AIR POLLUTION
FROM
NITRATION PROCESSES
TASK ORDER NO. 22
CONTRACT NO. CPA 70-1
MARCH 31, 1972
PREPARED FOR
OFFICE OF AIR PROGRAMS
ENVIRONMENTAL PROTECTION AGENCY
SUBMITTED BY
PROCESSES RESEARCH, INC.
INDUSTRIAL PLANNING AND RESEARCH
CINCINNATI, OHIO
-------
AIR POLLUTION
FROM
NITRATION PROCESSES
Task Order No. 22
Contract No. CPA 70-1
March 31, 1972
Prepared for
Office of Air Programs
Environmental Protection Agency
Submitted by
PROCESSES RESEARCH, INC.
Industrial Planning and Research
Cincinnati, Ohio
1
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AIR POLLUTION
FROM
NITRATION PROCESSES
INDEX
Section Title Page
I Introduction
A. Scope of Study 1
II Manufacturing Technology
A. Classes of Processes 6
B. Discussion of Industries, Processes, Products,
Sources and Emissions 6
C. Catalog of Sources 11
D. Air Pollution Control Devices of Nitric Acid Plants 167
III Conclusions
A. Pollution by Processes 170
B. Control Devices 170
C. Instrumentation 172
D. Upsets 172
E. Incentives for Control of Emissions 172
F. Adsorption 173
G. Size Factor 173
IV Recommendations
A. Adaptation of Existing Control Devices 174
B., Development of New Control Devices 174
C. Process Upsets 175
V Bibliography 176
ii
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SECTION I - INTRODUCTION
A. SCOPE OF STUDY
During the Sixties, the production of nitric acid approximately doubled,
from 6.6 to 12.9 billion pounds. For the Seventies, the production is expected
to do ible again, with the making of 25 billion pounds per year by 1980. Chart 1
shows a plot of the nitric acid production data.
Using 1970 as the key year, those compounds which had a production of
over 1 million pounds utilizing nitric acid or its oxides were selected as impor-
tant nitration compounds, and these were studied in this report. Table 1 lists
these compounds, their formulas, their 1970 production, and the amount of nitric
acid utilized in their production. The listings of this table account for about
95 percent of the nitric acid uses. The remaining 5 percent of the nitric acid
production is used to make minor nitration compounds and industrial explosives.
Over 75 percent of the nitric acid production is used to produce ammonium nitrate,
while another 9 percent is used to make adlpic acid. The remaining uses of
nitric acid are small.
Probably because of the color of nitric oxides fumes, nitration processes
have long been considered to have the potential for atmospheric pollution. There-
fore, a survey of the processes employed for the production of the 14 most impor-
tant nitro products was undertaken.
Processes and production data were accumulated using forms and techniques
developed under Environmental Protection Agency, Office of Air Programs, Contract
70-1, Task Order No. A. An explanation of the system is shown in Section II of
this report.
1
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this study covers the pollution of atmospheric air by processes which
utilize nitric acid. It does not cover air pollution by nitric acid production,
or the nitric acid treatment by the fertilizer industry of phosphate rock. The
study identifies the air pollutants from 15 selected major nitration processes,
estimates the present and future quantities of pollutants, evaluates the appli-
cability of control devices presently used in nitric acid production for con-
trolling the air pollutants from the nitration processes, and recommends research
and development objectives for the monitoring and controlling of these air
pollutants.
The tariff commission does not publish production figures on explosives.
The Bureau of Mines, however, compiles statistics on the consumption of indus-
trial explosives and their figures Indicate a 6 percent annual growth rate. It
is estimated for 1970 that the consumption of industrial explosives was over
2 billion pounds. The important nitration compounds classified as explosives
are:
Ammonium nitrate
Nitroglycerine
Trinitrotoluene
Nitrocellulose
Dinitrotoluene
Dinitrobenzene
The main use of ammonium nitrate is as a fertilizer. About 1.5 million
pounds of nitrocellulose per year are used in plastics. About 300 million pounds
of dinitrotoluene per year are used in polyurethane production; this use has been
included in Table 1. Also, dinitrobenzene is an important intermediate. An
attempt has been made in the study to include all typical nitric acid reactions.
3
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TABLE 1 - LIST OF MAJOR NITRATION COMPOUNDS
Compound
Formula
1970
MPPY
As
HNO3
MPPY
Percent
HNO3
Production
Total
Compound
Production
Ammonium Nitrate
NH4NO3
12,400
9,760
75.6
Adlpic Acid
C6H10O4
1,300
1,200
9.3
Terephthalic Acid
c8o4h6
400(1>
230
1.8
1,300
Acrylonitrile
C3H3N
lood)
200
1.5
1,037
Nitrobenzene
C6H5NO2
515
278
2.15
Dinitrotoluene
Nitrochlorobenzene
C7H6(N02)2
c6h4cino2
290
100
223
45
1.73
0.35
Oxalic Acid
Nitroparaffins
C2H2O4
rno2
2(1)
20
15
16
0.12
0.12
23
Nitrocellulose
Nitroglycerine
Trinitrotoluene
c6h7n30h
C3H5N3O9
C7H5N3O6
65
23
65
23
0.50
0.18
No Data
Industrial
Industrial
Potassium Nitrate
Sodium Nitrite
KNO3
NaN02
126
100
117
96
0.90
0.74
HNO^ Accounted For
12,268
95
Nitric Acid
HNO3
12,920
(1) By nltro processes
4
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The principles discussed here may then be applied to any reactions that become
significant in the future.
Areas outside the scope of this study are:
a. Oxides of nitrogen from fuel burning.
t>. Oxides of nitrogen from explosives.
£. Process upsets; for example, the dumping of batches of explosives
into a drown tank.
cL Minor explosives such as urea nitrate or nitrostarch.
5
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SECTION II - MANUFACTURING TECHNOLOGY
A. CLASSES OF PROCESSES
Nitric acid has two important chemical properties. First, nitric acid
can nitrate a material. For example:
NH3 + HN03 NHaN03 or
C6H6 + HNO3 C6H5N02 + H20
Second, nitric acid or oxides of nitrogen can oxidize a material. For
example:
C6H4(CH3)2 + AHNO3 C6H4
-------
TABLE 2 - CLASSIFICATION OF NITRATION PRODUCT/PROCESSES
Process
Product
1970 Production
Million Pounds
Reaction Phase
Temperature, C
Pressure
Process .Total
]lassl- Emissions
flcatlon Millions
Emission
No* Particulate
Factors
Others
of Pound!
Per Year
Nitration of Ammonia
Solution of
Ammonium Nitrate
3,360(3>
Liquid
50 - 80
Atm
1 0
Nitration of Ammonia
Prills of
Ammonium Nitrate
7,900
Liquid
50 - 80
Atm
I 3.4
0.86
Nitration of Ammonia
Granules of
Ammonium Nitrate
1,140
Vapor
200 - 240
50 psig
2 3.1
1.3 3.5
0.7 as NH3
Nitric Acid Oxidation of Cyclohexanol
Adipic Acid
1,300
Liquid
70 - 100
50 - 250 psig
3 9.0
12 1.8
Nitric Acid Oxidation of P-xylene
lerepntna nc
Acid
UUUW
(1,300 total)
Liquid
(Est) 100
Atm
3 2.8
13 1.8
--
Nitric Oxide oxidation of Propylene
Acrylonitrile
lUUv1'
(1,000 total)
Vapor
450 - 500
Atm
4 0.27
5.4 as C3H6
Nitration o£ Benzene
Nitrobenzene
515
Liquid
50 - 90
Atm
1 4.4
0.50
16.6 as C6H6
Nitration of Toluene
Dlnitrotoluene
290
Liquid
75 - 85
Atm
1 0.039
0.27
--
Nitration of Chlorobenzene
Nitrochloio-
benzenp
100
Liauid
20 - 50
Atm
1 0.21
0.9
3.2 as C6H5C1
Nitric Acid Oxidation of Glucose
Oxalic Acid
2UJ
(23 total)
Liquid
70
Atm
3 0.006
4.5 1.8
Nitration of Paraffins
Nitropropane
21
Vapor
370 - 450
125 - 175 psig
2 0\075
1.5
__
Nitric Acid Oxidation of Potassium
Chloride
Potassium Nitrate
and Chlorine
126
Liquid
(Est) 100
20 psig
3 0.82
0.1 12.9
0.001 as BrCl
Nitric Oxide Oxidation of Sodium
Carbonate
Sodium Nitrate
100
Liauid
(Est) 100
Atm
4 0.018
1.8
..
Nitration of Glvcerine
Nitroalvcerine
renW
Liquid
15
Atm
1 0.063
1.9
Nitration of Toluene
Trinitrotoluene
(23)<2>
Liquid
50
Atm
1 0.52
17
27 as CyHg
Nitration of Cellulose
Nitrocellulose
--
Liquid
30
Atm
1
31
65 as SO2
(1) By this process
(2) Industrial explosives only
(3) Part of Prill process
-------
therefore, have not been studied. The 14 compounds have been classified Into
four SIC Industry numbers as established by the Department of Commerce. The
Department of Commerce publishes, on a routine basis, SIC compound production
data.
In an earlier EPA-OAP project (Contract No. CPA 70-1), a computer
program was set up to catalog and record air pollution sources. The data of
this study have been organized on the basis of this program.
For the computer program, a system of nomenclature involving the basic
categories of "Industry," "process," and "source" was developed, using defini-
tions for each category which were believed applicable to all industries. A
subcategory "product" was created to facilitate handling of data in those indus-
tries where many polluting processes, sometimes producing identical products, are
found. It is anticipated that this subcategory will be used only for the more
complex industry groups. The definition for each category follows:
Industry. An industry, as defined for cataloging purposes, will cor-
respond with headings in the SIC Manual. That manual is subdivided into "Major
Group," each with a unique two-digit numerical code, amd subcategories within
each Major Group called "Group Number," each of which has a number of designated
subgroups called "Industry Number." For example, Major Group 28 "Chemicals and
Allied Products" Includes the Group Number 281 "Industrial Inorganic and Organic
Chemicals," which is further subdivided into Industry Number groups such as 2818 -
"Industrial Organic Chemicals Not Elsewhere Classified" and 2819 - "Industrial In-
organic Chemicals Not Elsewhere Classified," Under each four-digit Industry number
a listing of included products is shown.
8
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Process. As the term is used here, it includes processes in which a
-single product is prepared by a specific procedure Involving chemical change or
change in state, and unit operations where a class of products is .manufactured
by use of essentially identical equipment and operations. For example, the
product sulfuric acid is produced both by the chamber process and by the contact
process, and both would be Included as processes. Also included would be the
unit operations such as galvanizing, degreaslng, and other operations used in
the manufacture of many fabricated metal products. All processes fall within
some industry category as previously defined.
Product. As the term is used for this study, a product is a subcategory
useful for relating process to Industry in the SIC codes as described above.
Also, it is useful as a subdivision for certain Industries, such as 2818 - Indus-
trial Organic Chemicals, where a large number of processes are included despite the
fact that the smallest subdivision in the SIC Manual is used for definition of
the industry.
Source. As defined for this study, a source is a piece of equipment,
essential to the operation of a process, from which air pollution emissions occur
unless the emissions are prevented by application of pollution control technology.
By contrast, a piece of equipment installed for the primary purpose of minimizing
air pollution emissions is considered control equipment for a source. Thus, a
specific type of equipment, such as a scrubber, may be classifiable as a source
or as control equipment, depending on its role in the process.
9
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Data Limitations. Complete and valid data were not always available.
Therefore, it was necessary in some instances to estimate emission factors,
source control factors, processes, and production levels. To qualify the validity
of the data, the following code was used:
A ¦ Valid data. The result of census or experiment.
B => Estimated data. Estimate based on limited census or experimental
data.
C = Estimated data. Estimate based on little or no census or
experimental data.
Emission factors which were used are an average factor for all sources,
and the source factor (estimated percent of existing sources which are controlled)
is a national average. Application of such numbers to individual plants or to a
small number of plants in a given geographical area could yield erroneous results.
Product Discussion. Under each of the 14 nltro products, the various
methods of producing the compound are discussed. Production and capacity data
from 1960 are also shown, along with the major uses. A 1980 production forecast
is included.
Process Discussion. Each process is described in detail covering feed
preparation reaction conditions, product purification, recycle systems, raw
materials, by-products, and sources of air pollution. A process flow sheet has
also been included.
Process Data Tabulation. On the attached form, AQCR means Air Quality
Control Region, and the capacity is in millions of pounds per year.
10
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Source Data Tabulation. On this form, the emission factors are in
pounds per ton of product, the efficiency factor shows the portion of pollutant
retained in the control device as a decimal, and the source factor is the por-
tion of the plants equipped with control devices, expressed as a decimal.
C. CATALOG OF : SOURCES
1. Cyclic Intermediates - SIC Industry No. 2815
Establishments primarily engaged in manufacturing cyclic organic
intermediates. Important products of this industry include:
Derivatives of benzene, toluene, naphthalene
Synthetic organic dyes
Synthetic organic pigments
Cyclic crudes
Some of the nitro cyclic intermediates are:
Nitroanillne
Nitrobenzene
Nitro dyes
Nitrophenols
This study includes, for Industry No. 2815, nitrobenzene, terephthalic
acid, dinitrotoluene and nitrochlorobenzene. The production of these four products
consumes about 6 percent of the nitric acid production.
11
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SIC. NO.
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12
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18 20
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21 23
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YR
42
DATE ISS.
REV. NO.
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
13
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Product: Nitrobenzene
Nitrobenzene is produced by reacting benzene and nitric acid In the
liquid phase,
c6h6 + H0N02 C6H5N02 + H20
In the Sixties, the annual growth rate was 12 percent. For the Seventies,
an annual growth rate of 10 percent is expected. Chart 2 shows a plot of the
production data for nitrobenzene.
About 97 percent of the nitrobenzene production is used to make aniline.
14
-------
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-------
Process: Nitration of Benzene to Nitrobenzene
£. Feed Preparation
A mixed acid is used in the reactor. This acid has a composition
of 53 percent H2SO4, 39 percent HNO3, and 8 percent H2O. The mixed acid is pre-
pared by mixing 93 percent H2SO4, 97 percent HNO^ and 50 to 60 percent HNO3. The
benzene requires no feed preparation.
Is. Reaction Conditions
The reaction is carried out either in batches or continuously.
For batch operation, the kettles are sized for 1000 to 1500
pound quantities of benzene, and are equipped with agitators. They are jacketed
and also have internal colls for cooling.
The reaction cycle requires two to four hours. The benzene is
charged to the reactor along with a heel of spent acid. The mixed acid Is added
slowly below the surface of the benzene. The temperature is maintained at 50 to
55C, but is allowed to rise to 90C toward the end of the reaction to promote
complete reaction.
The reactor vents to an absorber.
An emergency drown tank is provided, located below the reactor.
In case of a runaway reaction in the reactor, the batch is dumped to the drown
tank, which contains water to kill the reaction.
When the reaction is complete, the reactor batch Is transferred
to a separator tank. The overall process yield from benzene is 95 to 98 percent.
16
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c. Product Purification
In the separator tank, the crude nitrobenzene separates from the
spent acid by gravity. The spent acid either goes to provide a heel for the next
reactor batch or to acid concentration. There Is a loss of 0.5 percent yield of
nitrobenzene in the spent acid.
If the nitrobenzene is to be used to make aniline (most of the
nitrobenzene which is made is so used), the crude nitrobenzene from the separator
is transferred to the aniline process.
If a nitrobenzene of high purity is desired, the crude nitro-
benzene is transferred to a washer where it is washed with water and sodium
carbonate solution to remove residual spent acid. The crude is then distilled
to obtain the desired pure nitrobenzene product. The residuals from distillation
are wastes.
d. Recycle Systems
The vents from the reactor go to an absorber, where any N0X is
oxidized with air and absorbed in water to produce nitric acid. The unreacted
air is vented. The acid stream goes to acid concentration.
In the acid concentration system, spent acid and acid from the
reactor vent absorber first go to the top of a denltrating tower, which is heated
with steam. As the liquids flow down through the tower, rising vapors strip all
HNO3 and oxides of nitrogen. The water in the feed remains with the sulfuric
acid, which is drawn off the bottom of the tower. The overhead gases go to the
bleacher. The dilute sulfuric acid goes to a sulfuric acid concentrator.
17
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In Che bleacher the vent gases are oxidized with air and pass
through a reflux condenser where any HNO3 present condenses and drops back to
the bleacher. Nitric acid with a concentration of 97 percent is drawn off from
the bottom of the bleacher, and goes to the mixed acid system.
The off gases from the reflux condenser go to an absorber column,
where additional oxidation takes place and the oxides of nitrogen are absorbed in
nitric acid and water to produce nitric acid. The nitric acid from the bottom of
the column is recycled to the denitrating column. The air from the absorber is
vented.
The sulfuric acid from the bottom of the denitrating column
goes to a sulfuric acid concentrator where the acid is concentrated to 93 percent
sulfuric acid. The sulfuric acid produced goes to the mixed acid system. The
water removal is a waste.
e. Raw Materials
The major raw materials are benzene and 50 to 60 percent nitric
acid. Other raw materials are 93 percent sulfuric acid to make up for process
losses and sodium carbonate which is used in the washer.
f. • By-productB
There are no by-products.
Sources of Air Pollutants
There are two sources of air pollution. These are the absorber
on the reactor vents and the absorber on the acid concentration system. Both of
these vent air and unabsorbed oxides of nitrogen.
18
-------
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20
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EMISSION FACTOR
Q
TYPE
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Q
SOURCE
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Q
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DATE ISS.
REV.NO.
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
-------
SI WE DATA TABULATION
INOUSTRY
NO.
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INDUSTRY
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PROCESS :
-------
Product: Terephthalic Acid
Terephthalic acid is made by oxidizing P-xylene. About 30 percent of
the terephthalic acid production is oxidized by nitric acid,
C6H4(CH3)2 + 4HN03 C6Ha(COOH)2 + 2H20 + 4N0
The remaining production is made by air oxidation,
C6h4(CH3)2 + 302 CgH^ (COOH)2 + 2H20
In 1970, about 1-1/2 billion pounds of terephthalic acid were produced.
Dacron is polyethylene terephthalate. An annual growth rate of about 30 percent
is expected to continue. See Chart 3.
23
-------
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24
-------
Process: Oxidation of P-xylene to Terephthalic Acid
a. Feed Preparation
No feed preparation is required.
b. Reaction Conditions
The reaction is a liquid phase reaction in which paraxylene and
nitric acid (40 to 50 percent) are nixed,and react. (The operating temperature
and pressure have not been published.) Terephthalic acid crystallizes out of
the solution during the reaction. The slurry formed in the reactor goes to a
filter. NO gas, which is generated by the reaction, goes to recovery.
c_. Product Purification
When the slurry from the reaction step is filtered, the mother
liquor (consisting of water and unreacted nitric acid) goes to the NO recovery
system.
The cake from filtration is dried to become the terephthalic
acid product for feed to a Dacron process.
4. Recycle Systems
The NO off gas from the reactor is fed to an oxidizer column,
where it is mixed with air. This oxidizes some of the NO to NO2. The mother
liquor from filtration is fed to the top of the oxidizer column and absorbs the
oxides of nitrogen to form a dilute nitric acid solution. The spent air from
the oxidizer column is vented.
The dilute nitric acid produced in the oxidizer column is con-
centrated to AO to 50 percent nitric acid and recycled to the reactor.
25
-------
e^. Raw Materials
Two raw materials are used. Paraxylene is the chief raw material.
Some nitric acid (40 to 50 percent) is required to make up for process losses.
f_. By-products
There are no by-products.
£. Air Pollution Sources
There are two sources of air pollution. The vent from the NO
oxidizer column will contain air and unabsorbed oxides of nitrogen. The dryer,
if it uses air to pick up the moisture, will have a vent which contains air,
moisture, and probably product particulates.
26
-------
PR 109
lob
FLOY/ DIAGRAM
TE_REPH T HA LIC ACID MANUFACTURE:
E pa pgecEssss esssAffiee,inc. f.i.
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27
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RELATED INDUSTRIES
BIBLIOGRAPHY
29
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<3
DATE ISS.
REV. NO.
REV.DATE
FOR PROOUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
j El BLIOGRAPHY
[
30
i
-------
Product: Dinitrotoluene
Dinitrotoluene is an explosive. It is mixed with NH4NO3 and acts as a
promoter. Therefore,; there is little production data on mono or dinitrotoluene.
However, in the Sixties, dinitrotoluene has become an important Industrial inter-
mediate for the production of polyurethanes. In the late Sixties, some production
data have been published on dinitrotoluene, as shown on Chart 4.
Dinitrotoluene is made by nitrating nitrotoluene,
C6H4CH3N02 + H0N02 C6H3CH3(N02)2 + h2o
An annual growth rate of about 20 to 25 percent is expected. Also, for
nitrotoluene production, it should be noted that toluene nitrates easier than
benzene.
31
-------
CflA^r -4-
/yc: a
/07a
/?£4
/?ffo
-------
Process: Nitration of Nitrotoluene to Dlnitrotoluene
a. Feed Preparation
This process uses a mixed acid with an approximate composition
of 72 percent H2SO4, 17 percent HNO3 and 11 percent H2O. The mixed acid is pre-
pared by mixing 50 to 60 percent HNO3 with 93 percent H2SO4. The nitrotoluene
requires no feed preparation.
b^. Reaction Conditions
The process may be either batch or continuous. The same process
steps are used for either process. For the continuous process, the reaction
step consists of one or more reaction vessels in series, with all the feed going
to the first vessel and with any subsequent vessels providing additional time
for the reaction to go to completion. The reactors are provided with agitators
and jackets or colls for cooling.
Mixed acid (as described under feed preparation), and either
ortho or paranitrotoluene are fed separately and continuously as liquids to the
reactor. A stoichiometric ratio of nitrotoluene to nitric acid in the mixed acid
\
is used. The reaction is exothermic, and is controlled at 75 to 85C. The liquid
product from the reactor overflows to the decanter. The reactors vent to an
absorber. The yield is 96 percent.
Product Purification
The liquid product from the reaction step is separated in the
decanter to give a spent acid layer and a crude 2,4-dinitrotoluene layer. The
spent acid layer Is recycled (see recycle systems).
33
-------
The crude 2,4-dinitrotoluene is washed and neutralized continu-
ously in a series of steps. In the Meisener process these steps are as follows.
The crude is washed, with water and with the waste water from the second step
washing, in a column in which both liquids flow upward concurrently. Air is fed
to the bottom of the column, and flows upward with the liquids to provide agitation.
The liquids flow out the top of the column to a continuous de-
canter. The air vents to atmosphere from the top of the column. In the decanter
the wash water separates out and is discarded. The organics layer is fed to a
second stage column which operates in the same manner as the first column described
above. The wash water consists of the waste water from the third washing step
and a dilute solution of sodium bicarbonate which neutralizes any acids present.
The liquids from this second column flow to a continuous decanter. The air is
vented. In the decanter, a water layer separates from the organic layer and is
fed to the first washing column. The organic layer is fed to a third stage of
washing, which consists of a column and decanter similar to the other two stages.
Water is used for washing. The organic stream from this stage is the product.
If orthonitrotoluene is used as the feed material, there will be
some 2,6-dinitrotoluene present in the product. If a high purity 2,4-dinitro-
toluene product is desired, it is obtained by distillation of Che pTOduct from
the third washing step.
d,. Recycle Systems
Two recycle systems exist. The first system involves the spent
acid from the reaction system. This acid is fed continuously to the spent acid
34
-------
washer, where it is mixed with a continuous flow of fresh nitrotoluene. Any
residual nitric acid in the spent acid reacts with the nitrotoluene to form
2,4-dinitrotoluene and to produce a spent acid that does not require denitrifi-
cation. The spent acid and nitrotoluene are separated in a continuous decanter.
The nitrotoluene layer becomes feed to the reaction step. The spent acid is fed
to an H2SO4 concentrator, where the acid is concentrated to 93 percent H2SO4 for
feed to the mixed acid system.
The second recycle system involves the absorber. The vents from
the reactors go to the absorber, where any NO is oxidized and absorbed in water
to produce nitric acid. The nitric acid is fed to the mixed acid system. The
air is vented.
e. Raw Materials
The major raw materials are 50 to 60 percent nitric acid and
either orthonitrotoluene or paranitrotoluene. Minor raw materials are 93 percent
sulfuric acid to make up for process losses, and sodium bicarbonate used in the
washing operations.
f_. By-products
No by-products are produced.
£• Sources of Air Pollution
There are two sources of air pollution. One is the vent from the
absorber, which will consist of air and any unabsorbed oxides of nitrogen. The
second is the vents from the washers, which will be air saturated with water and
2,4-dinitrotoluene.
35
-------
PR 10?
Job
FLOW Pi AG-RAM
Z-4 D!N/TRQ TOLUENE MANUFACTURE
t. P. A PROCESSES RESEARCH, INC. f.i. h. 3382L
Lo< at ion
INDUSTRIAL PLANNING
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43
DATE ISS.
REV.Na
REV.DATE
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FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
38
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INDUSTRY
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DATE ISS.
REV.NQ
REV.DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
19
-------
Product: Nltrochlorobenzene
Nitrochlorobenzene Is produced by nitrating chlorobenxene,
C6H5C1 + H0N02 *»C6H4C1N02 + H20
The chloro group increases the reactivity of benzene, making the reaction
easy to carry out.
The alternate route to nitrochlorobenzene, namely, nitration of benzene
followed by chlorination, does not proceed smoothly, and has lower yields and
more side reactions. There is no industrial process based on these reactions.
Chart 5 shows a plot of the production data of all nitrochlorobenzenes.
About 80 percent of this production is for paranitrochlorobenzene, a plot of
which is also shown. Due to fluctuations in the pesticide market, no sustained
growth in nltrochlorobenzene production is expected. Nitrochlorobenzene is used
as an intermediate.
40
-------
CHAVT-
/90Z.
-------
Process: Nitration of Chlorobenzene
a. Feed Preparation
Mixed acid containing 53 percent H2SO4, 35 percent HNO3 and
12 percent H2O is prepared by mixing 50 to 60 percent HNO3 with 93 percent H2SO4
and 97 percent HNO3. The latter two acids are produced in the acid concentration
system.
b. Reaction Conditions
The reaction is usually a batch process. A typical process uses
I
a 2,640 gallon reactor equipped with an agitator and with a jacket and Internal
coils for cooling. The reactor Is charged with 5,500 pounds of spent acid and
10,000 pounds of monochlorobenzene. The agitator is started, and 15,600 pounds
of mixed acid is fed over a period of 9 hours. The temperature is permitted to
rise from 20C to 50C during the 9 hours. When the reaction is complete, the
batch is allowed to settle for 3 hours. The spent acid layer is drawn off to the
spent acid washer and the crude chloronitrobenzene is transferred to the crude
washer.
The spent acid is washed with a fresh charge of monochlorobenzene,
to be used in a subsequent nitration batch to remove nltrobodies from the acid.
The acid is then sent to acid concentration.
The overall process yield is not available.
c^. Product Purification
The crude chloronitrobenzene is washed three times with water,
followed by washing with dilute caustic and water. The charge is then dried at
90 to 100C under vacuum.
42
-------
The crude chloronltrobenzene contains about 65 percent of the
para Isomer, about 34 percent of the ortho isomer and 1 percent of the'meta
isomer. These are separated and purified by alternate crystallization and dis-
tillation steps.
The crude is first cooled to 16C in a crystallizer. About
SO percent of the para isomer crystallizes out as a pure component and is sepa-
rated from the mother liquor. The mother liquor is then distilled under vacuum.
The first cut is primarily unreacted monochlorobenzene, with traces of meta
chloronltrobenzene. This is redistilled to recover the chlorobenzene for recycle
and a meta crude product containing 60 percent meta chloronltrobenzene. The
second cut is predominantly the para isomer. This is crystallized out to obtain
the para isomer as a product, while the mother liquor is recycled to the mother
liquor tank. The third distillation cut is a slop cut and is returned to the
mother liquor tank. The still residues are distilled without the column. The
overheads go to a crystallizer, where the ortho isomer product crystallizes out.
The mother liquor from this crystallization is returned to the mother liquor
tank. The residues from the final distillation are a waste material. Product
purities are not available.
d. Recycle Systems
There are several recycle streams which result during the pro-
duct purification steps. These were discussed under product purification.
Another recycle stream is the spent acid stream from the reaction.
This acid is fed to the denitratlng column. In this column, the oxides of
43
-------
nitrogen and any HNO^ are driven overhead as a gas while the water is held back
by the sulfuric acid. The sulfuric acid leaves the bottom of the column at about
60 to 70 percent H2SO4 and is fed to a sulfuric acid concentrator where the water
is driven off and a 92 to 93 percent sulfuric acid is produced for feed to the
mixed acid tank. The overheads from the denitrating tower go to a bleacher,
where they contact air and the NO is oxidized. The gases then pass through a
reflux condenser where 97 percent HNO3 is condensed and returns to the bleacher
and is transferred to the mixed acid tank. The gases from the reflux condenser
go to the absorber where the oxides of nitrogen are absorbed in water and some
fresh nitric acid. The bottoms from this absorber are recycled to the denitratioo
tower.
e. Raw Materials
This process uses two raw materials, monochlorobenzene and 50
to 60 percent nitric acid. Some makeup sulfuric acid is required.
f_. By-products
This process produces ortho chloronitrobenzene, para chloro-
nitrobenzene, and a crude containing 60 percent meta chloronitrobenzene.
Sources of Air Pollution
There are two usual sources of air pollution. The first is the
vent from the reactor, which contains oxides of nitrogen. The second vent is
from the absorber in the acid concentration system, which contains air and un-
absorbed oxides of nitrogen. If the plant has a drum type sulfuric acid concen-
trator, instead of a distillation type concentrator, a vent exists which will
contain flue gases and entrained sulfuric acid vapor and organics vapor.
44
-------
f/ CHLOFPO /V/T7? 0 8 E N2.ENE
nONOC HLORO benzene:
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46
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S0IICE Mil TABUIAM
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FOB PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
47
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SOURCE DATA TABSLAWR
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SIC. NO. : c
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2. Industrial Organic Chemicals, Not Elsewhere Classified - SIC Industry
No. 2818
Establishments primarily engaged in manufacturing industrial organic
chemicals not elsewhere classified. Important products Include:
Non-cyclic organic chemicals
Solvents
Polyhydric alcohols
Synthetic perfume and flavoring materials
Rubber processing chemicals
Plasticizers
Synthetic tanning agents
Chemical warfare gases
Esters, amines, etc., of polyhydric alcohols
Some of the nitro compounds are:
Acrylonitrile
Adipic acid
Adlponltrile
Ethyl nitrite
Malononitrlle
Oxalic acid
For this study, these products have been studied:
Nitroparaffins
Adipic acid
Oxalic acid
Acrylonitrile
The production of these four products consume about 11 percent of the nitric acid
production.
49
-------
Product: Nitroparaffins
Nitroparaffins are made by nitrating light aliphatics in the vapor phase,
C3Hg + HONO3 +- C3H7NO2 + H20
Commercial Solvents has pioneered this family of compounds, having their
main production plant in Louisiana with a semi-works in Peoria. The nitroparaffins
are used as intermediates and solvents. The annual growth rate is estimated at
less than 5 percent. There Is no published production data. Chart 6 shows the
capacity data.
50
-------
IOPl.
¦
fc-T/a
-------
Process: Nitration of Paraffins
a. Feed Preparation
There Is no feed preparation.
]>. Reaction Conditions
The reaction is carried out continuously. Propane is vaporized
and heated to 370 to 450C, and is fed to the reactor at 125 to 175 psig* In the
reactor, 50 to 60 percent nitric acid is sprayed into the propane gas. About
five moles of propane per mole of HNO3 are fed. The heat of reaction vaporizes
the nitric acid. The reactor operates adiabatically.
The desired reaction products are nltromethane, nltroethane,
1-nitropropane and 2-nitropropane. A typical distribution is 10 percent nltro-
methane, 25 percent nltroethane, 25 percent 1-nitropropane, and AO percent
2-nitropropane. By varying the reaction conditions, the relative amounts of
nitroparaffin may be controlled. Normal ranges, with propane as a raw material,
are nltromethane 10 to 30 percent, nltroethane 20 to 25 percent, nitropropanes
55 to 65 percent.
The purities of the finished nitroparaffin products are all
99 percent plus nitroparaffins. The minimum purity of the individual products
is nltromethane 95 percent, nltroethane 90 percent, 1-nitropropane 94 percent,
and 2-nitropropane 94 percent.
With recycling, the nitroparaffin yield, based on nitric acid,
approaches the theoretical yield. Some 90 plus moles of nitroparaffins are
produced per 100 moles of HNO3 used up. No Information is available on yields
based on propane fed.
52
-------
c. Product Purification
The product gases from the reactor pass through a cooler and
condenser In series. .The nltroparaffins condense and the mixture is brought
down to atmospheric pressure. The remaining vapor contains nitric oxides, some
inerts, unreacted propane, and a small quantity of aldehydes, ketones, etc.
The cooled mixture is fed to an absorber where all components
except nitric oxides, inerts, and unreacted propane are absorbed in a solvent
such as hydroxylamine hydrochloride. The off gases go to a recovery process
which is discussed under recycle systems. The main reason for the absorption
step is to insure that the aldehydes, ketones, etc., are not recycled with the
propane. The bottoms from the absorption column go to the stripper where steam
is used to strip the reaction products from the solvent. The solvent is removed
from the bottom of the stripper and is recycled to the absorber. The overheads
from the stripper are condensed and fed to a decanter. The bottom layer, which
is water, is returned to the stripper. The light layer is fed to the heads
column, where aldehydes, ketones and other light boilers are separated as over-
heads and become a by-product.
The bottoms from the heads column are treated with chemicals
(unidentified) and then washed with water to remove chemical products that would
cause corrosion in the subsequent purification steps.
The reaction products, after the washing step, consist of nltro-
paraff Ins and higher boiling compounds saturated with water. This mixture is
fed to a drying column where the water is removed overhead and returned to the
decanter following the washing step. The bottoms from the drying column are fed
53
-------
to four distillation columns in aeries, where the nitroparaffins are separated
into four products, nitromethane, nitroethane, 2-nitropropane, and 1-nitro-
propane. The bottoms from the last column are high boilers (heavies) and are
a waste product.
_d. Recycle Systems
The off gases from the absorber consisting of nitric oxides,
unreacted propane, and CO2 are fed to a separation system. Details of this
syBtem are not available. However, it is assumed that It consists of an adsorp-
tion step which separates the unreacted propane from the nitric oxides and CO2.
The propane is recycled to the reactor. The nitric oxides and CO2 pass through
an oxidizer where NO is oxidized. This is followed by an absorber where the
oxides of nitrogen are absorbed in water to produce nitric acid. The nitric
acid is recycled to the reactor. The off gases, consisting of air, N2, CC^t
and unabsorbed oxides of nitrogen, are vented.
£. Raw Materials
Two major raw materials are used. These are propane and 50 to
60 percent nitric acid. Minor raw materials are the unidentified chemicals used
in the chemical treatment step, and hydroxylamine hydrochloride required for
makeup for losses in the absorption and stripping steps.
£_. By-products
This process produces one by-product, the overheads from the
heads column, containing aldehydes and ketones. This is either a waste product
or undergoes further processing to produce salable products.
54
-------
&• Sources of Air Pollution
The only pollution source is the vent from the nitric acid
absorber. This vent will contain air, C02 and uaabsorbed oxides of nitrogen.
55
-------
nt iw
Job.
FLOW DIAGRAM
N!TRO PARAFFINS MANUFACTURE
EPA '¦ -i PROCESSES RESUBM,INC. f,u No 3382.
localtoa .
s.bj.
-------
SIC. NO:
28-lfc
UOTT
1-14- ni
INDUSTRY
Toe
PSOGESS DATA
PRODUCT
SH I OF I
AHT(Lo PM-A FFt^i
PROCESS —
AJ l T fLA-rfc/J oF L I Cr iAT
f\ I > p (4 a t i c s CpAR^ ^ ^ M
COMPUTER CODE NOS.
SIC. NO. : •
z
a
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8
COLS.
PRODUCT : M
I
0
COLS.
PROCESS : 9-i3
5
8
PBOfiOCTIOH DATA
AQCR
COMPANY
LOCATION
PRODUCTION
(ipC
CdKk^ fJXlCsC- ^SeC 1/c-mTS
"ST^O-Ci/oC-TfM. £-A
S \
GOMPOTEB eSOE NOS.
AQCR
19 22
STATE
23 24
CITY
2B 38
COMPANY
37 48
BO 61
C/
52
VPA
CITY
66
0
8*
YE
P
AR
58
('¦
'
—
MISCELLANEOUS
RELATED SIC. NOS:
57
-------
INDUSTRY
NO.
es is ¦
INDUSTRY
X o C
PRODUCT
COMPUTER COOE
NOS.
SIC. NO.
4
z
8
I
ft
DATE
PREPARED
n-ic- ni
PROCESS f7 ]cfc-p t °/•J
OF LlC-l+TQM'rW)
f\L.[ p UA-r ic 5
SOURCE
PRODUCT: ^
I
4
0
COLS.
PROCESS : 9-i3
5
8
COLS.
SOURCE : 14-17
X
I
POLLUTANT
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
Q
TYPE
EFF.
FACTOR
Q
SOURCE
FACTOR
Q
No*
/ 5
C
-
COMPOTE!! CODE m.
PNO
18 20
CNO
21 23
UNCON EMISS
24 30
Q
31
CEF
32 35
Q
5»
SCF
37 40
Q
YR
4?
DATE ISS.
REV. NOl
REV. DATE
I
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
58
-------
Product: Adipic Acid
Adlpic acid is made by oxidising crude cyclohexanol. The oxidizing
agent can be nitric acid,
C6H110H + 2hn03 P (COOH)2(CH2)a + N20 + 2H20
by which over 90 percent of the adlpic acid ia made. Or it can be air,
C6HuOH + 2 1/2 02 (COOH)2(CH2)4 + 2H20
In 1970, the production of adipic acid had exceeded 1.3 billion pounds.
For the Seventies, a 20 percent growth rate is expected. See Chart 10 for
production data. Adipic acid is a nylon intermediate.
59
-------
©
o *
o
¦ i
W
£
-------
Process: Oxidation of Cyclohexanol to Adlpic Acid
a. Feed Preparation
The cyclohexanol feed is a crude mixture of cyclohexanol and
cyclohexanone. This crude is usually obtained by the air oxidation of cyclo-
hexane at 125 to 160C and 50 to 250 psi in the presence of cobalt naphthenate
catalyst. The reactor product is distilled to remove water and unreacted cyclo-
hexane. Another method for obtaining the cyclohexanol crude is from the
hydrogenation of phenol at 300F and 50 psig in the presence of a palladium
catalyst. The cyclohexanol crude leaves the reactor as a vapor with unreacted
hydrogen. The cyclohexanol crude is separated from the hydrogen to become the
desired feed material for adiplc acid production.
b. Reaction Conditions
Cyclohexanol crude is oxidized to adlpic acid using AO to
50 percent nitric acid. The nitric acid fed Is at least 1.5 times stoichio-
metric. The reaction is carried out at 50 to 150C and 50 to 250 psig In the
presence of a catalyst consisting of ammonium metavanadate and copper. Based
on cyclohexane content of feed, a yield of 60 to 70 percent adiplc acid is
obtained.
c. Product Purification
The reactor liquid product is air stripped to remove nitrous
oxide. It is then steam distilled to remove unreacted nitric acid and low
boiling organlcs (as overheads).
61
-------
The liquid from the bottoms of the steam still are cooled to
40 to 50C. This crystallizes out the adipic acid. The crystals are separated
from the mother liquor, redissolved in water, and recrystallized to remove im-
purities. The crystals are dried to produce the adipic acid,
cl. Recycle Systems
The reaction produces nitrous oxide as a gas. This is oxidized
with air, and scrubbed with water to produce nitric acid, which is recycled to
the reactor.
The overheads from the steam still contain nitric acid which
is recovered and recycled to the reactor.
A portion of the mother liquor from the first crystallization
step, which contains nitric acid and catalyst, is recycled to the reactor.
Another portion is fed to a still. The overheads from the still, containing
water and nitric acid, are recycled to the reactor. The bottoms are cooled to
crystallize out adipic acid, which is combined with the crystals from the first
crystallization step. The mother liquor is distilled to recover any nitric acid
present. This is concentrated and recovered. The bottoms is either a waste
material or undergoes additional processing to recover the catalyst.
e. Raw Materials
The raw materials consist of the crude cyclohexanol (which is
discussed under feed preparation), 50 percent nitric acid which is obtained by
recycle from the process, and the catalyst which is ammonium vanadate and copper
turnings.
62
-------
_f. By-products
the process yields no salable by-products.
Sources of Air Pollutants.
There are two sources of air pollutants. The first is the
effluent from the oxidizer. This effluent will be air with any residual unoxi-
dized and unabsorbed nitrous oxide or nitrogen dioxide. The other source ip the
vent from product drying which will contain product particulates as a contaminate.
63
-------
PR 109
Job .
Location
FLOW DIAGRAM
AD/PIC ACID MANUFACTURE
t PA PROCESSES RESSi®C»,«ll«. y.i. «« 33 8Z M.
Cfetkcd by
I NOUS TBI Ai; PLANNING
AND BISEARCH
. Dale
10 - XX . 'I I
....... nitration study ,|W,ot, t-H* b. Sfr D.„ io^i
.... j
mcctr^S: nitric acid OXlDATjON of crude cyclohexa nol
STEAM, PROD. PART,
CYC LP HEX ANOL
CATALYST
TO
ORG AN ICS
f HNO-i
REC.OVEM
SCRUBB
OXIDIZE*
100 F
STILL.
STEAM
T
Am
REACTORS
STRIPPER
sot. NITRIC ACID
oAI.Q3
FEED 7MA
TO HN02
CONCENTRATION
$
WATER
WATER
1
STILL
CRYSTAL/ZE/f
\
CRYSTAUZER
i
CRY5TALI7.ER
PRODUCT
T
CENTRIFU 0-E
C^NTRtFUC? j
\aiastE
CFUTRJFUGF
WASTE
64
-------
SIC. NO.
2S t 8
T5ATT
l(- /4 rII
INDUSTRY
SZT &c
TR5CE55 —
PRODUCT
AOlPic A-C(0
O¦
i
R
80 61
CAPACITY
82 65
Q
6?
YEAR
87 58
—
-
MISCELLANEOUS
RELATED SIC. NOS:
65
-------
INDUSTRY
NO.
2.8 IS
mm ui
INDUSTRY
Toe
HA IABULAI1U
PRODUCT
/VbiPi'c AciO
COMPUTER CODE
•
GO
o
2
SIC. NO.
COLS.
1-4
-A
2
e
i
6
DATE
PREPARED
II- /4-1l
PROCESS CXl&AT IOAJ
Of- CHC CoMP.XAlJoL
SOURCE
A&So JifcjF/L
¦ Co i D 11
-------
INDUSTRY
NO.
29 IS
INDUSTRY
SOURCE 01
ITA IftBULAltUn
PRODUCT
Ab l PI c ftc i b
COMPUTER CODE
Z "= L
NOS.
SIC. NO. : c^s"
-X
e
8
i
8
DATE
PREPARED
PROCESS A / i /
SOURCE
D V-^teX
PRODUCT:„
A
i
1
^ \ u n r i ^
°F CYCLdH£*A/JoL
PROCESS : ^jf
5
COLS.
SOURCE : 14-17
X
1
1
POLLUTANT
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
Q
TYPE
EFF.
FACTOR
Q
SOURCE
FACTOR
Q
PfOT lc L, (-
/. a
a
COMPUTER CODE NOS.
PNO
18 20
CNO
21 23
UNCON EMISS
24 30
Q
31
CEF
32 3B
Q
SCF
37 40
Q
41
YR
4?
DATE ISS.
REV.Nd
REV.DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
67
-------
Product: Oxalic Acid
The main source of oxalic acid Is as a by-product from citric acid pro-
duction, using fermentation,
Mold
(Sugars) —^ (C00H)2 + (By-products)
Oxalic acid is also made from formates,
NaOH + CO »» HCOONa
2HC00Na (COONa), + H
2 2
(COONa) 2 + Ca(0H)2 +• Ca(COO)2 + 2 NaOH
Ca(COO)2 + H2SOA (COOH)2 + CaSOA
It is estimated that about 10 percent of the oxalic acid production Is
made by a third process, the nitric acid oxidation of glucose,
c6H12°6 + 6hn03 3(COOH)2 + 6H20 + 6N0
with 70 percent yields and a high purity product.
In 1970, about 23 million pounds of oxalic add was produced. Its main
uses are textile finishing, metal cleaning, and as an Intermediate. Chart 8
shows a plot of the production data. For the Seventies, little growth in oxalic
acid production is expected.
In the late Sixties, there was a shift in oxalic acid producers. Hooker,
Stauffer, Miles, and Victor abandoned this business, while Pfizer and Allied
expanded.
68
-------
10CL_
HART 3
H--H
/•?: ..
ye.
/?fc&
/«?92.
/ V '?£.
1*00
69
-------
Process: Oxidation of Glucose Co Oxalic Acid
£. Feed Preparation
Glucose is obtained from raw starch. The raw starch (85 per-
cent) is dispersed by slurrying it in approximately an equal amount of 11 percent
oxalic acid solution at 75 to 80C. After refluxing for approximately 6 hours,
virtually all the starch is hydrolyzed to a monosaccharide, chiefly glucose,
b. Reaction Conditions
The process is usually run as a batch process. The hydrolyzed
starch solution, containing about 60 percent glucose (monosaccharide), is mixed
with oxalic acid mother liquor recovered from the filtration step of a previous
run. This mother liquor is fortified with sulfuric acid and catalyst to compen-
sate for process losses. The adjusted mother liquor contains approximately
50 percent sulfuric acid, 5 percent oxalic acid, 0.5 percent ferric iron (as
ferric sulfate), and 0.005 percent vanadium (as vanadium pentoxide). The glucose
mother liquor solution is heated to about 70C with agitation. Nitric acid of
65 to 95 percent strength is gradually added at a rate as necessary to maintain
the temperature at 70C. External cooling is generally used. One part of 60 per-
cent glucose solution is used with 2.5 parts of 90 percent nitric acid and 7.5
parts of 50 percent sulfuric acid liquor. Oxides of nitrogen evolved during
the reaction go to the absorption concentration system (discussed under recycle
systems).
The solution from the reactor is cooled in a crystalllzer to
24 to 35C. The resulting slurry is filtered. The mother liquor is returned to
a subsequent reactor run.
70
-------
The filter cake from the filter can be dried to give an oxalic
acid dihydrate of 90 percent purity, or it can be dissolved in an equal weight
of water at 6SC and recrystalllzed at 24C. In the latter case, the Blurry is
filtered, the mother liquor is returned to the dlssolver, and the filter cake
is dried at less than 65C to yield an oxalic acid dihydrate product which assays
97 to 99 percent.
£. Recycle Systems
The nitric oxides from the reactor are passed to an absorber
where they are oxidized with air and absorbed in dilute nitric acid. The off
gases are vented.
The nitric acid from the absorber is fed to a nitric acid dehy-
drator which uses sulfuric acid to dehydrate the nitric acid. The 90 percent
nitric acid produced is recycled to the reaction step, while the dilute sulfuric
acid formed goes to a sulfuric acid concentrator to be concentrated to 93 percent
sulfuric acid, for recycle to the nitric acid dehydrator.
d. Raw Materials
The major raw material is starch, which is hydrollzed to glucose.
Other raw materials are makeup 93 percent sulfuric acid, makeup 90 percent nitric
acid, and makeup catalyst, i.e., ferric sulfate and vanadium pentoxide.
e. By-products
There are no by-products.
71
-------
Sources of Air Pollution
There are two sources of air pollution. The vented air from
the product dryer will contain product particulates. The vent from the absorber
will contain air saturated with water and also unabsorbed oxides of nitrogen.
72
-------
PR 109
Job
E PA
FLOW DIAGRAM '
OXALIC ACID MANUFACTURE
PROCESSES KSfftfitti, HK?. m> Mn 3382. u„. h.
location
Subie
-------
SIC. NO.
28 IB
"BSTE
H-iB-ni
INDUSTRY
ZLoc
POCKS BA A
PRODUCT
SH
Of
oxA<-ie Aztb
PROCESS
0>Cl5AT(^A/ G-L^C(5S£
COMPUTER COOE NOS.
SIC. NO.
COLS.
1-4
PRODUCT : ^
COLS.
PROCESS : 91,3
1
e
/
8
l_
4
3
~
£
PMHCTIN IITI
AQCR
COMPANY
LOCATION
PRODUCTION
2-f ALLIED
/5 ALLIED
6aFFftL6 , A/Y
MftR-cus Hoo<,PA
A
to
la
c
c
CMPITil (DDE IDS.
AQCR
19 22
STATE
23 24
CITY
25 »
1? 48
SO 61
CAPACITY
B2 SB
O
Sff
YEAR
67 SB
—
MISCELLANEOUS
RELATED SIC. NOS:
74
-------
INDUSTRY
NO.
2818
SOURCE Di
INDUSTRY
Toe
Uk TABULATION
PRODUCT
OXALIC
COMPUTER CODE
/ £
NOS.
SIC. NO. : ct^s
x
a
8
i
6
DATE
PREPARED
11- 19 '11
PROCESS OX. iQ/VTU'/O
Or £ C U C ° 5
-------
INDUSTRY
NO.
28 IP:
INDUSTRY
"Toe
PRODUCT
6XA.LIC AciD
COMPUTER CODE NOS.
SIC. NO. : °?Jf •
0
Z
8
I
s
DATE
PREPARED
PROCESS q £ lO A T1 oaJ
Op GLucoSB
SOURCE
0 fa £
PRODUCT: m
*
I
3
PROCESS : C°tf
I
SOURCE r'i+.'il
1
1
POLLUTANT
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
Q
TYPE
EFF.
FACTOR
Q
SOURCE
FACTOR
Q
falTtcuLA IB
/.a
6
AJojjsz,
COMPUTER tm NOS.
PNO
18 20
CNO
21 23
UNCON EMISS
24 30
Q
31
CEF
32 36
Q
38
SCF
37 40
Q
41
YR
43
DATE ISS.
REV.NOL
REV. DATE
I
¦
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
76
-------
Product: Acrylonitrile
About 16 percent of the acrylonitrile ia produced by this reaction,
which will be studied-here,
4C3H6 + 6N0 —!—^ 4C3H3N + N2 + 6H20
About half of the acrylonitrile production is made by the Sohio process,
which appears to be the process of the future,
C3H6 + NH3 + 1-1/2 02 C3H3N + 3H20
(Air)
The remaining acrylonitrile is made from acetylene,
C2H2 + HCN ~- C3H3N
There is a fourth process, using ethylene oxide, which is obsolete.
Chart 9 shows a plot of the production data. An annual growth rate of 13 per-
cent is forecast. About 61 percent of the acrylonitrile is used for fibers.
The next larger use, 17 percent, is for resins.
77
-------
10OOO
-3
TitnJ -
r/&
Gor5
/?8a
-------
Process: Oxidation of Propylene to Acrylonitrlle
£. Feed Preparation
None
b. Reaction Conditions
Nitric oxide is reacted with proplyene in the vapor phase at
450 to 500C and atmospheric pressure. There is a large excess of propylene in
the feed. The reaction mixture is diluted with air or nitrogen. The catalyst
is either lead titanate or silver/silica. A product yield of 80 percent is
obtained at a conversion of 12 percent.
£. Product Purification
The reaction gas product stream passes through a water scrubber
where all the reaction products except nitrogen and the dilution air are absorbed.
The nitrogen and air are vented. The product and by-products are recovered and
purified in a train of distillation columns. Unreacted propylene is recovered
and recycled to the reaction step.
d. Raw Materials
The raw materials used in the process are propylene and nitric
oxide.
e. By-products
The process produces the following by-products: acetone,
1,5-hexadiene, benzene, and hydrogen cyanide.
Sources of Air Pollution
There is only one point where atmospheric emission occurs.
This point is the vent from the scrubber. Normally, the emission will consist
of nitrogen and air saturated with water vapor.
79
-------
PR 109
Job .
EPA
Lout ion
Sub.e.t nitration study
- ' FLOW DIAGRAM
AC-RYL ON ITR iLE MANUFACTURE
PROCESSES RESEARCH, IMC.
file No
3382.
INDUSTRIAL PUNNING
AND RESEARCH
-Sheet No
Date _
CINCINNATI N6W YORK
fl0~2 £" W
^^^<=3 H6
... NO...>
aj. R.. or Ma
PROPYLENE
WATER
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siwrnn
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STOPPER
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? _ 1-3 HEXADiENB (BY PRODUCT'^
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\HYDROGEN CYANiDE (BYPRODUCT)
Q
-------
SIC. NO.
2g /s
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ll-il'l i
PROCESS DATA TABULATION
INDUSTRY PRODUCT
sh ' of I
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COMPUTER COOE NOS.
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COLS.
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PROCESS
COLS.
: 9-13
L
3
PRODUCTION DATA
AQCR
COMPANY
LOCATION
PRODUCTION
52.
f)u o
AJ »
2o
a
A
COMPUTER CODE I0S.
AQCR
16 22
STATE
23 24
CITY
28 38
COMPANY
37 48
80 61
CAPACITY
82 88
0
YEAR
87 88
-
miscellaneous
RELATED SIC. NOS:
81
-------
S6HCE DATA TAMA TIM
INDUSTRY
NO.
'2.$ 1 8
INDUSTRY
Too
PRODUCT
1 TR t <- £
COMPUTER CODE
NOS.
SIC. NO.
COLS.
1-4
x
2
e
1
6
DATE
PREPARED
II- n-rM
PROCESS /J i "FI2L < c
0 K i DAT i
P>R-c ,o (L
SOURCE
PRODUCT
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&«
1
4
4
PROCESS
COLS.
9-13
c
I
SOURCE
COLS.
14-17
X
I
POLLUTANT
CONTROL DEVICE
DESCRIPTION
EMISSION FACTOR
Q
TYPE
EFF.
FACTOR
Q
SOURCE
FACTOR
Q
C* He
5-4
C,
/^6aJ£
COMPUTER CODE NOS.
PNO
18 20
CNO
21 23
UNCON EMISS
24 30
Q
31
CEF
32 35
Q
38
SCF
37 40
Q
41
YR
42
DATE ISS.
REV.NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
[BIBLIOGRAPHY
82
-------
3. Industrial Inorganic Chemicals.Not Elsewhere Classified - SIC
Industry No. 2819
Establishments primarily engaged in manufacturing Industrial inorganic
chemicals,not elsewhere classified. Important products of this industry Include:
Inorganic salts
Inorganic compounds
Rare earth metal salts
Elements
Some of the nitro compounds of Industry No. 2819 Include:
Ammonium compounds
Potassium compounds
Sodium compounds
For this study, these products were Included:
Ammonium nitrate prills
Ammonium nitrate granules
Potassium nitrate
Sodium nitrite
The production of these four products consumes about 77 percent of the nitric
acid production.
83
-------
Product: Ammonium Nitrate Prills
Ammonium nitrate is made by the direct reaction between ammonia and
nitric acid:
NH3 + HN03 » nhano3
To make prills, the reaction is carried out in the liquid phase using
water as the solvent. Part of the prill tower feed is sold directly as ammonium
nitrate solution.
To make granules, the reaction is carried out in the vapor phase, pro-
ducing liquid ammonium nitrate. This process is discussed elsewhere.
Ammonium nitrate is the largest consumer of nitric acid, using about
75 percent of the nitric acid production in 1970. Chart 10 shows a plot of the
total production of ammonium nitrate. An annual growth rate of about 10 percent
is expected. About 8 percent of the ammonium nitrate is made into granules,
41 percent into solution, and 51 percent into prills. Most ammonium nitrate
plants are very flexible, being capable of producing a wide distribution of
products.
Ammonium nitrate has two major uses. Over 90 percent is used as a
fertilizer, and the remainder is used for explosives.
84
-------
C H A g-T 10
/9ie
-------
Process: Nitration of Ammonia to Ammonium Nitrate Prills
a. Feed Preparation
None.
b. Reaction Conditions
Ammonia gas is reacted with a slight excess of nitric acid as a
liquid at SO to 80C and atmospheric pressure. The reaction is exothermic. The
heat of reaction is used to evaporate a portion of the water which is present to
give an 83 percent ammonium nitrate solution from the reactor. The process yield
is 98 percent.
£. Product Purification
No product purification is required. However, additional
process steps are necessary after the reaction step.
The 83 percent ammonium nitrate solution is sold for fertilizer,
or it is further concentrated to 93 percent ammonium nitrate solution and sold.
If a prilled product Is desired, the 83 percent ammonium nitrate
from the reactor Is concentrated in one or two stages of evaporation to produce
a 95 to 97 percent solution. This solution is fed hot to a prilling tower. The
product from the prilling tower is screened, dried to less than 0.5 percent
moisture, cooled, and rescreened. The final screened product Is coated to prevent
caking and deterioration in storage. The product purity is 99 percent before
coating.
d. Recycle Systems
The oversize and undersize materials from the screening operations
are dissolved in water and are recycled to the reactor.
86
-------
All equipment In the dry solids handling steps is vented to a
water scrubber to recover any product which is present. The water from the
scrubber is combined with the solids and recycled to the reactor,
e. Raw Materials
The raw materials used in the process are 50 to 60 percent
nitric acid, anhydrous ammonia, and the coating material (such as dlatomaceous
earth).
By-products
There are no by-products.
Sources of Air Pollution
There are three primary vents in the process. Two of these have
a single control device. These are the vent from the reactor, which contains
steam and acid fumes, and the vent collection system from the dry product handling
equipment. These vents pass through a common scrubber before discharge to the
atmosphere. The third vent is from the prilling tower and contains air and prod-
uct particulates.
87
-------
« 109
job.
FLOW DIAGRAM
ammonium nitrate manufacture
epa Processes kxsearci, inc. 33 8 z
. Io
-------
PHHSS MTt T&HLATiSH
SIC. NO.
a bi
-------
PAGES
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PAGE 3
INDUSTRY
NO.
INDUSTRY
PRODUCT
AMrtONlUfJ NITRATE
NHf N03
COMPUTER CODE
NOS.
SIC. NO.
COLS
1-4
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-------
INDUSTRY
NO.
INDUSTRY
PRODUCT
AMMONIUM NITRATE
N Hq N03
COMPUTER CODE
101
5.
SIC. NO.
X
DATE
PREPARED
PROCESS
NITRIC ACID
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-------
INDUSTRY
NO.
INDUSTRY
PRODUCT
AM no N tVM NITRATE
NH+ NOj
COMPUTER CODE
NO!
5.
SIC. NO.
COLS
1-4
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NITRIC ACID
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INDUSTRY
NO.
INDUSTRY
PRODUCT
AMMONIUM NITRATE-
Nfy N03
COMPUTER COOS
m.
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X
DATE
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FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
iE-rSLiOGRAPHY
96
-------
SOURCE Nil TU8UTIW
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NO.
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Q
TYPE
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Q
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FACTOR
Q
Pa;-(
-------
Product: Ammonium Nitrate Granules
Gaseous ammonia is reacted with vaporised nitric acid to produce * on
cooling, granules of ammonium nitrate;
NH3(g) + HN03(g) NH4N03(1)
About 8 percent of the total production of ammonium nitrate is made
into granules or over a billion pounds in 1970. The main use of ammonium nitrate
granules is for explosives. Chart 10 shows a plot of the total production of
ammonium nitrate, which Includes granules, prills and solution.
98
-------
lOp^Ooo
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-------
Process: Nitration of Ammonia to Ammonium Nitrate Granules
£. Feed Preparation
None required,
b. Reaction Conditions
The process is known as the Stengel process. SO to 60 percent
nitric acid is vaporized and heated to 140 to 165C. The vapor Is fed to the
reactor where it mixes with ammonia which has been preheated to 145 to 150C
before it is fed to the reactor. The reaction occurs as the mixture flows down-
ward through vertical packed tubes. The temperature in the reactor rises to
200 to 240C as the reaction proceeds. The reactor pressure is 0 to 50 psig.
The product out of the reactor is molten ammonium nitrate mixed with steam.
This mixture passes to a separator where the molten ammonium nitrate drops out
and flows downward through a packed section in the bottom of the separator. Air
at 205C is fed to the separator below the packed section. This air flows upward
through the separator and picks up the steam. The air and steam mixture flows
out at the top of the separator to two condensers in series, where the steam
condenses and any unreacted ammonia and entrained product particulates are
absorbed in the condensate. The molten ammonium nitrate, containing less than
0.5 percent moisture, flows out of the bottom of the separator. The process
yield is 98 percent.
£. Product Purification
No product purification is required. However, additional steps
are required to obtain a granular product.
100
-------
The molten ammonium nitrate from the separator is fed to a
water-cooled belt where it freezes to a solid sheet. The solid sheet passes
through a breaker as it leaves the belt. The solids are then ground and screened
to obtain the desired product size. The product cut from screening is coated to
prevent product caking and deterioration in storage. All equipment following
the cooling belt is blanketed with controlled humidity air. This air is vented
to a water scrubber, where entrained ammonium nitrate particles are removed.
The solution from the scrubber is recycled to the reactor. The product purity
is 99 percent before coating.
cK Recycle Systems
In addition to the liquid recycled from the scrubber to the
reactor, the fines from screening and the liquid from the condensers are re-
cycled to the reactor.
The; oversize material from the screen is recycled to the grinder.
£. Raw. Materials
The' raw materials used are ammonia, 50 to 60 percent nitric acid,
and the diatomaceous: earth used as a product coating.
_f. By-products
There are no by-products.
£. Sources of Air Pollution
There are two sources of air pollution. These are the vent from
the condensers and the vent from the scrubber. Both of these vents emit air
saturated with water vapor, and may contain product particulates.
101
-------
PR 109
Job .
FLOW O/AG RAM
AMMONIUM NITRATE MANUFACTURE
EPA PROCESSES RESEARCH,INC. r,i. No 338Z No
lotJlion
INDUSTRIAL PIANNIN6
AND RESEARCH
0«le .
Subieii NITRATION STUDY
CINCINNATI
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PAGE 3
INDUSTRY
NO.
INDUSTRY
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COMPUTER CODE
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PAGE]
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INDUSTRY
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INDUSTRY
PRODUCT
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COMPUTER CODE
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PAGE 3
INDUSTRY
NO.
INDUSTRY
PRODUCT
AMMON/VM NITRATE
NH+ NOj
COMPUTER CODE
VOS.
SIC. NO.
COLS
1-4
X
DATE
PREPARED
PROCESS
NITRIC ACID
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5-8
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-------
PAGE 3 &
INDUSTRY
NO.
INDUSTRY
PRODUCT
AMMONIUM NITRATE
NHf NOj
COMPUTER CODE
MOS.
SIC. NO.
COLS
1-4
X
DATE
PREPARED
PROCESS
NITRIC AC/D
HND AMMONIA
SOURCE
PRODUCT
COLS
5-8
A
PROCESS
COLS
9-13
QUALITY
COL.
14
X
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COMPUTER CODE NOS.
AQCR
19 22
STATE
23 24
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26 38
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DATE ISS.
REV.NQ
REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
110
-------
SOURCE DATA TABULATION
7. -p Z.
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REV. DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
111
-------
Product:- Potassium Nitrate
There la one plant in the United States reacting potassium chloride
with nitric acid in a two step process:
3KC1 + 4HN03 3KN03 + N0C1 + Cl2 + 2H20
2N0C1 + AHNO3 — *• CI2 + 6NO2 + 2H20
The plant which started production in 1962 produces 126 million pounds
of KNO3 and 59 million pounds of Cl2 per year. No expansion of the process is
expected. See Chart 11 for plot of data.
The KNO3 is used as a fertilizer, and Cl2 is sold as a valuable by-
product.
112
-------
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113
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79U
/?0o
-------
Process: Oxidation of Potassium Chloride for Chlorine and Potassium
Nitrate
a. Feed Preparation
Solid potassium chloride is mixed vith 65 percent nitric acid
and the mixture is fed to the reactor. The nitric acid is chilled to below IOC
before the mixing operation to minimize the reaction until the mixture is in
the reactor. The potassium chloride-nitric acid mixture enters the reactor
through a seal leg to prevent blow back, since the reactor operates above atmos-
pheric pressure.
b. Reaction Conditions
The reaction system consists of three steps. These are the
reactor, which is an agitated tank, the muriate reactor, which is a column and
has a combination of valve and sieve trays, and the gas reactor, which is also
a column and is made of glass-lined steel. The reaction system operates at
20 psig. The temperature is not known.
The initial reaction (3KC1 + AHNO3 3KN03 + N0C1 + CI2 +
2H20) starts in the reactor and goes to completion in the muriate reactor. An
excess of nitric acid is used.
A HNO3 heater and vaporizer produces hot nitric acid liquid,
which is fed to the reactor in order to promote the reaction, and nitric acid
vapor, which is fed to the bottom of the muriate column to strip the chlorine
and chlorides from the HNO3-KNO3 solution down to 0.004 percent or less. The
bottoms from the muriate reactor column, a mixture of HNO3 and KN03, contains
the desired potassium nitrate, and goes to the water stripper. The overheads
are returned to the reactor.
114
-------
The gas stream from the reactor goes to the gas reactor column
where the second main reaction (N0C1 + 2HNO3 ^ 3N02 + 1/2 CI2 + H2O) occurs.
A HNO3 concentration above 70 percent is required. The reflux condenser on this
column keeps nitric acid and water out of the overhead product. The bottoms
stream from the gas reactor column is returned to the reactor. The overheads
stream is totally condensed and is fed to the CI2 still.
No information 1b available on process yields.
£. Product Purification
The HNO3/KNO3 solution from the bottom of the muriate column is
fed to the water stripper. The water stripper works In conjunction with the
1
KNO3 saturator to increase the concentration of KNO3 in the water stripper.
This shifts the azeotrope concentration to produce a stronger HNO3. The over-
heads from the water stripper go to the water rectifier where water is removed
overhead as a waste. The bottoms product is 65 percent HNO3, which is recycled
to the reactor. The bottoms from the water stripper go to the vacuum crystal-
llzers where the KNO3 crystallizes out. The overhead vapor is condensed and fed
to a separator.
The slurry from the cryBtallizers is centrifuged. The mother
liquor is returned to the cryBtallizers. The crystals are dried in a direct-
fired dryer to produce technical grade potassium nitrate. The product purity
is about 95 percent.
A prilled product of 99.3 percent purity can be produced by
removing the slurry from the first stage of the evaporator (as shown by dotted
115
-------
lines on the flow diagram). This slurry Is centrlfuged. The crystals are dried
and then melted. The melt Is fed to a prill tower. The prills are cooled to
yield the 99.3 percent purity prilled product.
A second product (or a by-product) results from this process.
This is liquid CI2 with a purity of 99.5 percent. This is obtained by distilla-
tion at 40 pslg in the CI2 still of the overhead product from the gas reactor
column. The bottoms from the Cl£ still is fed to the N2O4 still.
d_. Recycle Systems
There are several recycle systems in addition to the recycles
between the reaction columns and the reactor (discussed under reaction conditions),
the recycle from the water rectifier (discussed under product purification), and
the recycle of the mother liquor from the centrifuge (also discussed under product
purification).
The condensed vapor from the vacuum crystallizers goes to a
separator. This is a nitric acid solution. The liquid phase goes back to the
gas reactor column, while the vapors return to the water rectifier.
The bottoms from the CI2 still contain NO2CI, NOC1, BrCl and
N2O4. This is fed to the N2O4 still. A bleed stream from the overheads of this
still is fed to the BrCl still where the BrCl is concentrated in the overheads
and goes to a scrubber where it is neutralized with caustic. The water solution
from the scrubber is a waste product. The scrubber is vented to atmosphere.
The bottoms from the BrCl still are returned to the N2O4 column.
116
-------
The main overhead product from the ^0^ column contains N0C1
and NO2CI plus ^0^, CI2, and BrCl. This is returned to the gas reactor column
for oxidation with nitric acid in accordance with the second main reaction.
The.bottoms from the N2O4 still is primarily N2O4. This goes
to an agitated reactor tank where it is mixed with 55 percent HNO3 and air to
cause the regeneration reaction (2NC>2 + H2O + 1/2 (>2 » 2HNO3) to tpke place.
The liquids and unreacted N2O4 (NO2) goeB to a two-stage HNO3 absorption column
system, where the regeneration reaction is continued by the addition of more air.
This absorption system produces a 65 percent nitric acid solution which is re-
cycled to the reaction steps. The off gases from the HNO3 absorber system,
containing air and unabsorbed oxides of nitrogen, are vented,
e. Raw Materials
There are two raw materials, 55 percent nitric acid and solid
potassium chloride.
f_. By-products
There is one by-product. This is liquid chlorine with a purity
of 99.5 percent.
&. Sources of Air Pollution
There are five sources of air pollution. The vent from the
scrubber in which BrCl is absorbed and neutralized may contain BrCl and oxides
of nitrogen. The vent from the HNO3 absorber system will be primarily air with
traces of unabsorbed oxides of nitrogen. The product dryer is direct fired and,
therefore, it will vent combustion gases and some product particulates. The prill
tower will vent air and some product particulates, as will the cooler following
the prill tower.
117
-------
/^CC& 55 -
NITRATI ON OF POTASSIUM CHL OF? IDF V\ZiTH MiTFtlC ACID
no*, BrCl
PROD. PART
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BIBLIOGRAPHY
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RELATEO INDUSTRIES
BIBLIOGRAPHY
124
-------
Product: Sodium Nitrite
Sodium nitrite is made by reacting nitric oxide with sodium carbonate
under oxidizing conditions:
2N0 + Na2C03 + 1/2 O2 » 2NaN02 + C02
(Air)
There is little production data. Chart 12 shows a plot of the only
point. Little growth is expected.
The main use of sodium nitrite is as a corrosion Inhibitor for iron
and steel. About 15 percent is used to produce azo dyes.
125
-------
100.0
/J" 72
-------
Process: Oxidation of Sodium Carbonate to Sodium Nitrite
a. Feed Preparation
A solution of about 21 percent sodium carbonate is prepared by
dissolving solid sodium carbonate In water.
Nitric oxide gas (NO) is obtained by catalytic oxidation of
ammonia (NH3) with air. This reaction is the same as for nitric acid manufac-
ture; however, the secondary air is carefully controlled to give a ratio of
NO/NO2 in the product gas so that a minimum of NaN03 is produced in the reaction
step.
b. Reaction Conditions
The process is either batch or continuous. For a continuous
process, several absorption towers are operated in series. The description of
a three-stage reactor follows.
The 21 percent sodium carbonate solution is fed to the third
absorber in the series, and after passing through that absorber, it is trans-
ferred to, and passes through, the second absorber. Additional sodium carbonate
may be added to the solution in the second stage to make up for that which has
reacted. The solution is then sent to, and through, the first absorber and
comes out with most of the sodium carbonate reacted. The NO gas plus air (or
the NO-NO2 gas mixture from the catalytic oxidation of ammonia) is fed to the
bottom of the first absorber. It passes up through the first absorber and out
the top, and then to the bottom of the second absorber. The gases pass through
the second absorber and on to, and through, the third absorber in the same manner
as for the first absorber. The gases from the third absorber are vented.
127
-------
As the gases pass through the absorber, the NO and oxygen (or
NO2) react with the sodium carbonate to form sodium nitrite (NaN02) and carbon
dioxide (C02).
The liquid from the bottom of the first absorber may contain
25 percent sodium nitrite, 5 percent sodium nitrate, and 0.5 percent sodium car-
bonate. It is transferred to a storage tank.
c. Product Purification
The liquor in the storage tank is transferred to the feed tank
where it is blended with mother liquor from the first stage crystallization and
redissolved crystals from the second evaporator.
A portion of the solution in the feed tank is fed to the first
evaporator, while another portion is used to dissolve the crystals from the
second stage evaporation (to be discussed later). In the evaporator, the
solution is concentrated to about 50 percent sodium nitrite.
The solution from the evaporator passes to a vacuum crystal-
lizer. The slurry from the vacuum crystallizer is filtered. The mother liquor
from this filtration is split into three streams. About 10 percent is returned
to the evaporator feed tank, about 45 percent goes back to the first stage
absorber and about 45 percent goes to a second evaporator.
The filter cake from the above filtration is dried and becomes
the sodium nitrite product.
In the second evaporator, the solution is concentrated to about
50 percent of the original volume. This concentration crystallizes out sodium
nitrite. This slurry is filtered.
128
-------
The filter cake from the second evaporator Is high in sodium
nitrite. It is redissolved in solution from the first evaporator feed tank.
The resulting solution is sent back to the first evaporator feed tank.
d. Raw Materials
The raw materials for the process consist of sodium carbonate
and either NO gas or an NO-NO2 mixed gas from the controlled catalytic oxidation
of ammonia.
e. By-products
The mother liquor from the second filtration is dried and ground
to become a by-product containing about 55 percent sodium nitrite and 40 percent
sodium nitrate.
Sources of Air: .Pollution
There are two sources of air pollution. The vent on the third
absorber will contain air, carbon dioxide and unabsorbed oxides of nitrogen.
The vent from the drum dryer will contain air, water vapor, and product
particulates.
129
-------
PR 109
Job .
FLOW DIAGRAM
SODJUM N!TRlTE MANUFACTURE
E P A PROCESSES RESEARCH, INC. f.i. n„ 3382. u.„
Lotttitn
S„b,e«i NITRATION STUDY
INDUSTRIAL PLANNING
AND RESEARCH
. Dile.
CINCINNATI
Checked by ______
NEW YORK Co«p»l»d by G" N.7~, D*i> ll~2rll
E/Zccsss-. MO PL US AIR^. REACT/ON WITH SODIUM CARBONATE
PROD. PART.; fjoX) CO^ , A IR
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SODIUM CARBONATE
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NO + AIR
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(SOLUTION)
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SODIUM NITRITE' PKQVUCT
130
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REV.DATE
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
132
-------
:^Sii6E DM
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DATE ISS.
REV. NO.
REV. DATE
•
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
133
-------
4. Explosives - SIC Industry No. 2892
Establishments primarily engaged in manufacturing explosives.
Some important nitro compounds of industry No. 2892 include:
Nitrocellulose
Nitroglycerin
Nitromannitol
Nitro starch
Nitro sugars
TNT
For this study, these three products have been Included:
Nitroglycerine
Nitrocellulose
TNT
134
-------
Product: Nitroglycerine
Nitroglycerine Is an explosive which has been In commercial use for
over 100 years. Hovever, there Is very little production data on it. See
Chart 13 for industrial production. The main use of nitroglycerine is as an
explosive.
Nitroglycerine Is made by nitrating glycerine,
C3H3(OH)3 + 3H0N02 —^ C3H5(0H02)3 + 3H20
Starting in the early Nlneteen-flftles, nitroglycerine has been made in
the United States by a continuous process, which has no emissions.
135
-------
c /3
Ev
-------
Process: Nitration of Glycerine
a. Feed Preparation
A mixed acid is used for the nitration reaction. The composi-
tion is given as 49.5 percent H2SO4 and 52 percent HNO3. This acid is prepared
by mixing 60 percent oleum with 93 percent H2SO4 to produce a 40 percent oleum.
This mixture is then mixed with 97 percent HNO3 to give the desired mixed acid.
The 97 percent HNO3 is obtained by concentrating 50 to 60 percent HNO3 In the
acid concentration^ system.
b. Reaction Conditions
One of the continuous processes for making nitroglycerine is
the Biazzi process. The nitrator has a capacity of about 32 gallons. It is
uninsulated, has Internal coils for cooling, and is equipped with an agitator.
For emergency drowning there Is a 6 Inch opening in the bottom and a quick open-
ing valve.
In operation, glycerine (and sometimes ethylene glycol) and
mixed acid are fed separately to the nitrator. The mixed acid is fed to the
surface of the liquid. The glycerine Is fed below the surface. The reaction
is controlled at about 15C when glycerine alone Is fed. It Is controlled at
12C when the feed :1s 50 percent ethylene glycol and 50 percent glycerine. The
reaction product overflows continuously to the acid separator. The reactor is
vented to an absorber. The process overall yield is 96 percent.
137
-------
£. Product Purification
The reactor product la separated continuously In the add
separator, which is a specially designed centrifuge. The spent acid leaves the
separator and goes to a dilution tank, where water is added at a rate of 2 per-
cent of the acid flow to dissolve suspended nitroglycerine. Further processing
of the spent acid is discussed under recycle systems.
The nitroglycerine liquid from the add separation step goes to
the washers, where It is washed with 13 percent sodium carbonate In water. The
mixture of sodium carbonate, water and nitroglycerine overflows continuously
from the first washer and through two additional washers In series to insure
complete neutralization of any add In the nitroglycerine. The washers are
vented to the absorber.
The emulsion of nitroglycerine and soda water overflows the
third washer and then flows by gravity through a pipe to a building where the
soda water separator is located. Water is mixed with the emulsion as it enters
the pipe through a break funnel. The water prevents deposition of salts in the
soda separator. The break funnel serves to prevent transmission of an explo-
sion in the soda water separator system to the reactor building. In the soda
water separator, the neutralised salts and water are separated from the nitro-
glycerine and wasted. The nitroglycerine is jetted with water to the jet water
separator. This system serves to water wash the nitroglycerine. The nitro-
glycerine then goes to storage for processing into dynamite.
138
-------
<1. Recycle Systems
There are two systems that can be called recycle systems. Both
involve the waste add.
The first system is not shown on the flow sheet, because it is
used only on shutdown of the reactor. On shutdown, waste acid is caused to flow
from a head tank into the bottom of the reactor (after the feeds have been shut
off and agitation stopped). This waste add displaces the nitroglycerine in the
reactor, causing it to overflow to the acid separator. The overflow on the
separator is adjusted so that the spent acid rises and pushes the last nitro-
glycerine out of the separator. (By means of bottom connections between the
washers, they are emptied to the soda water separator.)
The other system treats the spent acid and the nitric acid from
the absorber on the reactor and washer vents. This mixed acid is fed to the
top of a denitrating tower which is heated with steam. As the spent acid flows
down through the tower, it is stripped of HNO3 and oxides of nitrogen by the
vapors rising in the tower.
The gases from the top of the denitrating tower flow to the
bleacher where they mix with air to oxidize any nitric oxide present. The gases
flow upward and through a reflux condenser where any HNO3 and H2O condense and
flow back to the bleacher and out as 97 percent nitric acid. This 97 percent
acid goes to the mixed acid system, which is discussed under feed preparation.
The off gases from the reflux condenser are fed to an absorption tower where
additional oxidation of NO takes place, and the oxides of nitrogen are absorbed
139
-------
In water and 50 to 60 percent nitric add to form additional nitric acid. The
bottoms from this absorber is fed to the top of the denltrating tower. All the
makeup 50 to 60 percent nitric acid used in the process Is fed either to the
absorber or to the denltrating tower to be concdntrated to 97 percent HNO3.
The bottoms from the denltrating tower, which is 60 to 70 per-
cent sulfuric acid, is fed to the sulfuric acid concentrator. In the sulfuric
acid concentrator, water is removed from the H2SO4 and becomes a waste product.
A 93 percent sulfuric acid solution is produced by the concentrator. Only a
portion of this acid can be used In the mixed acid system. The excess 93 percent
H2SO4 is sold as a by-product or becomes a waste stream,
e. Raw Materials
The major raw materials are 60 percent oleum, 50 to 60 percent
nitric acid, glycerine, and, at some plants, ethylene glycol. A raw material
used In lesser amounts Is sodium carbonate.
£. By-products
The process produces one by-product. This is 93 percent
sulfuric acid contaminated with nitrobodles.
Air Pollution Sources
Thiere are two sources of air pollution. These are the vent
from the absorber oh the reactor vent and the vent on the absorber in the add
concentration system. Both vents will vent air and unabsorbed oxides of nitrogen,
and HNO^ fumes.
140
-------
Some plants will have a third air pollution source, if a drum
concentrator Is used for sulfuric acid concentration. The vent from this will
contain combustion gases, H2SO4 mist, and nltrobodles.
141
-------
f%cc£SS: CONTINUOUS NITRAT/ON OE GLYCERINE CBiAZZt PROCESS)
R
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BIBLIOGRAPHY
144
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I
FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
145
-------
Product: Nitrocellulose
Nitrocellulose Is a low explosive which has been In use for over a
century. It Is produced by nitrating cotton or wood dust,
C6H7<>2 (OH)3 + 3H0N02 CgHyC^ (ON02>3 + 3H20
Nitrocellulose Is also used In lacquers, at an average rate of about 1-1/2
million pounds per year. As Chart 14 shows, there Is no production data on nitro-
cellulose.
146
-------
-------
Process: Nitration of Cellulose
a. Feed Preparation
The cellulose Is prepared from cotton linters or from specially
prepared wood pulp. The starting material is purified for use in nitrating. The
cotton linters (or wood pulp) is first boiled with dilute caustic, and then is
washed several times with water. This is followed by bleaching several times
with bleaching powder or sodium hypochlorite in water. The linters, after drying
and loosening, are ready for feed to the reactor.
Mixed acid, with a composition which is approximately 21 percent
HNO3, 63 percent H2SO4, 0.5 percent N2O4 and 15.5 percent H2O, is prepared by
mixing 93 percent H2SO4, 50 to 60 percent HNO3, and 97 percent HNO^.
The nitrocellulose prepared using the above mixed acid contains
12.6 percent nitrogen and is called pyrocotton. Other grades of nitrocellulose
are pyroxylin (with 8 to 12 percent nitrogen) which is prepared by using mixed
acid that is weaker in nitric acid than above, and guncotton (with 13 to 14
percent nitrogen) which is made with a stronger acid.
b. Reactor Conditions
The reaction is usually carried out in a du Pont "mechanical
dipper" nitrator, which processes 32 pounds of cellulose per batch. This charge
of cellulose is mixed with 1500 pounds of mixed acid at 30C for 25 minutes.
The entire batch is dropped into a centrifuge where the spent acid is separated
from the nitrated cellulose. The spent acid goes to the acid concentration
system. The nitrocellulose Is dropped from the centrifuge to a flume where it
148
-------
is flushed with water to the boiling tub. One reason for the small batch size
Is that the nitrocellulose picks up moisture from the air in the centrifuge.
This causes denltrificatlon of the nitrocellulose, with a buildup of heat, and
If it is not drowned quickly enough explosive conditions can occur.
The reactor and the centrifuge are vented to an absorber where
any NO is oxidized and absorbed in water to produce a nitric add solution.
This solution goes to add concentration.
£. Product Purification
The nitrocellulose in the boiling tub is washed several times
with hot water. It is then transferred to a beater, where it is treated with
dilute sodium carbonate. It is then washed several times with boiling water and
with cold water. The nitrocellulose is then centrifuged to remove excess water.
The product nitrocellulose, which contains 23 percent water, is stored wet until
it is processed either to explosives or to celluloid or lacquers.
-------
The dilute sulfuric acid is Chen fed Co a sulfuric acid concen-
Crator where Che waCer is removed as a waste material. The concenCrator produces
93 percent sulfuric acid which Is recycled to the nixed acid system.
In the bleacher any NO in overheads from the denitrating tower
is oxidized with air. The gases then pass through a reflux condenser where
HNO3 condenses out and drops back to the bleacher. A 97 percent nitric acid
solution is withdrawn from the bleacher and goes to the mixed acid system.
The vent gases from the reflux condenser go to an absorber,
where further oxidation of NO takes place and the oxides of nitrogen are absorbed
in nitric acid and water. Dilute nitric acid is removed from the bottom of the
absorber and is recycled to the denitrating tower. Air is vented from the top
of the absorber.
£. Raw Materials
The major raw materials are cotton llnters or specially prepared
wood pulp and 50 to 60 percent nitric acid. Other raw materials are 93 percent
sulfuric acid to make up for process losses, calcium or sodium hypochlorite which
is used in the cellulose bleaching and sodium hydroxide and sodium carbonate.
£. By-products
There are usually no by-products. Some plants sell the spent
acid, instead of concentrating it.
Sources of Air Pollution
There are two major sources of possible air pollution. These are
the vents from the absorber in the reactor section and the absorber In the acid
concentration section. These vents contain air and any unabsorbed oxides of
nitrogen. Another pollution source could be the boiling tub, where steam and
acid vapors are vented.
150
-------
* 109
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FLOW DIAGRAM
N!TROCELL UL 05E MANUFA CTURF ,
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BIBLIOGRAPHY
153
-------
SOURCE DATA TABULATION
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FOR PRODUCTION CAPACITIES SEE PRODUCTION LISTING
RELATED INDUSTRIES
BIBLIOGRAPHY
154
-------
Product: Trinitrotoluene
Trinitrotoluene, TNT, is a high explosive which was first used in World
War I. Its only use, is as an explosive. Chart 15 shows the single industrial
production figure. The reaction is,
C6H5CH3;+ 3H0N03 o C^CHjCNC^) 3 + 3H20
As indicated in the first section, Industrial explosives have an estimated annual
growth rate of about 6 percent.
155
-------
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156
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Process: Nitration of Toluene to Trinitrotoluene
a. Feed Preparation
A mixed acid, which has a composition of 83 percent total sul-
furic acid and 23 percent nitric acid is prepared by mixing oleum with a "semi-
mix" acid containing 62 percent total sulfuric acid and 43 percent nitric acid.
The mixed acid above is called a "tri-mix" acid.
b. Reaction Conditions
The reaction of toluene with nitric acid to produce trinitro-
toluene is usually In three steps, each carried out In a separate building as a
safety measure. In: the first step, mononitrotoluene is produced. The crude
nitrotoluene from the first step is nitrated to dinitrotoluene in the second
step; in the third step, the dinitrotoluene crude from the second step is
nitrated to trinitrotoluene.
Each step of the reaction process consists of one or more
nitration reactors piped in series and followed by a separator, such as a
decanter or a centrifuge, to separate the crude nitrotoluenes produced from the
spent acid. The mixed acid and the toluene or nitrotoluenes flow cocurrently
through each step until separated, and counter-current between steps. The
reaction conditions are different in each step. Each reactor system is vented
to a fume scrubber.
The "tri-mix" acid (discussed under feed preparation) is fed
to the third reaction step in the process. The third step reactors operate
at 80 to HOC and atmospheric pressure. The ratio of "tri-mix" acid to crude
157
-------
dinitrotoluene which Is fed to the third step reaction is such that little or
no excess nitric acid;remains in the spent acid.
The Spent acid from the third step nitration is fortified with
50 to 60 percent nitric acid. This fortified acid, called "bi-mix" acid, is
used in the second reaction step. The "bi-mix" acid has a composition of 54 per-
cent sulfuric acid, 13 percent nitric acid, 17 percent nitrosylsulfuric acid,
8 percent water and 8 percent nitro compounds. The reaction is controlled at
75 to 85C and is at atmospheric pressure.
The spent acid from the second step reaction is fortified with
50 to 60 percent nitric acid to give a "mono-nix" acid with a composition of
48 percent sulfuric acid, 14 percent nitric acid, 17 percent nitrosylsulfuric
acid, 19 percent water and 2 percent nitro compounds. This acid is used in the
first stage reaction. The reaction conditions are 40 to 55C and atmospheric
pressure.
The ppent acid from the first step reaction goes to the deni-
trating tower in the acid concentration section. (See recycle systems.)
£. Product Purification
The crude trinitrotoluene from the third stage reaction system
is purified in a series of washing and neutralization steps. The wash water
flows counter-current; to the nitrotoluene between steps. In the Meissner
process the washers are columns in which the nitrotoluene and wash water are
fed to the bottom and flow out of the top to a separator. The nitrotoluene
layer from the separator goes to the next column while the water layer goes to
158
-------
the column of the previous step. The wash water from the first step is a waste
product. The trinitrotoluene from the last separator is product.
Each wash column is agitated by air which is sparged into the
bottom of the column and vented at the top of the column.
The usual wash sequence consists of four treatments. The crude
trinitrotoluene is first washed with one or more water washes. This is followed
by a dilute caustic wash using sodium bicarbonate to neutralize any inorganic
acids. The crude is then treated with sodium sulfite. This reacts with any
unsymmetrical trinitrotoluenes and makes them soluble in water. The crude is
finally given one or more water washes.
The trinitrotoluene from the last washing step is the product
for use in making dynamites.
cl. Recycle Systems
There is one recycle system. The spent acid from the first
reaction is fed to the top of the denitratlng tower. This tower is heated by
steam in the bottom. The rising vapors strip the HNO3 and oxides of nitrogen
from the liquid. These nitrogen compounds pass out the top to the bleacher.
The water is retained by the H2SO4 and flows out the bottom of the tower and
then to the H2SO4 concentrator.
The nitrogen compounds from the denitratlng tower are mixed
with air in the bleacher. This converts NO to NO2. The gases rise through
the bleacher and pass through a reflux condenser. This condenses nitric acid
with a concentration of 97 percent HNO3. The acid flows back through the
159
-------
bleacher absorbing NO2 and forming more nitric acid. The concentrated nitric
acid is withdrawn from the bleacher for use in the semi-mix acid (discussed
under feed preparation). The gases that leave the reflux condenser go to an
absorption system, consisting of one or more columns. The gases enter the
bottom and flow upward, counter-current to a flow of dilute nitric acid. Further
oxidation of NO occurs in the absorbers, and additional nitric acid is formed.
This acid is fed to the denitrating tower to be concentrated. The absorption
system is vented.
The water and sulfuric acid from the bottom of the denitrating
tower is concentrated to 93 percent H2SO4 in the H2SO4 concentrator. The water
removed is a waste product while the 93 percent sulfuric acid produced goes
partly to the semi-mix acid and that portion which cannot be used for semi-mix
acid is a by-product.
£. Raw Materials
The major raw materials used in the process are toluene, SO to
60 percent nitric acid and oleum. Minor raw materials are caustic, sodium
bicarbonate and sodium sulfite.
f_. By-products
One by-product Is produced, the 93 percent sulfuric acid. It
contains nitrobodies which limit its marketability.
Sources of Air Pollution
There are about eight vents on the process. Three of the vents
are on the three scrubbers associated with the three reaction steps. These
160
-------
will vent any oxides of nitrogen from the reactors that were not absorbed in the
scrubbers. Four (or more) vents are on the product washing columns. These will
vent air saturated with water and nitrotoluenes. The last vent is the vent from
the absorber in the acid concentration section. This vent is mainly air. It
will also contain some oxides of nitrogen and HNO3 fumes.
161
-------
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MISCELLANEOUS
RELATED SIC. NOS:
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SOURCE DATA TABULATION
INDUSTRY
NO.
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MLATIO M0USTMS
9IBUOQRAPMY
165
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SlliltCE DATA TABULATION
INDUSTRY
NO.
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D. AIR POLLUTION CONTROL DEVICES OF NITRIC ACID PLANTS
1. Process Description
Over 95 percent of the nitric acid is produced by the high pressure
air oxidation of ammonia,
NH, + 20, 135 P8ia HNO, + H20
3 (Air) 90<}C Q 3
There are two other processes, low pressure air oxidation and the Hoko, neither
of which are used in the United States.
The absorber tower is the last piece of equipment in the nitric
acid process train. The vent from the absorber tower usually contains 3000 ppm
of N0X, half as NO and half as N0£. The main component of the vent is nitrogen,
along with 1 to 5 percent oxygen.
2. Control Devices
In the United States the most widely used control device on the
gaseous effluent from the nitric acid absorber is a one-or two-stage non-
selective catalytic reducer. In the first stage, the NO2 and oxygen are reduced
by fuel gas (methane) to carbon dioxide, water, and nitric oxide. After the
effluent is cooled, the nitric oxide is reduced in the second stage with addi-
tional fuel gas to nitrogen, water, and carbon dioxide. If the effluent from
the absorber has a low oxygen content, say less than 2 percent, then a single
stage catalytic reducer is used as a control device. The nitric oxide content
of the effluent from the catalytic reducers can be controlled down to less
than 50 ppm, but efficiency factors average 80 percent. The unit is considered
flexible and adequate. Caustic scrubbers are used to a very minor extent as
167
-------
control devices on nitric acid plant absorbers. Caustic scrubbers produce sodium
nitrate, a solids disposal problem. Catalytic reducers produce the natural com-
ponents of air. The efficiency factors of caustic scrubbers average 90 percent.
3. Utilization
a. Catalytic Reducers
It is thought that catalytic reducers of nitric acid plants
could be used effectively on these five nitro processes.
Nitration of benzene
Oxalic acid by the oxidation of monosaccarides
Nitration of toluene to trinitrotoluene
Nitroparaffins from propane
Dinitrotoluene
The vents from these flue processes are dilute streams of N0X.
The streams also contain hydrocarbons which would compliment the added fuel
(methane).
b. Scrubbers
Where particulate is the main emission, water or alkali
scrubbers would be effective with these four processes:
Ammonium nitrate prills
Ammonium nitrate granules
Sodium nitrite
Potassium nitrate
Caustic scrubbers would also be effective with these two
nitro processes:
Nit: ion of glycerine
Nitration of cellulose
The remaining four nitro processes will require the development
of different types of control devices.
168
-------
SECTION III - CONCLUSIONS
A. POLLUTION BY PROCESSES
In Table 3 the four classes of processes have been listed according to
their percentage of total pollutant emission based on total product capacity and
emission factors. The liquid phase nitric acid oxidations, Class 3, is the
largest polluting class of processes, emitting about half the air pollutants while
consuming only about one eighth of the total nitric acid production.
TABLE 3 - POLLUTION BY PROCESSES
Process Description
Liquid phase nitric acid
oxidations
Nitric oxide oxidations
Vapor phase nitrations
Liquid phase nitrations
Process
Classification
Number
3
4
2
1
Percent of Total
Pollution
Emissions
52
1
13
34
Percent of
Nitric Acid
Consumption
12
2
8
72
For the Nineteen-seventies, it is expected that only minor changes will
occur in the above figures. It is expected that ammonium nitrate production will
continue to dominate nitric acid utilization, which is a major factor affecting the
above.
In general, nitro processes are not significant polluters, accounting
for only 0.06 percent of the total emissions of oxides of nitrogen to the atmos-
phere. Their significance is important as local source pollution.
169
-------
B. CONTROL DEVICES
1. Catalytic Reducer
As discussed In Section II D the major control device Incorporated In
nitric acid plants Is a nonselective catalytic reducer. This control device
probably can be utilized on the following nltro processes:
Process
Class
1
1
1
2
3
Product
Nitrobenzene
Dlnltrotoluene
Trinitrotoluene
Nitroparaffins
Oxalic acid
Major
Pollutant
Organic
N0X
Organic
N0X
N0X
Total Uncontrolled
Emission Rate
Pounds/Ton of Product
17.1
0.27
44
1.5
6.3
2. Caustic Scrubber
To a minor extent, caustic scrubbers are control devices for nitric
acid plants. Caustic scrubbers would be effective control devices on these two
nltro processes:
Process
Class
1
1
Product
Nitroglycerine
Nitrocellulose
Major
Pollutant
N0X
S02
Total Uncontrolled
Emission Rate
Pounds/Ton of Product
1.9
96
3. Other Types of Control Devices
For the remaining nitro processes, the following control devices
probably would be effective:
170
-------
Total Uncontrolled
Process Major Emission Rate
ClaBS Product Pollutant Pounds/Ton of Product
a. Water Scrubbers
1 Ammonium nitrate prills Particulate 0.86
2 Ammonium nitrate granules Particulate 5.5
3 Potassium nitrate and
chlorine Particulate 13
4 Sodium nitrite Particulate 1.8
b^. Two-Stage Caustic Oxidizing Scrubber
3 Adipic acid (N2O) 14
3 Terephthalic acid (N2O) 15
c_. Vent Condenser
1 Nitrochlorobenzene Chlorobenzene 4.1
d. Flare
4 Acrylonitrile Organic 5.4
The bottoms from the water scrubbers can be recycled, eliminating
the problem of disposing of the solute.
For the emissions from the adipic acid and terephthalic acid pro-
cesses, the standard catalytic reducers cannot be utilized because of the high
N2O content which will react with the fuel, causing high fuel consumption and
high temperatures. The two-stage caustic scrubber must be oxidizing (air
present) in nature in order to maintain the optimum NO/NO2 ratio for efficient
absorption.
Due to the chlorine content in the effluent from the nitrochloro-
benzene process, the catalytic reducers and caustic scrubbers will not be effective
as control devices. It is expected that a vent condenser would be most effective
control device.
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For control devices on the air effluents from acrylonitrile plants
using the NO/propylene process, a flare would be satisfactory since the main
component of the effluent is hydrocarbons.
C. INSTRUMENTATION
Adequate instrumentation for process control of nitro processes and for
the utilization of pollution control devices is currently applied for process
plants.
D. UPSETS
Although process upsets, when the reaction gets out of control, are
outside the scope of this study, certain items should be noted.
The liquid phase nitration processes, Class 1, are the most serious
source of air pollution from process upsets. Up to the present time, minor
development of control devices for such processes has been done.
E. INCENTIVES FOR CONTROL OF EMISSIONS
At a cost of 4 cents per pound, the recovery of nitric acid and the
oxides of nitrogen (N0X) can be economically done. This is a significant
incentive to minimize atmospheric emissions.
The oxides of nitrogen have undesirable physiological effects, hut are
not really hazardous. Therefore, this is a weak Incentive.
Concentrations of N0X from chemical process sources are readily visible
as a brown-red gas. Therefore, this is a strong incentive to reduce the plume
and its connotation of pollution.
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F. ADSORPTION
Due to the presence of water vapor in the air effluent from most nitro
processes, development work on adsorbents would not be productive. Furthermore,
the N0X level desired in the exit gases from adsorbent bed control devices
appears to be beyond the effective limit achievable by most adsorbents.
G. SIZE FACTOR
Other than ammonium nitrate and adipic acid, and possibly terephthalic
acid, acrylonitrile, nitrobenzene, and dinitrotoluene, the production of nitro
products is small compared, say, to the chloro products. Even with growth of the
industry and the development of continuous process trains, control will continue
to be most important on a local source basis with local economical conditions
governing.
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SECTION IV - RECOMMENDATIONS
A. ADAPTATION OF EXISTING CONTROL DEVICES
Ic is recommended these existing control devices can be adapted for use
on these nitro processes where local source conditions require control device
utilization.
Product
Control Device
1. Nonselective catalytic
reducers
2. Caustic scrubbers
3. Water Scrubbers
4. Flare
5. Vent condenser
Nitrobenzene
Dlnitrotoluene
Trinitrotoluene
Nltroparaffins
Oxalic acid
Nitroglycerine
Nitrocellulose
Ammonium nitrate
prills
Ammonium nitrate
granules
Potassium nitrate
Sodium nitrite
Acrylonltrile
Nitrochlorobenzene
Process
Nitration of benzene
Nitration of toluene
Nitration of toluene
Nitration of paraffins
Oxidation of monosac-
charides
Nitration of glycerine
Nitration of cellulose
Nitration of ammonia
Nitration of ammonia
Oxidation of potassium
chloride
Oxidation of sodium
carbonate :
NO - propylene
Nitration of chlorobenzene
B. DEVELOPMENT OF NEW CONTROL DEVICES
For some of the Class 3 type of processes, nitric acid oxidation, it is
recommended that an improved design for oxidizing caustic scrubber be developed
as a control device. To be more effective, the scrubber should be selective for
NO/NO2 mixtures. When further developed, the control device could be used on
the nltro processes of adlplc acid and terephthalic acid.
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C. PROCESS UPSETS
It is recommended Chat development work be done on confining the vapors
from a drown tank, when a nitration reactor is dumped. Vapors should be
collected and fed to a caustic scrubber before being allowed to vent to the
atmosphere.
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1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
SECTION V - BIBLIOGRAPHY
Kirk and Othmer Encyclopedia of Chemical Technology, 2nd Ed., 1963-1970,
Wiley.
Standard Industrial Classification Manual, 1967, Office of Statistical
Standards.
Faith, Keyes, Clark, Industrial Chemicals, 3rd Ed., 1965, Wiley.
Sittig, Organic Chemical Process Encyclopedia, 1967, Noyes.
Synthetic Organic Chemicals, TC Publication, US Production and Sales.
Hahn, The Petrochemical Industry, 1970, McGraw-Hill.
Public Health Service Publication No. 999-AP-27, 1966.
National Air Pollution Control Administration Publication No. AP-67, 1970.
Oil, Paint and Drug Reporter, 1969, 1970, 1971, Schnell Publishing Co.
Shreve, Chemical Process Industries, 3 Ed., 1967, McGraw-Hill.
Groggins, Unit Processes in Organic Synthesis, 5 Ed., 1958, McGraw-Hill.
Kent, Riegels Industrial Chemistry, 1962, Reinhold.
Urbanski, Chemistry and Technology of Explosives, 1964, McMillan.
McGraw, Air Pollutant Emission Factors, 1970 US Dept. of H., E., and W.
Census of Manufacturers, Group 28, Chemical and Allied Products, 1968,
US Dept. of Commerce.
Processes Research, Inc., Catalog of Atmospheric Pollutant Sources and Pilot
Computer Program, 1971.
1960
1961
1962
1963
1964
1965
1966
1967
1968
1969
TC Publication 34
TC Publication 72
TC Publication 114
TC Publication 143
TC Publication 167
TC Publication 206
TC Publication 248
TC Publication 295
TC Publication 327
TC Publication 412
TC 1.33:960
TC 1.33:961
TC 1.33:962
TC 1.33:963
TC 1.33:964
TC 1.33:965
TC 1.33:966
TC 1.33:967
TC 1.33:968
TC 1.33:969
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