentration of NOX,
estimated to be on the order of 9.8 x 105 kg/year. The National Emission Data
System emission factor for HN03 concentrators indicates a level of 2.0 mq NO /kq
TNT produced. Factors for H2S04 regeneration indicate 7.5 mg SOX and 1.0 mgx
NOx/kg TNT. A summary of gaseous emission data from SAR including sulfuric
acid regeneration and concentration operations is presented in Tables 15 and
16. The tables include data from one commercial facility and six Army ammu-
nition plants, three of which are currently out of operation.
43
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6. EPA Source Classification Code - Source Classification Codes for spent
acid recovery processes have been established only for those considered part
of TNT production processes. These are: HN03 Concentrator: 3-01-010-02
H2S04 Regeneration: 3-01-010-03
7. References -
1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propellents Production Industry. 3 Vols.
Washington, D.C., Oct. 1975.
2) Environmental Protection Agency, Mid-Atlantic Region. Report on
Waste Disposal Practices, Radford Army Ammunition Plant, Radford,
Virginia. Philadelphia, Pa., May 1973.
47
-------
TNT Production Processes
The production of TNT follows the same chemical process, regardless of
variations in physical facilities or manufacturing methods. Liquid toluene
is nitrated by treatment with mixed nitric and sulfuric acids. Following
the nitration reaction, undesirable isomers as well as residual dinitrotoluene
(DNT) are removed by conversion to soluble salts and extraction.
Figure 5 is a flow chart for TNT production. Three processes are described:
Nitration (Process No. 4), Purification (Process No. 5), and Finishing (Process
No. 6).
The nitration process is descriptive of both batch and continuous produc-
tion methods. The continuous production process is merely a modernized version
of batch production. As developed by Canadian Industries, Limited (CIL),
nitration is carried out in six nitrator-separator stages with the organic
phase flowing countercurrent to the acid phase. The CIL process, like all
continuous processes, features smaller inventories of explosive material at any
stage in the production line. It also features more efficient control of
process conditions and better utilization of recycle streams, resulting in
some reduction in waste stream generation.
Purification (Process No. 5) is likewise descriptive of both batch and
continuous processes. As in nitration, the CIL purification operation is an
improvement over batch operation but the principle and chemistry remains the
same. In the CIL process countercurrent washing and sellite treatment in
multiple stages provides a more efficient utilization of the reagents used
for purification. The CIL process differs from batch purification mainly in
that 1) water is used in place of sodium carbonate solution for initial re-
moval of free acid and 2) sellite is prepared directly from dry sodium sul-
fite rather than through the S02-carbonate reaction. Finishing operations
are identical for both batch and continuous processes.
Dinitrotoluene (DNT) may be prepared in a TNT plant, but at present all
DNT used in military propel!ant formulations is purchased from commercial
sources. When toluene is subjected to dinitration (see Process No. 4) the
"bi-oil" produced contains approximately 75 percent of the 2, 4-isomer.
Dinitrotolune produced commercially is removed from the reaction at this
point, washed free of acid and sold. A complete description of DMT produc-
tion processes appears in Chapter 6, Industrial Organic Chemicals, Part 2.
When used in propellant manufacture, DNT is purified by fractional freezing
or "sweating." Purification of DNT is essentially a pollution-free operation
because the separated impurities are all fed to the TNT manufacturing operation
for conversion to TNT. Aqueous effluents are limited to uncontaminated cool-
ing water. For these reasons, and because DNT is an interim product in TNT
manufacture, process descriptions for DNT manufacture are not included in this
study.
48
-------
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49
-------
TNT PRODUCTION
PROCESS NO. 4
Nitration
1. Function - The production of TNT by nitration of toluene is a three-step
process, performed in a series of reactors. The mixed acid stream flows
countercurrent to the flow of the organic stream during the process, as ill-
ustrated in Figure 6. It can be seen that the mixed acid stream in its most
concentrated state is fed to the last reactor and emerges as spent acid from
the first reactor.
The overall chemical reaction may be illustrated by the following schematic
equation.
CH
3 HN03
H2SOt
V
NO 2
- TNT
02 N02
(4-1)
Feed chemicals to the first reaction step consist of toluene and spent
acid from dinitrotoluene production, fortified with a 60% HN03 solution. Heat
exchange coils in the reaction vessel control the temperature of the exothermic
mononitration. The predominant product is ortho-nitrotoluene but the meta-and
para-isomers are also formed.
The organic layer, often called "mono-oil," is decanted and pumped to the
second reactor.
The "mono-oil" is subjected to further nitration with acid from the third
reactor fortified with additional HN03. During the continuous flow (CIL) pro-
duction process, a recycle stream known as "yellow water" joins the process
stream in the second reactor.
50
-------
TOLUENE-
SPENT
ACID '
YELLOW
WATER
1ST
NITRATION
NITROTOLUENE
(
i
2ND
NITRATION
MAKE-UP
HNO3
DNT TNT
^ NITRATION ^ CONCENTRATED
A . AC.D
I
FIGURE 6. NITRATION OF TOLUENE TO FORM TRINITROTOLUENE
51
-------
The organic product from the second nitration step, known as "bi-oil,"
consists of a mixture of all possible isomers of dinitrotoluene (DNT). The
"bi-oil" is pumped to the third reactor.
The final nitration is accomplished by treatment of the "bi-oil" with a
fresh feed acid mixture of nitric acid and oleum. The crude TNT from this
third nitration consists primarily of 2,4,6-trinitrotoluene (a-TNT) contami-
nated with small quantities (approximately 5%) of the 6 or 2,3,4- and Y- or
3,4,6-isomers.
i
The crude mixture is purified in Process No. 5.
2. Input Materials - Basis - 1.0 kg crude TNT
Toluene - 0.458 kg
Nitric Acid - 0.57 kg. This figure is not corrected for HNO;! replenish-
ment or "butting up" in the first and second nitrators. Concentrated (98%)
HN03 is used in the preparation of the mixed-acid feed stream which enters
the reaction in the third nitration step. Spent acid from this step is forti-
fied with 60% HN03 and used as feed acid for the second nitrator. Spent acid
from the second step is again fortified with 60% HN03 and feeds the first
nitrator.
Sulfuric Acid - 1.858 kg - oleum (109% sulfuric acid) is used as the
second component to the binary mixed acid which is fed to the reaction in
the third nitration step. As one.of the constituents of the spent acid from
trinitration, the diluted H2S04 feeds the second nitration step and subsequently.
the first nitration.
The composition of the mixed acid as it moves through the process is
shown in Table 17.
Table 17. ACID COMPOSITION IN THE THREE NITRATION REACTORS
Reactor HN03 HzSO^ ONOS03H Nitrobodies Water
1
2
3a
14%
13%
23%
48%
54%
83%
17%
18%
-
2%
8%
-
19%
8%
-
aThe total is greater than 100% because the oleum is 109% based on S03 analysis.
Yellow Water - quantities unknown - A dilute solution composed of crude TNT
in water and acids from the first crystallization and water wash in the CIL puri-
fication process is recycled to the reaction in the second nitration step of the
CIL continuous flow process.
52
-------
3. Operating Parameters - Temperature Control: Temperature control
data for continuous flow (CIL) production of TNT were not found in the sources
consulted for this study. In the batch production process the mono-mix acid
is cooled to 36 to 38ฐC. Toluene is added under the surface of the acids and
the exothermic reaction mixture is cooled sufficiently to hold the temperature
at about 40ฐC during addition. The temperature of the reaction mixture is then
allowed to increase to 57 to 60ฐ, where it is held for one hour. The mixture
is then cooled to 38ฐC and the mono-oil is separated from the spent acid. In
the second nitration the mono-oil is added to bi-mix acid which has been cooled
to 77ฐC. Upon addition of mono-oil the reaction mixture warms to 82 to 85ฐC,
where it is "cooked" for 8 minutes and then is cooled to 77ฐC. The tri-mix
acid is cooled to 80ฐC. Bi-oil is added at a rate sufficient to cause a temp-
erature increase of 0.5ฐC/min, to a maximum of 90ฐC. After being held at that
temperature for several minutes, the mixture is allowed to warm at the rate of
lฐC/min to 110ฐC. Temperature is maintained at that level for 20 minutes, then
cooled with continuous stirring to 107ฐC. Stirring is discontinued, and the
temperature is reduced to approximately 93ฐC as the tri-oil or crude TNT is
allowed to separate from the tri-spent acid.
Pressure: The reaction occurs at atmospheric pressure.
Flow Rate: A typical line for continuous flow production of TNT yields approxi-
mately 44,000 kg/day purified explosive with an input of 20,150 kg toluene,
25,430 kg nitric acid and 82,850 kg sulfuric acid. A typical batch production
line at full operation can produce 45,830 kg/day purified explosive. Data
specifying batch size were not found in sources consulted for this study.
Miscellaneous: Sulfuric acid acts to catalyze the nitration of toluene by
forming a hydrated molecule with the water of reaction, thus shifting the re-
action equilibrium to the right.
4. Utilities - Water: Based on reported total water usage for a typical
continuous-flow TNT production facility of 19,492 m3/day at 131.5 Mq/day
production (18,925 m3 cooling + 567 m3.process) total water usage corresponds
to 0.148 mVkg of refined product. Details of water usage for individual
processes have not been found in sources consulted for this study.
Electricity: No data available.
Fuels: No data available.
5. Haste Streams - Gaseous emissions from the nitrators and separators,
containing CO, C02, NO, N02s N20 and trinitromethane (TNM), are passed through
a fume recovery system for recovery of NOX as nitric acid, then vented through
scrubbers to the atmosphere. Final emissions contain quantities of unabsorbed
NOX as well as TNM. One reference source indicates rated capacity for a typi-
cal fume recovery system operation as part of a continuous flow production line
as 272 kg HN03 per hour. The same source, however, indicates that a visible
orange plume is emitted from the vent stack during operation and that an
estimated 245 Mg/year of NOX are discharged to the atmosphere. Table 18
presents summary emission data for acid fume recovery (AFR) systems at three
Army ammunition plants. Only two of the plants listed are currently in oper-
ation (Radford and Volunteer) and only Volunteer is currently engaged in TNT
production.
53
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Waste-water generated during the nitration-separation process consists
primarily of cooling water from the reactor vessels. Process water, for
the most part, is carried through acid recovery and discharged following
that process. No data on waste-water from fume recovery systems have been
found in sources consulted for the study.
6. EPA Source Classification Code - Nitration Process: 3-01-010-01
7. References -
1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propellants Production Industry. 3 Vols.
Washington, D.C., Oct. 1975.
2) Davis, Tenney L. The Chemistry of Powder and Explosives. N.Y.,
Wiley, 1941, 1943.
3) Environmental Protection Agency. Development Document for Interim
Final Effluent Limitations Guidelines and Proposed New Source Per-
formance Standards for the Explosives Manufacturing Point Source
Category. EPA 440/1-76/060-j, Group II. Washington, D.C., March
1976.
4) Environmental Protection Agency, Mid-Atlantic Region, Report on
Waste Disposal Practices, Radford Army Ammunition Plant, Radford,
Virginia. Philadelphia, Pa., May 1973.
5) Explosives. In: Kirk-Othmer Encyclopedia of Chemical Technology.
Vol. 8. H. F. Mark, ed. N.Y., Wiley, 1966, pp. 581-718.
6) Processes Research, Inc. Air Pollution from Nitration Processes.
Contract No. CPA 70-1, Task 22. Cincinnati, Ohio, March 1972.
55
-------
TNT PRODUCTION PROCESS NO. 5
Purification
1. Function - Following nitration, crude TNT is washed with water to remove
free acid. In the batch process neutralization with soda ash (Na2C03) is the
first step, followed by water washes. In the continuous process the crude
TNT is subjected to a series of water washes, the water flowing countercurrently
to process flow. The TNT is then neutralized with soda ash and treated with a
16% aqueous sodium sulfite (sellite) solution to remove contaminating isomers.
A single sellite treatment is used for batch production while a double, countercur-
rent treatment with the sellite solution occurs during continuous production.
Sellite (Na2S03) purification is accomplished by the replacement of the nitro
group in the meta-position in 8- and y-TNT by a sodium sulfonate group, forming
highly soluble sodium salts of the corresponding dinitrotoluenesulfonic acids.
The sellite also reacts with a small quantity of y-TNT forming hexanitrobibenzyl,
giving the red color. The sellite-treated TNT receives a final series of
countercurrent extractions with water and is transferred to the finishing process
as a slurry. Water from these extractions, combined with the sellite solution,
constitutes the "red water" which is concentrated and either sold to the paper
industry or evaporated to dryness and incinerated.
2. Input Materials - Basis - 1.0 kg purified TNT.
Crude TNT - 1.1 kg - product of the nitration process, contaminated with 3 to
5% 3- and y-TNT isomers and residual nitration acids.
Soda Ash - 0.06 kg - 3% solution in water.
Na2S03 - 0.06 kg - as sellite (16% Na2S03 in water). This is usually prepared
by burning sulfur to produce S02 and countercurrent scrubbing to remove the
trioxide and other impurities. This is followed by reaction with 22% Na2C03
in a countercurrent packed tower with recirculation to achieve process strength.
(In CIL continuous nitraton process, sellite is prepared directly from dry Na2S03-)
Process Water - 0.89 a.
3. Operating Parameters - Sources consulted for this study were devoid of
information relating to process temperatures, flow rates, or operating pressures.
4- Utilities - Fuel: Red water incineration at one production facility,
processing over 10.4 Gg/yr of red water, uses natural gas as a primary fuel at
a rate of 19,600 m3/month.
Water: Data from one facility producing TNT by the continuous flow method
indicates, for TNT purification, total process water use is 0.89 il/kg TNT.
Of this, approximately 0.09 ฃ/kg becomes yellow water which is returned to
the continuous nitration line and 0.44 ฃ/kg occurs as red water from the
sellite wash. The balance is scrubber water.
56
-------
Data relating to the consumption of other utilities in the purification of
TNT have not been found in the sources consulted for this study.
5. Haste Streams - Waste water is generated from three sources described
below.
Yellow water: The acidic effluent from the first water washing of crude
TNT during continuous flow production is returned to the nitration process at
the dinitration step. Excess yellow water, above the volume returned to nitra-
tion, is combined with other waste process water for treatment.
Red Water: The effluent from sellite treatment and subsequent washing
of crude TNT has a typical composition of 77.6% water, 17.3% organics, 5.2%
NaNO , and 2.9% Na2SO . (Due to conflicting analytical methods, the total ex-
ceeds 100%.) The production of red water amounts to 0.34 kg/kg TNT produced,
consisting of 0.26 kg process water, 0.06 kg organics (nitrotoluenes and
nitrotoluenesulfonic acid salts), and 0.02 kg dissolved inorganics (NaNOx
and Na2SO ).
X
Red water is concentrated to 35 to 40% solids and either sold to the
paper industry as a source of sulfite liquor or incinerated. Incineration
results in atmospheric emissions of NO and S02 as well as solid waste (ash).
It is reported that, at one facility producing TNT by batch nitration, 0.179
kg ash is produced/kg TNT manufactured. The ash, consisting primarily of
NaaSO^ is disposed of in sanitary landfills or by stockpiling on open land.
The ash, reported to be 90% soluble, is susceptible to leaching by rain water,
creating a potential source of contamination to surface as well as ground water.
Pink Water: This waste stream is generated by the TNT manufacturing pro-
cess as well as by LAP operations. Pink water from manufacturing plants arises
from nitration fume scrubber discharge, red water concentration distillates,
finishing operation hood scrubber and washdown effluents, and possibly spent
acid recovery wastes. The first two sources of pink water may contain isomers
of DNT as well as of TNT. One source indicates that nitrobody content in
discharges from the TNT spent acid recovery plant at Radford AAP ranged from
15 to 168 kg/day. Laundry waste waters have also been reported to contain TNT.
Table 20 summarizes available data on nitrobody content of pink waters from
various sources. Pink waters currently are discharged to sumps to remove
settleable solids. Effluent from the sumps may be treated by carbon adsorption
or by evaporation/leaching. Sludge from the sumps is removed at regular
intervals and disposed of by open burning.
The National Emission Data System emission factor listing indicated 16 g
particulates, 1 g S0x and 19 g N0x emissions/kg TNT produced as a result of
red water incineration. Exhaust emissions from sellite manufacture are
factored at 0.35 g/kg TNT produced. Table 19 presents available emission
data from miscellaneous sources at the only Army ammunition plant currently
engaged in TNT production.
6- EPA Source Classification Code - Sellite exhaust: 3-01-010-06
Red water incineration: 3-01-010-04
57
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59
-------
7. References -
1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propellents Production Industry. 3 Vols.
Washington, D. C., Oct. 1975.
2) Booz-Allen Applied Research, Inc. A Study of Hazardous Waste
Materials, Hazardous Effects and Disposal Methods. 3 Vols.
Vol. II, PB 221-466, Bethesda, Md., 1973.
3) Environmental Protection Agency, Mid-Atlantic Region, Report on
Waste Disposal Practices, Radford Army Ammunition Plant, Radford,
Virginia. Philadelphia, Pa., May 1973.
60
-------
TNT PRODUCTION PROCESS NO. 6
Finishing
1. Function - TNT crystals from the purification process are slurried with
water and pumped to a melt tank where the TNT is melted and most of the water
is removed by evaporation. The molten TNT is then passed through hot air
dryers for evaporation of residual water. The dehydrated product is then
solidified on a water-cooled flaker drum or stainless steel belt. The
solidified TNT is scraped from the belt or drum with a beryllium blade.
The resultant flaked TNT is boxed and transferred to a storage or loading
area.
2. Input Materials - Crystalline TNT from the final water wash in the
Purification Process (No. 5) and process water are the input materials for
finishing.
3. Operating Parameters - Hot air is supplied to dryers at 100ฐC or higher.
Data on other operating parameters were not found in sources consulted for
this study.
4- Util ities - Data were not found in sources consulted for this study.
5. Waste Streams - A waste-water stream results from this process. So-called
"waste acid" from the finishing process results from spillage, floor drainage
and washings from the finishing area. Effluent is treated with lime or soda
ash to neutralize residual acids and discharged to the chemical sewer. A
report of a study performed on waste acid treatment at one facility indicated
overall performance of the treatment plant is inadequate.
Neutralization of acidic waste is adequate under normal conditions, but
some waste parameters are not suited to treatment by such a neutralization
facility. This is evidenced by an average effluent content of 13,254 kg/day
dissolved solids, 245 kg/day NO , 1800 kg/day SO , 818 kg/day COD and 10.6
kg/day a-TNT. x x
Sources consulted for this study were not specific on dryer venting but
it may be assumed that venting is to the atmosphere with water vapors the
sole constituent of the waste stream.
6. CPA Source Classification Code - None exists for this process.
7. References -
(1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propellants Production Industry. 3 Vols.
Washington, D. C., Oct. 1975.
(2) Environmental Protection Agency, Mid-Atlantic Region, Report on
Waste Disposal Practices, Radford Army Ammunition Plant, Radford,
Virginia. Philadelphia, Pa., May 1973.
61
-------
3) Explosives. In: Kirk-Othmer Encyclopedia of Chemical Technology.
Vol. 8. H. F. Mark, ed. N. Y., Wiley, 1966, pp. 581-718.
62
-------
Nitrocellulose (NC) Production Processes
Nitrocellulose (NC), or more properly cellulose nitrate, is a fibrous
white solid resembling the cotton 1 inters or wood pulp from which it is pre-
pared. Nitrocellulose is generally graded or characterized according to the
degree of nitration. Dry uncolloided cellulose nitrate is a violent and
sensitive explosive. Treatment with selected plasticizers produces a
colloidal dispersion of nitrocellulose molecules, rendering the material
less sensitive and more prone to burning than to detonation.
The various grades of NC are used chiefly in manufacturing lacquers,
plastic compositions and propellant powders, with only a small amount being
used for the manufacture of gelatin-type dynamites. The inclusion of NC
production in the explosives industry is predicated upon its suitability
as a basic material for propellent formulation.
A flow chart for NC production is presented in Figure 7. Two processes
are described: Nitration (Process No. 7) and Purification (Process No. 8).
Four different processes have been used historically for the nitration
of cellulose. These are 1) the pot, 2) the Thompson displacement,
3) the centrifugal, and 4) the mechanical dipper processes. The mechanical
dipper process, as described in Process No. 7, is the least hazardous,
and is the only one now used in the United States. A newly developed
continuous nitration processing line is currently being installed at one
Army ammunition plant.
Gaseous emissions from NC production are generally associated with
nitration of the cellulose molecule (Process No. 7) whereas liquid waste
streams are generated mainly during purification.
Purification of NC, which -?s described in Process No. 8, is actually
a chain of individual processes for treating and washing the fibrous pro-
duct. Neutralization of reaction acids trapped within the cellular
structure of NC is extremely difficult but is absolutely necessary to
insure stability of the final product.
63
-------
CONG.
HN03
H2S04
Mg
-------
NITROCELLULOSE (NC) PRODUCTION
PROCESS NO. 7
Nitration
1. Function - Raw cellulose (cotton 1 inters or specially prepared wood pulp)
must be purified for use. The raw material is first boiled with dilute
caustic and then washed several times with water. This is followed by
several bleachings with bleaching powder or sodium hypochlorite in water.
After drying and shredding, the material is ready for the reactor.
In batch production pre-purified cotton 1 inters or wood pulp (dry and
shredded or fluffed) are added to mixed nitric and sulfuric acid in metallic
reaction vessels known as "dipping pots" and the mixture is stirred with
cooling to control temperatures of the exothermic reaction. The reaction
is represented by the following idealized formula.
mixed
acid
(7-1)
Theoretically, complete nitration of all hydroxyl groups would yield a
final nitrogen content of 14.14%. In practice, nitrogen content is held
to between 10.5% and 13.8%, representing a substitution of 1.8 to 2.9
hydroxyls per glucose anhydride unit in the chain. Substitution values are
controlled by the proportions of the mixed acids used for nitration, the
value varying directly with acid concentration.
Following nitration the crude NC is "wrung" in a centrifuge to remove
most of the spent nitrating acids and then dumped into a "drowning tub"
filled with water to stop the reaction. The crude NC/water slurry from the
drowning tub is then transferred to the purification area.
2. Input Materials - Values for input quantities/unit of product are based
on rated capacities for two production facilities of approximately 3818 kg
NC/hr at 263 kg cellulose/hr feed input. Theoretical values may be calculated
as 0.54 kg cellulose and 25.3 kg mixed acid/kg crude NC. Both rated and
theoretical values are relative and will show some degree of variation,
depending on acid ratios e.nd level of nitration in the product.
Basis: 1.0 kg crude nitrocellulose as guncotton.
65
-------
Pre-purified cellulose fibers (0.69 kg) and mixed acid (32.4 kg) con-
stitute the feed stream to this process. The mixed acid is prepared from
HN03 and HaSOi,. The relative concentrations of acids control the extent of
nitration and the nature of the resultant product, as illustrated in
Table 21.
Table 21. REPRESENTATIVE MIXED ACIDS USED IN PREPARING VARIOUS GRADES
OF NITROCELLULOSE
Mixed Acid
Product Su'furic % Nitric % Nitrosylsulfuric % Water
Pyroxylin (8-12% N)
Pyrocellulose (12.6% N)
Guncotton (13.2-13.4% N)
45
58
60
35
22.5
26.5
_
4
4.5
20
15.5
10
3. Operating Parameters - Sources consulted indicated control of reaction
temperature in the ranges of 30ฐC to 34ฐC as well as 37ฐC to 4Uฐ(J. Reaction rime
for batch nitration in dipping pots is 25 minutes for the standard 15 kg batch.
Continuous nitration lines produce crude NC at the rate of approximately
68 to 70 kg/min.
4. Utilities - No data for utilities consumption specific to the nitration
process in NC production were found in the sources consulted for this study.
See Figure 8 for a schematic of total daily water consumption for a typical
NC batch facility at full production.
5. Waste Streams - The reactor and centrifuge (or wringer) are vented to an
absorber where any NOx is oxidized and absorbed in water. The weak HN03 solution
thus produced is transferred to the acid concentration system. Concentrated
acids from this system are recycled to the mixed acid system. Absorbers are
vented to the atmosphere. Emissions consist of NOX from the first absorber
and NOx + SOX from the second. The National Emission Data System emission
factor listing indicates 0.65 g SOx and 1.05 g N0x/kg NC emissions from the
reactor pots with 32.5 g SOX and 14.5 g N0x from acid concentrators. Table 22
presents summary emission data from three army ammunition plants (GOCO), two
of which are currently inactive. No quantitative data pertaining to solid
or waterborne waste specific to the nitration process were found in the
sources consulted for this study. Cleanup operations generate virtually all
of the waste water from the nitration process. Thus, waste water may be
expected to have a low pH and to contain relatively high levels of N03-N, and
suspended solids.
6. EPA Source Classification Code - Reactor pots: 3-01-041-01
H2S04 Concentrators: 3-01--041-02
66
-------
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7. References
1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propellants Production Industry. 3 Vols.
Washington, D.C., Oct. 1975.
2) Processes Research, Inc. Air Pollution from Nitration Processes.
Contract No. CPA 70-1, Task 22. Cincinnati, Ohio, March 1972.
69
-------
NITROCELLULOSE (NC) PRODUCTION
PROCESS NO. 8
Purification
! Function - Purification of nitrocellulose is an involved and tedious
operation. The basic cellular structure of the parent material (cotton
linters or wood pulp), which is retained on nitration, acts to entrap resid-
ual spent acids. Failure to remove the traces of spent acid renders NC
unstable during storage.
Purification of the crude nitrocellulose takes place in a number of
discrete steps, each taking place in a so-called "house," as follows:
Boiling tub house - the NC/water
separated, and the water vehicle
is discharged to the boiling tub
to the wet NC in the boiling tub
to 0.25 to 0.50%. Steam is then
the large wooden boiler tubs and
slurry from the drowning tub is
(approximately 3% total acidity)
pits. Sufficient water is added
to bring total acidity level
passed through heating coils in
the material is boiled for an
extended period of time. This acid hydrolysis, or "sour boil," de-
stroys unstable sulfate esters and nitrates of partially oxidized
cellulose. After completion of the sour boil, water is drained
to the boiling tub pits and the NC is washed with recovered or
then is treated in two neutral boils using
is washed with recovered or filtered
Water from the two neutral boils and
the boiling tub pits. The NC is then
filtered water. The NC
filtered water. The NC
water after each boil.
washes is discharged to
slurried in water and pumped to the next purification step.
Beater house - Di
boiling tubs unti
material is then
beaters, pulping
dustry. Here the
more amenable to
the NC is reduced
the
LUC no ii ieuuocu
by settling tests
water, the NC is
lute Na2C03 is added to the NC slurry from
1 the material is slightly alkaline. The
pumped through primary and secondary Jordan
devices similar to those used in the paper in-
fibrous material is reduced to a physical state
purification. The operation is continued until
to the desired degree of fineness, as determined
. After settling and decantation of the alkaline
transferred as a slurry to the next step.
Poacher house - Sodium carbonate solution is added to the slurry
from the beaters and the material is boiled. The soda ash treatment
is followed by several fresh water (neutral) boils and a minimum
of two washes with fresh water. The material is screened to
remove unpulped fibers and separated by centrifugation. The
centrifugate is discharged to the poacher settling pits and the
NC precipitate is reslurried and pumped to the next operation.
Blender house - In this step the NC is circulated as a water slurry
and sampled for final product quality. At this stage NC fines
known as "pit cotton" recovered from the settling pits are added
when making up bler.c's which contain both low-grade and high-grade
nitrocellulose.
70
-------
Final wringer house - The NC slurry from the blender house is
"wrung" by centrifugation to approximately 30% moisture content
and then stored or processed in accordance with specific end-use
requirements for the batch.
2. Input Materials - Nitrocellulose enters the purification process as a
water slurry with a total acidity of approximately 3% and is transported
as a slurry through the entire purification process. Soda ash (Na2C03) is
added to the slurry entering the beater house on the basis of 1 g Na?C03/kg
NC. In the poachers soda ash is added to the slurry on the basis of 4 to
5 g Na2C03/kg NC. Process water requirements for purification are shown
in Figure 8 in Process No. 7.
3. Operating Parameters - Residence time for NC in the boiling tubs varies
according to the product being treated. Pyrocellulose and pyroxylin are
subjected to 40 hours of boiling treatment that involves three changes of
water. Guncotton is subjected to a sour boil for 60 hours, followed by
two 5-hour neutral boils. Hydrolysis (sour boil) is performed at an acid
content of 0.25 to 0.50%, calculated as HzSOi,. In the poachers the NC
slurry is subjected to a four-hour boil in soda ash solution, followed
by a two-hour neutral boil in filtered water. According to information
contained in one source, the NC may be subjected to two additional neutral
boils of one-hour durations. The poached NC is then allowed to settle for
up to one hour before separation and transport to the blender house. All
boiling and poaching operations are carried out at 96ฐC. Specific data
relating to batch size were not found in sources consulted for this study.
However, from examination of known values for such parameters as 1) daily
production level, 2) time for purification, and 3) batch size in the nitration
process, it is evident that crude NC is pooled for purification and that
large quantities of crude NC are purified in each batch.
^' Uti1ities - Figure 8, Process No. 7 shows the general product flow and
water balance for a typical batch NC production line. Data on consumption
of steam for heating the various purification boilers, of fuel used in
steam production, or of other energy expenditures were not found in the
sources consulted for this study.
5. Waste Streams - The extremely large volumes of process water associated
with the manufacture of NC makes the treatment and disposal of waste water
a formidable problem. Acidic wash waters and noil ing tub washes drain to
settling pits where NC fines are removed.
Overflow from the pits flows to waste acid neutralization facilities
where CaC03 (as a lime slurry) is added to neutralize the acids present.
After neutralization, the material is either discharged directly or trans-
ferred to settling lagoons. Approximately 13.6 x 10ft kg CaSO(1 sludge is
generated yearly as a result of waste acid neutralization at one NC pro-
duction facility. The settling lagoons for this specific plant are drained
at 3 to 6 month intervals and the sludge is removed for burial on adjacent
land. The burial site is locatad on flat land and shows no visible signs
of leaching.
71
-------
Waste water from the beater, poacher and blender houses flows to another
settling pit area where NC fines settle out. Effluent from the pit is
either recycled to the wash lines or is discharged.
NC fines constitute a major portion of the total suspended solids in
the waste water discharges of NC production facilities and can be expected
to approximate the NC fines lost during the various processing steps. One
source lists the following losses during NC purification:
Boiling tub house - 68.2 kg/day
Jordan beater house - 295 kg/day
Poacher house - 295 kg/day
A summary of overall waste water discharges as a result of NC production
at two manufacturing facilities is shown in Table 23.
Possible sources of air emissions are the boiling tubs where steam
and acid vapors are vented. The National Emission Data System emission
factor for this process predicts 2.0 g N0x/kg NC produced.
6. EPA Source Classification Code - Boiling tubs: 3-01-041-03
7. References -
1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propel 1 ants Production Industry,, 3 Vols.
Washington, D.C., Oct. 1975.
2) Environmental Protection Agency, Mid-Atlantic Region, Report on
Waste Disposal Practices, Radford Army Ammunition Plant,, Radford,
Virginia. Philadelphia, Pa., May 1973.
3) Explosives. In: Kirk-Othmer Encyclopedia of Chemical Technology.
Vol. 8. H. F. Mark, ed. N.Y., Wiley, 1966, pp. 581-718.
4) Processes Research, Inc. Air Pollution from Nitration Processes.
Contract No. CPA 70-1, Task 22. Cincinnati, Ohio, March 1972.
72
-------
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/ -i
-------
RDX/HMX Production Processes
Cyclotrimethylenetrinitramine or RDX is widely used as ^n inoredient
of bursting charges and "plastic" explosives. This material, also known
as Cyclonite, is currently replacing tetryl as a base charge in military
detonators. RDX offers distinct logistical advantages over explosives
dependent on petroleum derivatives as a base material. In addition, its
stability is superior to that of PETN or tetryl and nearly equal to that
of TNT.
The nitration reaction producing RDX results in low level contamination
(<10%) with the related compound cyclotetramethylenetetranitramine (HMX).
In its B-crystalline form HMX has little effect on the performance of RDX.
By manipulation of reactant concentrations the reaction may be driven to
HMX production. For this reason, RDX and HMX production processes are
considered as one in this study.
Figure 9 is a flow chart for RDX/HMX production. Two processes are
described: Nitration (Process No. 9) and Refinement (Process No. 10).
RDX/HMX may be prepared by direct nitrolysis of hexamine or by inter-
action of formaldehyde, ammonium nitrate and acetic anhydride. The method
described, a combination of these two methods, was originally developed
during World War II. Refinement (Process No. 10) consists of nothing more
than selective recrystallization from type-specific solvents.
74
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75
-------
RDX/HMX PRODUCTION PROCESS NO. 9
Nitration
1. Function - The chemistry of RDX/HMX manufacture reveals a combination
of two reactions. The first produces RDX by direct nitrolysis of hexamine
and is ideally represented by:
NN02
KN,, + 4 HN03 ^H2CX \H2 + 3 HCHO + NH4N03 (9-1)
02NN NN02
CH2
The second, known as the Canadian reaction, produces RDX by the interaction
of equivalent amounts of formaldehyde, ammonium nitrate and acetic anhydride
according to the following scheme:
NN02
3 HCHO + 3 NH4NO, + 6(CH3CO)20 ^H2CX CH2 + 12 CH.fC02H (9-2)
I I
02NN NN02
From the above it may be seen that the two by-products of direct nitrolysis
are raw materials for the Canadian reaction. Since the nitrolysis reaction
will occur under conditions favorable for the Canadian reaction, simple
addition of reactions (1) and (2) yields:
NN02
(CH2)6Nlt + 4 HN03 + 2 NH,N03 + 6(CH3CO)20 ^2 H2CX \H2 + 12 CH3C02H
02NN NN02
^CH2/ (9-3)
A solution of hexamine in glacial acetic acid is introduced to the
batch nitration vessel. Acetic anhydride is added, followed by a pre-
mixed ammonium nitrate-nitric acid solution. The initial crude product
contains RDX and HMX in varying proportions, according to reactant ratios
as mentioned above. Various nitrated and acetylated derivatives of hexamine
fragments contaminate the crude RDX/HMX.
After the nitration reaches completion, the reaction mixture is aged
and simmered to hydrolyze the contaminating intermediates and then cooled
to effect crystallization of crude RDX/HMX. Table 24 indicates the changes
in composition of product as a result of the aging and simmering steps.
76
-------
Table 24. EFFECT OF AGING AND SIMMERING ON COMPOSITION OF PRODUCT
(RDX/HMX MANUFACTURE)
Reaction Products
Fresh Slurry
kg %
Aged Slurry
Simmered Slurry
kgb %
RDX
HMX
BSXa
Other intermediates
Total
20.
1.
1.
2.
25.
61
59
43
30
93
79.
6.
5.
8.
99.
48
13
51
87
99
22
1
1
1
26
.57
.66
.34
.05
.62
84.
6.
5.
3.
99.
78
73
03
94
99
22.57
2.21
0
0
24.78
91.
8.
0
0
100.
08
92
00
'BSX: Major reaction intermediate (CH3COOCH2-N(NO?)-CH?)?-N-NO?
Indicates kg of product from total batch weight of 100 kg of the following
feed stream: 9.17 kg hexamine
14.97 kg acetic acid
30.57 kg ammonium nitrate/nitric acid
44.96 kg acetic anhydride
0.33 kg water
The crude RDX/HMX crystals are slurried in water and sent to a refining
process. The filtrate from post-nitration filtration, along with the first
wash water, is sent to a recovery facility where HN03 is neutralized with
NaOH. The material is pumped to a primary evaporator where about 80 percent
of its volume is volatilized and condensed as 60% acetic acid. The sludge
remaining is diluted, heated to 100ฐC and seeded with RDX slurry. Additional
RDX/HMX crystallizes as the mixture is cooled to 30ฐC. The explosive is
recycled to the washing step of the line while the supernate is routed to
a secondary evaporator for additional acetic acid recovery. The remaining
sludge is steam stripped to recover residual acetic acid. All recovered
acetic acid is purified, concentrated and recycled, and the stripped sludge
enters the waste stream.
2- Input Materials - basis - 1.0 kg RDX produced
Input materials to this process consist of hexamine (0.406 kg) and
acetic acid (0.633 kg), part of which is used as a solvent for the hexamine.
Acetic anhydride (1.992 kg) and a premixed nitric acid/ammonium nitrate
(1.354 kg) solution make up the balance of the feed stream.
77
-------
Table 25 illustrates the different proportions of reactants used in
making RDX and HMX.
Table 25. A COMPARISON OF REACTANT WEIGHT PROPORTIONS
FOR RDX AND HMX PRODUCTION
Reactant
Hexamine
Acetic Acid
NH4N03 - HN03
Acetic Anhydride
RDX Production (%)
9.2
15.0
30.8
45.0
HMX Production
17.0
18.0
11.0
54.0
W
3. Operating Parameters - The ingredients are charged to the reactor at
75ฐC, which temperature is maintained during nitration and aging steps by
circulating water through heat exchange coils in the reactor. Temperatures
for simmering or first crystallization were not specified, nor were resi-
dence times for the reactants in any stage of this process.
4. Utilities - Specific data relating to consumption of utilities were not
found in the sources consulted for this study.
5. Waste Streams - The reactor vessel, aging tank and simmer tank are vented
to a scrubber where acid vapors are recovered and recycled as dilution liquor
for the simmering step. Atmospheric emissions from the scrubber vents include
NO , acetic acid, and traces of formic acid and methyl nitrate. Data for N0x
emission during RDX/HMX production are presented in Table 26.
The stripped sludge from acetic acid recovery is treated with NaOH, con-
verting the ammonium nitrate to sodium nitrate and ammonia; any residual
acetic acid to sodium acetate; and any residual RDX and HMX to ammonia,
formates, amines and sodium nitrate. Small amounts of ammonia vent to the
atmosphere as the vaporized ammonia is condensed. The condensate contains
traces of impurities such as methylamine and dimethyl amine which preclude
its reuse in the nitration process. It is, however, generally disposed of
for use as fertilizer, along with sludge residue, consisting mainly of
sodium nitrate. Small amounts of ammonia and amines are discharged in the
effluent waste-water.
Examination of Table 27 reveals that overall waste-water discharges from
the RDX/HMX nitratation process (which, for the purpose of this study, includes
78
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filtration and washing of the crude RDX/HMX crystals) total approximately
9900 m3 during a typical production day. In general process effluents
containing substantial amounts of product, by-product or spent reactants
are recycled for recovery of the material. Only relatively uncontaminated
process water, cooling and pump seal water, and floor washings are dis-
charged as waste water, first to catch basins and then to sewers.
Table 28 gives some indication of the effectiveness of catch basins
in reducing the pollutant level in the effluent from RDX/HMX production.
The current practice for disposal of materials recovered from catch basins
is open burning.
6. EPA Source Classification Code - None exists for this process.
7. References -
1) American Defense Preparedness Assn. Wastewater Treatment
in the Military Explosives and Propellents Production
Industry. 3 Vols. Washington, D.C., Oct. 1975.
2) Booz-Allen Applied Research, Inc. A Study of Hazardous
Waste Materials, Hazardous Effects and Disposal Methods.
3 Vols. Vol. II, PB 221-466, Bethesda, Md., 1973.
3) U. S. Office of Scientific Research and Development,
National Defense Research Committee, Div. 8. The
Preparation and Testing of Explosives. Summary
Technical Report of Division 8, NDRC. Washington,
D. C., 1946, pp. 6-12.
81
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82
-------
RDX/HMX PRODUCTION PROCESS NO. 10
Refinement
1. Function - An organic solvent (cyclohexanone or acetone, depending on the
desired product) is added to the RDX/HMX slurry received from the nitration
process. The RDX/HMX crystals dissolve in the organic solvent and the solution
is distilled. The residual solvent, supersaturated with RDX/HMX, is allowed
to cool, and the explosive recrystallizes. The recrystallized RDX/HMX is
filtered out and reslurried in water. The slurry is dewatered to approximately
10% H20 prior to formulation in compound explosives.
2. Input Materials - RDX/HMX enters the process as a water slurry from
Process No. 9. The solvent used for recrystallization may be acetone
(for HMX production) or cyclohexanone (RDX) in quantities not specified.
Process water makes up the balance of the feed stream to this process.
Specific data relating to quantities of the above materials in the feed
stream for this process were not found in sources consulted for this study.
3. Operating Parameters - Specific data relating to temperature for distilla-
tion or recrystallization wer
-------
Nitroglycerin (NG) Production Processes
Nitroglycerin is commonly manufactured by two processes. Commercial
production generally takes place using the older "batch" method while most
military production utilizes a continuous flow process. Figure 10 presents a
flow chart illustrative of either production method. Differences between
the two methods are mechanical rather than chemical in nature. Greater
volumes of reactant and/or product are present at any particular stage during
batch processing, but relative concentrations and operational sequences are
similar to those found in continuous flow production.
Two military production plants have "batch" NG lines, but one is not
in present use, and the second is scheduled for replacement by the con-
tinuous process. Once replacement is accomplished, all NG manufactured at
military facilities will be produced by the Biazzi continuous flow method.
Review of processes at a number of commercial NG production facilities also
indicates a general trend toward conversion to the continuous process.
The Biazzi process for continuous nitration of glycerin is one of the
safest methods known for the production of this highly unstable explosive
compound. Like all continuous processes, the Biazzi method is characterized
by a very small inventory of raw nitroglycerin at any stage in the production
line and by careful balancing of flow rates and cooling. Despite the small
quantities present at any one time, a typical plant in continuous operation
can produce 1000 kg/hr.
Spent acid recovery systems and their resultant waste streams are
virtually identical for batch and continuous methods. As shown in Table 29,
waste waters generated by batch and continuous flow production are markedly
similiar. For these reasons, and because it is expected that the bulk of NG
produced in the future will result from continuous flow processes, a detailed
description of batch production methods will not be made in this report.
84
-------
H2 SO4 OR
M3(N03)2
T0 M1XED
ACID
PREPARAT.ON
r M,XED \
[ AC.D J
GLYCERIN
[
TO RECYCLE
OR
DISPOSAL
O GASEOUS EMSSIONS
A UOUID EMISSIONS
D SOLID EMISSIONS
1 1
NITRATION
i n
SPENT ACID 3
RECOVERY
7
SPENT ACID
1(
i T r t
r-
NEUTRALIZATION
AND WASH
TO STORAGE, LAP
OR
PROPELLANT
FORMULATION
FIGURE "O FLOW CHART FOR NITROGLYCERIN PRODUCTION
35
-------
Table 29. AVERAGE WASTE WATER CHARACTERISTICS OF NITROGLYCERIN PRODUCTION
Biazzi Process
Military
Nitration and Acid NG Storage
Parameter Recovery Waste Water Waste Water
Flow, m3/d
PH
Temp. ฐC.
BOD
COD
Kjeldahl - N
Nitrate - N
Sulfate
Susp. Solids
Dissol . Solids
Nitroglycerin
Dinitroglycerin
56.775
8.6
NA
4.5
1228
NA
13280
1416
23.0
81626
1300
850
18.925
10.5
NA
3.2
912
NA
477
130
11.3
13905
266
130
Batch Process
Military Commercial
Total Total
Waste Water Waste Water
416.35
4.7
14.6
NA
109.1
2.5
116.6
242.6
NA
NA
NA
NA
36.714
2.7-10.0
-
NA
2260
23.0
5564
3154
NA
NA
315-12700
NA
Parameter values in g/m3 unless otherwise indicated
NA indicates data not available in sources consulted for this study.
Source: American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propellants Production Industry. 3 Vols
Washington, D.C., Oct. 1975.
86
-------
NITROGLYCERIN (NG) PRODUCTION (BIAZZI PROCESS)
PROCESS NO. 11
Nitration
1. Function - Chemically, nitroglycerin is glyceryl trinitrate and is pre-
pared by the nitration of glycerin with mixed nitric and sulfuric acids ac-
cording to the following idealized equation:
H
H-C
..[.
OH OH OH
C-H + 3 HN03
H H H
H - C - C - C - H + 3 H20 (11-1)
III
N03 N03 N03
Sulfuric acid catalyzes the reaction by forming a hydrated molecule with the
water of reaction, thus shiftirvg reaction equilibrium to the right.
Mixed acid and glycerin are metered into and through the nitration vessel.
Cooling of the reactor is accomplished by circulation of brine through heat
exchange coils contained therein. Glycerin flow is regulated with a propor-
tioning pump and is supplied at a rate dependent on the strength of the
nitrating acid. The effluent from the nitrator, consisting of nitroglycerin
and spent acid, is separated by continuous flow centrifugation. The spent-
acids flow to a recovery unit for treatment and the raw (acid contaminated)
nitroglycerin proceeds to neutralization and washing.
2. Input Materials - Basis - 1,0 kg NG. The feed stream to this process
consists of glycerin (0.422 kg) and a mixed acid containing 0.868 kg HN03 and
0.826 kg HzSO.,. The H2S04 is prepared by mixing 60% oleum with 93% H2SO^ to
produce a 40% oleum. This mixture is then mixed with 97% HN03 to give the
desired concentrations. Process yield is about 96% of theoretical.
3. Operating Parameters - The continuous flow nitration vessel has a
capacity of about 120 liters. It is uninsulated and is equipped with an
agitator and internal heat exchange coils for cooling. A 15 cm opening in
the bottom with a quick release valve allows emergency drowning of the re-
actor contents. The mixed acid is fed to the surface of the reactor charge
while glycerin is fed below the surface. Temperature is controlled at about
15ฐC; pressure is atmospheric.
4. Utilities - See Figure 11 for water balance for typical Biazzi NG pro-
duction line. Water consumption during the nitration process is approximately
4.92 m3/day at 2400 kg/day NG production rate or 2.05 x 10~lt m3/kg nitro-
glycerin produced. This water is used primarily for equipment and floor
wash down. Data relating tc consumption of other utilities were not found
in sources consulted for this study.
87
-------
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5. Waste Stream - The nitration reactor is vented through an absorber to
the atmosphere. Emissions include NOX and HMOs fumes in unknown quantities.
Typical NOX emission is estimated at 0.3 g/kg product. Specific levels of
waterborne pollutants are not specified for this process. Waste waters
emanate solely from building and equipment cleanup operations and can be
expected to contain minimal amounts of pollutants. The process for recovery
of spent acid from nitration of glycerin is identical with that for the re-
covery of other spent nitration acids. For a full description refer to
Process No. 3. A summation of combined waste-water discharge from nitration
and spent acid recovery processes in NG production was shown previously in
Table 29.
6. EPA Source Classification Code - None exists for this process.
7. References -
1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propellants Production Industry. 3 Vols.
Washington, D.C., Oct. 1975.
2) Processes Research, Inc. Air Pollution from Nitration Processes,
Contract No. CPA 70-1, Task 22. Cincinnati, Ohio, March 1972.
89
-------
NITROGLYCERIN (NG) PRODUCTION (BIAZZI PROCESS) PROCESS NO. 12
Neutralization and Wash
1. Function - Raw (acid-contaminated) nitroglycerin is neutralized by counter-
current washing in three successive soda ash baths. The effluent from the
third wash is separated by continuous flow centrifugation. The spent soda
ash solution flows to catch basins, and the neutralized NG flows to a double
fresh water wash. Another centrifugation follows the water wash, after which
the NG is reemulsified in a weak soda ash solution and transferred to temporary
storage. The wash water flows to catch basins for ultimate disposal.
2. Input Materials - Soda ash solutions used for acid neutralization contain
16% Na2C03. The soda ash solution used for final emulsification of neutralized
and washed NG contains 3% Na2C03. Consumption rate for 16% Na2C03 solution,
fresh water and 3% Na2C03 solution is 0.6308 I of each /kg NG. On a full
production basis with daily output of NG standing at 24,000 kg, approximately
15.14 m3/day of each reagent is consumed.
3. Operating Parameters - Data relating to operating temperature and pressure
were not found in sources consulted for this study. Flow rates for the re-
agents at 24,000 kg/day production may be determined from water balance data
presented in Figure 11 (see Process No. 11). Cooling water is supplied to the
16% soda ash washers at a rate of 27.25 m3/d during maximum productions.
4. Utilities - See Figure 11 for water balance for a typical Biazzi NG pro-
duct iorTTTneT" Water consumption stands at 72.6 to 113.6 m3/day. Of this,
41 m3 is line heating water, used only during winter months. Process water
amounts to 45.4 m3/day while cooling water during acid neutralization accounts
for the balance of 27.2 m3/day. The above figures are valid for a production
of 24,000 kg NG/day. Specific data relating to consumption of other utilities
were not found in sources consulted for this study.
5. Waste Streams - The washers are vented to the same absorber as the nitra-
tor and emissions are considered as part of the nitration process. Wastes from
neutralization and wash account for the bulk of waste loading contained in efflu-
ent waters described in Table 29 under Nitration and Acid Recovery Waste Water.
6. EPA Source Classification Code - None exists for this process.
7. References -
1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propellents Production Industry. 3 Vols.
Washington, D.C., Oct. 1975.
2) Processes Research, Inc. Air Pollution from Nitration Processes.
Contract No. CPA 70-1, Task 22. Cincinnati, Ohio, March 1972.
90
-------
NITROGLYCERIN (NG) PRODUCTION (3IAZZI PROCESS) PROCESS NO. 13
Separation
1. Function - Upon withdrawal from temporary storage, NG is separated from
the vehicle of 3% Na2C03. The weak soda ash solution is drained to catch
tanks where any suspended NG settles out for recovery. NG from the separator
is desiccated and transported to storage magazines or to a production area
for subsequent formulation into explosive or propellent mixtures.
2. Input Materials - An emulsion of NG in 3% Na2C03 constitutes the feed
stream to the process.
3. Operating Parameters - Specific data relating to operating parameters for
the process were not found in sources consulted for this study.
4. Utilities - No information was found in sources consulted for this study.
5. Waste Streams - The only significant waste stream generated by this process
stems from separation and disposal of the 3% Na2C03 vehicle. Specific con-
taminants found in waste water from separation of the NG/soda ash emulsion
are shown in Table 29.
6. EPS Source Classification Cpde_ - None exists for this process.
7. References -
1) American Defense Preparedness Assn. Wastewater Treatment in the
Military Explosives and Propellants Production Industry. 3 Vols.
Washington, D.C., Oct. 1975.
2) Processes Research, Inc. Air Pollution from Nitration Processes.
Contract No. CPA 70-1, Task 22. Cincinnati, Ohio, March 1972.
91
-------
Pentaerythritol Tetranitrate (PETN) Production Processes
Pentaerythritol tetranitrate (PETN) is produced by nitration of pentaery-
thritol. Unlike other organic nitrates, PETN is manufactured on a commercial
scale by the use of nitric acid rather than a mixture of nitric and sulfuric
acids.
Data for utilities consumed and waste streams generated during production
of this material are generally unavailable. A comparison with similar processes
indicates that certain characteristic waste products are to be expected, as
stated in the individual process descriptions.
Figure 12 is a flow sheet for the processes that follow. The processing
sequence presented here, consisting of Nitration (Process No. 14) and Stabiliza-
tion (Process No. 15), is considered typical of production in general and thus
is representative of batch, semicontinuous, or continuous production techniques.
92
-------
TO RECYCLE
HaSO4OR
TO DISTILLATION
& RECOVERY
/
OOASCOUS f MISSIONS
A LIQUID EMISSIONS
QSOUO EMISSIONS
ACETONE/
AMMONIUM
BICARBONATE
TO DISPOSAL
FIGURE 12.
TO FORMULATION
QR LAp
FLOW CHART FOR PETN PRODUCTION
93
-------
PENTAERYTHRITOL TETRANITRATE (PETN) PRODUCTION PROCESS NO. 14
Nitration
1. Function - Pentaerythritol (PE) is reacted with concentrated nitric acid
in a water-cooled reactor, forming crystals of the tetranitrate. This reaction
is represented by the following:
CH2OH CH2ON02
HOH2C-C-CH2OH + 4 HN03 ป 02NOH2C- C-CH2ON02 + 4 H20 (14-1)
I ?nฐr-??ฐr I
CH2OH *U L ^ L
The crystals so formed are separated from spent acid by centrifugation or
filtration and water washed to remove residual acid. Spent acid from the
nitration process goes to recovery. PETN crystals from the water wash are
further refined in the stabilization process.
2. Input Materials - Basis - 1.0 kg PETN. PE (0.462 kg) and nitric acid
(0.857 kg) are the sole constituents of the feed stream to this process.
The yield of PETN is approximately 93 percent of theoretical.
3. Operating Parameters - During batch nitration, initial acid temperature
in the water-cooled reactor is 18ฐC. PE is added at a rate sufficient to
elevate and maintain reaction temperature at 22ฐC to 23ฐC. After addition of
PE is completed, the reaction mixture is stirred and cooled for an additional
20 minutes. Specific data for temperature control or flow rates during con-
tinuous or semicontinuous operation were not found in sources consulted for
this study.
4. Utilities - Data relating to utilities consumption were not found in
sources consulted for this study.
5. Waste Streams - Data relating to specific gaseous or liquid wastes from the
nitration process were not found in sources consulted for this study. Waste
streams for recovery and concentration of spent HN03 should be similar to those
for HN03 spent acid recovery (see Process No. 3) from production of other ex-
plosives. Effluent from the first water wash becomes part of the waste stream
but no indication is made of any treatment prior to disposition as waste water.
6. EPA Source Classification Code - None exists for this process.
7. References -
1) Davis, Tenney L. The Chemistry of Powder and Explosives. N.Y.,
Wiley, 1941, 1943.
94
-------
2) Explosives. In: Kirk-Othmer Encyclopedia of Chemical Technology.
Vol. 8. H. F. Mark, ed. N.Y., Wiley, 1966, pp. 581-718.
3) Hedley, W. H., et al. Potential Pollutants from Petrochemical
Processes, final report. Contract 68-02-0226, Task 9, MRC-DA-406.
Dayton, Ohio, Monsanto Research Corp., Dayton Lab., Dec. 1973.
4) U.S. Office of Scientific Research and Development, National Defense
Research Committee, Div. 8. The Preparation and Testing of Explosives
Summary Technical Report of Division 8, NDRC. Washington, D.C., 1946.
95
-------
PENTAERYTHRITOL TETRANITRATE (PETN) PRODUCTION PROCESS NO. 15
Stabilization
1. Function - PETN crystals, water washed after separation from the nitrating
acid, are suspended in a dilute Na2C03 solution to neutralize residual acid.
The slurry is then filtered and the crystalline explosive is washed with water.
The washed PETN crystals are then dissolved in hot acetone containing a small
quantity of ammonium bicarbonate. The solution is filtered and PETN recrystal-
lized (or grained) by the addition of water. The PETN crystals are filtered
from the acetone/water/ammonium bicarbonate milieu and water washed to remove
traces of acetone. The acetone/water filtrate is digested with MaOH (pH 10) to
destroy any contaminating explosive and the acetone is recovered by distillation.
Still bottoms are discharged as part of the waste-water stream. The wet PETN
(40% H20) is considered the final product and is generally not dried before
being used in the production of formulated explosives or specific hardware items.
2. Input Materials - Wet PETN crystals from Process No. 14 constitute the
primary feed stream to this process. Sodium carbonate, acetone, and ammonium
bicarbonate in unspecified quantities are used as reagents for stabilization
of the crude PETN. Water acts as a vehicle for slurrying and as a washing agent.
3. Operating Parameters - Acetone at 50ฐC is used for dissolution of PETN
crystals. No other operating temperatures are specified, nor are any other
operating parameters, e.g., Na2COs or (NHijHCOs concentrations, acetone/water
ratio for recrystallization.
4- Utilities - No data were specified in sources consulted for this study.
5. Waste Streams - No data were found specifying volume or quality of waste
waters or gaseous emissions from this process. It is to be expected that waste
waters will be contaminated with traces of the basic salts used for stabiliza-
tion of PETN as well as nitrates formed by reaction of these basic salts with
residual nitric acid. In addition the waste stream may contain traces of acetone.
Emissions of acetone vapors may be encountered as fugitive gaseous emissions
from the distillation equipment in the acetone recovery system.
6. EPA Source Classification Code - None exists for this process.
7. References -
1) Environmental Protection Agency. Development Document for Interim
Final Effluent Limitations Guidelines and Proposed New Source Per-
formance Standards for the Explosives Manufacturing Point Source
Category. EPA 440/1-76/060-j, Group II. Washington, D.C., March
1976.
2) Hedley, H. W., et al. Potential Pollutants from Petrochemical
Processes, final report. Contract 68-02-0226, Task 9, MRC-DA-406.
Dayton, Ohio, Monsanto Research Corp., Dayton Lab., Dec. 1973.
96
-------
3) U.S. Office of Scientific Research and Development, National Defense
Research Committee, Div. 8. The Preparation and Testing of Ex-
plosives. Summary technical report of Division 8, NDRC. Washington,
D.C., 1946.
97
-------
APPENDIX A
RAW MATERIALS
99
-------
Table A-l. RAW MATERIALS FOR NITRATION PROCESSES
ammonia
magnesium nitrate
sulfur
acetic acid
sodium carbonate
ammonium bicarbonate
acetone
cyclohexanone
sodium sulfite
water
calcium carbonate
sodium hydroxide
toluene
cellulose - cotton linters or specially prepared wood pulp
hexamine
ammonium nitrate
gylcerine
pentaerythritol
100
-------
Table A-2. INGREDIENTS ADDED TO NITRATED ORGANIC COMPOUNDS IN FORMULATED
PRODUCTS
aluminum
ammonium perch!orate
calcium chloride
nitroguanidine
ammonium nitrate
ammonium picrate
polybutadiene
polyurethane
wax
sodium nitrate
polymeric binder
sodium chloride
sulfur
phenolic resin beads
bagasse
sawdust
wood flour
coal
corn meal
corn starch
grain and seed hulls and flours
trace inorganic salts
guar gum
gelling agents
fumaric acid
ethylene glycol
ammonium sulfamate
fuel oil
atticote
ferrophosphate
calcium silicate
mineral oils and jelly
azides
fulminate of mercury
picric acid
centralites
diphenylamine
diphenylurethane, ethyl N,-N'-diphenylcarbamate
ethyl N-phenylcarbamate
2-ni trodi pheny1 ami ne
phthalate esters
triacetin
ether
101
-------
Table A-2. INGREDIENTS ADDED TO NITRATED ORGANIC COMPOUNDS IN FORMULATED
PRODUCTS (Continued)
acetone
ethyl alcohol
graphite
carbon black
ammonium chlorate
potassium nitrate
barium nitrate
potassium sulfate
potassium chlorate
poly (methyl acrylate)
polyisobutylene
polystyrene
poly(vinyl chloride)
adipates
sebacates
102
-------
APPENDIX E
PRODUCTS
103
-------
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Major Characteristics
Cheesy, plastic substance; packed
in paper cartridges, may be slit
and tamped in borehole for
greatest blasting effect; fired by
detonator as are all d>namites;
heat, friction, shock, and
flame sensitive.
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straight d>numitcs; must be
waterproofed b> special
additi%ei
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4 EXPLOSIVES)
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small arn-s. aiul sporting aminunit
Dr\ guncotton in fiber form is used
Mat^r Characteristics
Burning Mle controlled b\ graining, hygro-
scopic, smokeless flame, with intense
flash. gehtim?ed w ith alcohol-ethel.
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Prorellant for mortars and sporting
nition, not used by U.S armed foi
to secure an average of I3.157T- N.
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face area, mor powerful and more readiK
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Propellant for large caliber naval gur
ignitable than straight N C. powders, causes
erosion of gun bores, can be detonated and
is subject to DDT.d
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such as the "Bazooka" {NG base);
na\al ammunition (NG base).
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rolled into sheets, flash reduced bv DNT,
potassium salts, etc
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Belter flnshless powder than FNH powders
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For driving turbines on submarines
rocket-fuel pumps; jet motors, laut
device for ram-jets.
For torpedo turbine drives.
need be removed.
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releases about 1000 Btu per pound. Sup-
plies oxygen to burn petroleum fuel
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Rocket motors.
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igniter and primer assemblies for pr
lants; pyrotechnics; NaNOj powdei
commercial black powder and for p
bombs and saluting charges; (it is b<
continued as blasting charge).
gases.
As above.
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smoky flame; very sensitive to faction,
spark, and heat, hygroscopic.
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APPENDIX C
PRODUCERS
109
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Table C-2. COMMERCIAL PRODUCERS OF EXPLOSIVE ORGANIC NITRATION PRODUCTS
LISTED IN 1976 DIRECTORY OF CHEMICAL PRODUCERS
Company
Location
Product1
Air Products and Chems., Inc.
Bofors America, Inc.
E.I. duPont de Nemours & Co., Inc.
Polymer Intermediates Dept.
Organic Chems. Dept.
Dyes and Chems. Div.
Plastics Products and Resins Dept.
Hercules, Inc.
Indust. Systems Dept.
Coatings & Specialty Products Dept.
Hummel Chem. Co., Inc.
Internat'l Minerals & Chem. Corp.
Chem. Group
Commercial Solvents Corp.,
subsid.
Trojan-U.S. Powder Div.
01 in Corp.
Winchester-Western Div.
Energy Systems Operations
Rubicon Chems., Inc.
Pensacola, Fla.
Linden, N.J.
DuPont, Wash.
Martinsburg, W.Va,
Louviers, Colo.
Deepwater, N.J.
Carneys Point, N.J.
Bessemer, Ala.
Parlin, M.J.
South Plainfield, N.J.
Springville, Utah
Seiple, Pa.
East Alton, 111.
Geismar, La.
DNT
PETN
NG
NG
PETN
DNT
NC
NG, PETN
NC
Tetryl
RDX, PETN
PETN
RDX
DNT
*DNT Dinitrotoluene
PETN Pentaerythritol tetranitrate
NG Nitroglycerine
NC Nitrocellulose
Tetryl Trinitrophenylmethylnitramine
RDX Cyclotrimethylenetrinitramine
Source: Nelson, T.P. and R. Pyle. Screening Study to Determine the Need for
New Source Performance Standards in the Explosives Manufacturing
Industry. Radian Corp. EPA Contract 68-02-1319 task 50. July 1976.
Ill
-------
RATION PRODUCTS
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ON COMMERCIAL PRODUCERS OF EXPLOSIVE (
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TECHNICAL REPORT DATA
(Please read iHttniciiom, on the reverse bejorc eomplctinv)
1 REPORT NO. 2.
EPA-600/2-77-023L
4. TITLE AND SUBTITLE
Industrial Process Profiles for Environmental Use:
Chapter 12. The Explosives Industry
7. AUTHOR(S)
Charles E. Hudak and Terry B. Parsons
9. PERFORMING OI1G AN 1 7. A 7 ION NAMt AND ADDRESS
Kadiun Corporation
8500 Shoal Creek Boulevard
P.O. Box 99^8
Austin, Texas 78766
12 SPONSORING AfjtNCi' NAME AND ADDRESS
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. ENVIRONMENTAL PROTECTION AGENCY
Cincinnati, Ohio 1+5268
3. RECIPIENT'S ACCESSION-NO.
5. REPORT DATE
February 1977
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION RLPORT NO
10 PROGRAM i Lt ML Ml NO
1ABG15: KOAP ^'JAFH-U^
TrrcaNTHACtTcTiANY'isro " """ " ~ ~
68-02-1319, Task 3^ |
!
13. TYPF. Of REPORT AND PERIOD COVEHED 1
Initial: 8/75-11/76 }
14. SPONSORING AGENCY CODE ;
EPA/600/12 '
1C- SUPPLEMENTARY NOTES
16. ABSTRACT
The catalog of Industrial Process Profiles for Environmental Use was developed
aid in defining the environmental impacts of industrial activity in the United
Entries for each industry are in consistent format and form separate chapters <.
study. The explosives industry as a vhole includes companies which manufacture
organic nitration products and formulate mixtures of chemicals vith explosive
properties. Five nitration processes are described along with the process for
production of nitric acid used in the nitration reactions. Six process flow ct.
and fifteen process descriptions have been prepared to characterize the indusLi
Within each process description available data have been presented on input mat
operating parameters, utility requirements and waste streams. Data related to
subject matter, including company, product and raw material data, are included
appendices.
arts
y.
the
as
7. KEY WORDS AND DOCUMENT ANALYSIS
.1 DESCRIPTOR?,
""Pollution " ' " ""
Explosive?.
Organic Nitrates
Nitric Acid
Nitration Reaction
Munitions
Pyrotechnics
Process Description
13. DISTRIBUTION STATEMENT
Release to Public
li. IC>ENTlFIEnS/OPi- Nl ENDFO TEFtMS
Air Pollution Control"
Water Pollution Control
Solid Waste Control
Explosive Disposal
19. SECURITY CLASS (This Report/
Unclassified
20. SECURITY CLASS (This page)
Unclassified
L COSATt I iclii i"r,; i; j
"" "0713 '
13C
19D
19A !
i
21. NO. <~>f >=AGtb
1?R
22. PRICE
EPA Form 2220-1 (9-73)
-117
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U.S. fcnvifonmemal Piotection Agency
n 5, Library (PL-12J)
Chicago. II 60604-3590
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