United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/2-79-019b
January 1979
Research and Development
-&EPA
Source Assessment:
Nitrogen Fertilizer
Industry Water Effluents
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped mto nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-019b
January 1979
Source Assessment:
Nitrogen Fertilizer Industry
Water Effluents
by
W.J,Search, J.R. Klieve, G.D. Rawlings,
J.M. Nyers, and R.B. Reznik
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45407
Contract No. 68-02-1874
Program Element No. 1AB015
EPA Project Officer: Ronald A. Venezia
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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PREFACE
The Industrial Environmental Research Laboratory (IERL) of the
U.S. Environmental Protection Agency (EPA) has the responsibility
for insuring that pollution control technology is available for
stationary sources to meet the requirements of the Clean Air Act,
The Federal Water Pollution Control Act, and solid waste legisla-
tion. If control technology is unavailable, inadequate, or
uneconomical, then financial support is provided for development
of needed control techniques for industrial and extractive
process industries. Approaches considered include: process
modifications, feedstock modifications, add-on control devices,
and complete process substitution. The scale of the control
technology programs ranges from bench- to full-scale demonstra-
tion plants.
The Chemical Processes Branch of the Industrial Processes
Division of IERL has the responsibility for programs to develop
control technology for a large number of operations (greater
than 500) in the chemical industries. As in any technical pro-
gram, the first question to answer is, "Where are the unsolved
problems?" This is a determination which should not be made on
superficial information; consequently, each of the industries
is being evaluated in detail to determine if there is, in EPA's
judgment, sufficient need for emissions reduction. This report
contains data necessary to make that decision for the water dis-
charges resulting from the production of nitrogen fertilizer.
Monsanto Research Corporation has contracted with EPA to inves-
tigate the environmental impact of various industries which
represent sources of pollution in accordance with EPA's respon-
sibility as outlined above. Dr. Robert C. Binning serves as
Program Manager in this overall program entitled "Source Assess-
ment," which includes investigation of sources in each of four
categories: combustion, organic materials, inorganic materials,
and open sources. Dr. Dale A. Denny of the Industrial Processes
Division at Research Triangle Park serves as EPA Project Officer.
In this study of the nitrogen fertilizer industry, Dr. R. A.
Venezia served as EPA Task Officer.
• • •
111
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ABSTRACT
This report describes a study of waterborne pollutants from the
manufacture of nitrogen fertilizers. It includes an evaluation
of the ammonia, ammonium nitrate, and urea manufacturing pro-
cesses, as well as the nitric acid process, which supplies acid
to the ammonium nitrate process.
Synthetic ammonia is commonly produced in the United States by
the catalytic reforming of natural gas using a six-step process.
Nitric acid solution is produced in a three-step ammonia oxida-
tion process where ammonia is catalytically oxidized to NO, and
further oxidized to NOa- N02 then reacts with water to form HNOa
and NO. Ammonium nitrate solution is produced by an exothermic
reaction of ammonia and nitric acid. The product ammonium
nitrate solution is sold, mixed with other fertilizers, or con-
verted to a solid form by various processes. Urea is produced
in a two-step reaction in which ammonia and carbon dioxide react
to form ammonium carbamate which is then dehydrated to form urea
and water.
Water effluents in a nitrogen fertilizer plant originate from a
variety of point and nonpoint sources. The major components in
the effluents are ammonia nitrogen, nitrate nitrogen, and organic
nitrogen. Low concentrations of other constituents may also be
present. The potential environmental impact of nitrogen ferti-
lizer effluents was evaluated by comparing the concentration of
a particular pollutant in a receiving stream as a result of dis-
charge to an acceptable concentratio (hazard factor). The ratio
of these two values is the source severity.
Source severities were calculated for plants producing ammonium
nitrate, urea, and both ammonium nitrate and urea. The consti-
tuents considered were un-ionized ammonia nitrogen (NH3°-N),
ammonium nitrogen (NH^-N) , nitrate nitrogen (N03~-N) , and
organic nitrogen (ORGHS). Source severities were calculated at
low and mean receiving water flow rates at receiving water pH's
of 7.6 and 9. At a mean receiving water flow rate and the
average pH of 7.6, ammonium nitrogen (NHi,+-N) was responsible
for the highest average source severity among the ammonium
nitrate, urea, and combined ammonium nitrate-urea source types;
5.9 x 10-3, 1.5 x 10-", and 1.1 x 10~2, respectively.
IV
-------
Control technologies are available and in use at some nitrogen
fertilizer plants. These technologies include containment, steam
stripping, air stripping, urea hydrolysis, biological treatment,
ion exchange, and condensate reuse.
This report was submitted in partial fulfillment of Contract
68-02-1874 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. The study covers
the period August 1977 to October 1978, and work was completed
as of October 1978.
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CONTENTS
Preface iii
Abstract v
Figures viii
Tables ix
Abbreviations and Symbols xi
1. Introduction 1
2. Summary 2
3. Source Description 7
Nitrogen fertilizer materials 7
Nitrogen fertilizer plants 8
Component process descriptions 10
Effluent origins 26
4. Effluent Parameters 30
Effluent characterization 30
Potential environmental effects 35
5. Control Technology 47
Types of control 47
Degree of application 56
6. Growth and Nature of The Industry 57
Present technology 57
Emerging technology . 57
Industry growth trends 59
Potential impact of controls 60
References . 61
Appendices
A. Raw Data 68
B. Calculation of Effluent Parameters 79
Glossary 89
Conversion Factors and Metric Prefixes 91
VI1
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FIGURES
Number Pag(
1 Conceptual diagram of the nitrogen fertilizer
industry 2
2 Potential interrelationships of various manufactur-
ing lines at a nitrogen fertilizer plant 9
3 Approximate percentage of nitrogen fertilizer
plants having single or specified combinations
of manufacturing processes 9
4 General process flow diagram of a typical ammonia
plant 11
5 Generalized flow sheet of ammonium nitrate
production processes 16
6 Physical states of ammonium nitrate products 16
7 Prilling process flow diagram 17
8 Stengel reactor 20
9 Block diagram of urea production process 21
10 Total recycle urea processes 22
11 Solidification of urea 22
12 Typical pressure system flowsheet 25
13 Process condensate steam stripper 31
14 Percent un-ionized ammonia in aqueous ammonia
solutions ammonia solutions of zero salinity. ... 37
15 Model of pilot steam stripper 49
16 Ammonia/condensate air stripping 50
17 Method for Treatment of Urea Crystallizer Condensate 51
18 Continuous ion exchange process 54
19 Ammonium nitrate effluent utilization 56
20 Growth factors for nitrogen-based fertilizers .... 59
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TABLES
Number
1 Nitrogen Fertilizer Production in the United States . . 3
2 Average Effluent Factors from Nitrogen Fertilizer
Processes . . 4
3 Average Source Severities for Nitrogen Fertilizer
Plants Based on Mean Receiving Body Flow Rates ... 5
4 Mass Balance Around the Condensate Steam Stripper—
Result of 65 Test Measurements .31
5 Effluent Discharge Factors for a Condensate Steam
Stripper . 32
6 Trace Metal Concentrations in Process Condensate . . .32
7 Trace Metal Effluent Discharge Factors from a
Condensate Steam Stripper 33
8 Average Effluent Parameters for Nitrogen Fertilizer
Plants 34
9 Effluent from Nitric Acid Plants with Single-Pass
Cooling Systems 35
10 Calculated Source Severities for Plants Producing
Ammonium Nitrate . .40
11 Calculated Source Severities for Plants Producing
Urea 40
12 Input Values of VD, CD, and VR Used To Calculate
Source Severity for Composite Nitrogen Fertilizer
Plants 42
13 Calculated Source Severities for Plants Producing
Ammonium Nitrate and Urea 43
14 Effluent Guidelines 44
15 Calculated Source Severities for A Condensate Steam
Stripper of An Ammonia Plant .44
16 Minor Constituents Present in Plant Effluents . . . . .46
17 Representative Waste and Treated Water Analysis
from Ion Exchange 54
18 Plant Locations Using Ion Exchange 55
IX
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TABLES (continued)
Number Page
19 Degree of Utilization of Nitrogen Control Tech-
nologies by Industry Segment 56
A-l Nitrogen Fertilizer Plants, Locations, and
Capacities . 69
A-2 Nitrogen Fertilizer Plants, Locations, and Wastewater
Receiving Bodies 71
A-3 Nitrogen Fertilizer Plants and Receiving Stream
Parameters 75
B-l Listing of Compiled Raw Data Characterizing The
Wastewater Streams from Ammonium Nitrate Plants . .80
B-2 Listing of Compiled Raw Data Characterizing The
Wastewater Streams from Urea Plants 81
B-3 Calculated Statistical Parameters Characterizing
Wastewater Streams from Ammonium Nitrate Plants . .84
B-4 Calculated Statistical Parameters Characterizing
Wastewater Streams from Urea Plants 85
B-5 Calculated Statistical Parameters Characterizing
Wastewater Streams from Ammonium Nitrate Plants . .86
B-6 Calculated Statistical Parameters Characterizing
Wastewater Streams from Urea Plants 86
B-7 Units for x.^ 88
x
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ABBREVIATIONS AND SYMBOLS
aq — denotes compound in aqueous solution
AN — ammonium nitrate
C,., — fraction of nitrogen in ammonium nitrate (0.47)
CD — concentration of a particular pollutant, g/m3
CD — concentration of given pollutant in ammonium nitrate
AN discharge, g/m3
Cn — concentration of given pollutant in urea discharge,
U g/m3
Cy — fraction of nitrogen in urea (0.35)
AH — change in enthalpy; the heat absorbed by a process
conducted at constant pressure, KJ/mole
F — hazard factor for particular pollutant, g/m3
g — denotes compound in gas phase
$, — denotes compound in liquid phase
LCA — Louisiana Chemical Association
LDeo — lethal dose of a test material that causes death in
50% of a population which has ingested the material
or into which the material has been injected
n — number of samples
NHa-N — ammonia nitrogen including both ionized and un-
ionized forms
NH3°-N — un-ionized ammonia nitrogen
NHa-N, — ammonia nitrogen discharged from the ammonium
nitrate plant, metric tons/day
NHa-N™ — total discharged ammonia nitrogen, metric tons/day
NH3-Nn — ammonia nitrogen discharge from the urea plant,
. metric tons/day
NH4 -N — ammonium nitrogen
NO3 -N — nitrate nitrogen
ORG-N — organic nitrogen
ORG-N-. — organic nitrogen discharge from the urea plant?
metric tons/day
P.., — weight of product ammonium nitrate per time, metric
tons/day
Pn — weight of product urea per time, metric tons/day
PN,N — weight of product nitrogen in ammonium nitrate form
per time, metric tons/day
PN., — weight of product nitrogen in urea form per time,
metric tons/day
XI
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PNT — total weight of product nitrogen per time, metric
tons/day
s — standard deviation
S — source severity for particular pollutant
T — temperature, °C
TKN — total Kjeldahl nitrogen, metric tons/day
TSS — total suspended solids, including organic or inor-
ganic particles physically held in suspension
VD — wastewater effluent flow rate, m3/s
V — volumetric flow rate from ammonium nitrate plant,
AN
VD — volumetric flow rate from total plant, m3/s
T
Vn — volumetric flow rate from urea plant, m3/s
UU
VR — volumetric flow rate of receiving body above plant
discharge, m3/s
w^ — plant output corresponding with X., metric ton/day
w. — plant output, metric tons/day
x — arithmetic mean
xi — individual of a column of numbers for which a
statistical parameter is being calculated
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SECTION 1
INTRODUCTION
Nitrogen fertilizers are those fertilizers whose main nutrient
contribution to the soil environment is nitrogen. For the pur-
poses of this study this definition is further restricted to the
primary nitrogen fertilizers from which all other nitrogen fer-
tilizers are derived; i.e., synthetic ammonia, ammonium nitrate,
and urea, with a consideration of nitric acid as an adjunct pro-
cess to that for ammonium nitrate. Production of all of these
fertilizers often occurs at a single plant location. Therefore,
this report characterizes entire plants as well as individual
processing streams.
This study is an assessment of those water effluents released to
the environment from nitrogen fertilizer plants. It describes
the many manufacturing processes for each of the basic nitrogen
fertilizers and identifies effluent sources. Operating parame-
ters are presented when available. Effluent parameters are
compiled and used to evaluate the impact of the nitrogen fertil-
izer industry on the aquatic environment. Effluent factors,
concentrations, and source severities for the several processes
as well as for a composite plant are given.
One section of the report discusses water pollution control tech-
nology available to the industry or under development. Major
technologies such as hydrolysis and ion exchange are described at
greater length, including operating parameters and degree of
application when available.
The final section considers projected industry growth trends and
discusses the potential impact of controls and growth on effluent
quality. Emerging technologies in several of the processes are
also presented in this section.
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SECTION 2
SUMMARY
This report is an assessment of the water effluents released to
the environment during production of nitrogen fertilizers. It
includes the three major manufacturing processes of ammonia,
ammonium nitrate, and urea, as well as the adjunct nitric acid
process that supplies acid to the ammonium nitrate process.
Excluded from study were the many blends of nitrogen fertilizers
with other components, e.g., micronutrients and phosphorus, even
though nitrogen may be their major nutrient. Studies on bulk
blending of fertilizers and the production of the various phos-
phate fertilizers have been reported in other source assessment
documents. Studies on air emissions from the production of am-
monia, ammonium nitrate, and urea have also been published. A
conceptual diagram of the nitrogen fertilizer industry is shown
in Figure 1.
Production statistics for the subject compounds are shown in
Table 1. The ammonium nitrate and urea produced were sold as
both solid and liquid. Approximately 80% of the synthetic
ammonia produced was used in the manufacture of other nitrogen
fertilizers or as a direct application fertilizer. In addition,
approximately 84% of the nitric acid produced was used to pro-
duce ammonium nitrate.
N2
NH3
PRODUCTION
NITRIC ACID
PRODUCTION
UREA
PRODUCTION
NITROGEN
> FERTILIZER
INDUSTRY
AMMONIUM
NITRATE
PRODUCTION
Figure 1. Conceptual diagram of the nitrogen fertilizer industry
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TABLE 1. NITROGEN FERTILIZER PRODUCTION IN THE UNITED STATES
(metric tons)
Compound Quantity produced
Ammonium nitrate (1976)
Urea (1975)
Ammonia (1976)
Nitric acid (1976)
7
3.
15
7.
.6
45
.2
16
X
X
X
X
106
106
106
106
A nitrogen fertilizer plant may incorporate one or more of the
three major processes. If ammonium nitrate is produced, a
nitric acid plant will commonly be on site. A consideration of
the three major processes reveals that 18% of the plants manu-
facture two out of the three fertilizers while 23% have facili-
ties to produce all three products.
In the United States 98% of the synthetic ammonia is produced by
the catalytic reforming of natural gas using a six-step process:
1) natural gas desulfurization, 2) catalytic steam reforming,
3) carbon monoxide shift, 4) carbon dioxide removal, 5) methana-
tion, and 6) ammonia synthesis. The other 2% of production ob-
tains feedstock hydrogen from electrolysis cells in chlorine-
caustic soda plants.
Ammonium nitrate solution is produced by an exothermic reaction
of ammonia and nitric acid. The solution may be sold directly
or blended with other fertilizer solutions (approximately 39% of
the solution produced), or converted into solid form (approxi-
mately 61% of the solution produced). Solids are made by prill-
ing, granulation, or graining. Prilling is the most common
method of solidification, accounting for 92% of the solids
produced.
Urea is produced by a two-step reaction. In the first reaction
ammonia and carbon dioxide react to form ammonium carbamate. In
the second reaction the ammonium carbamate is dehydrated to form
urea and water. Thirty-eight percent of the urea solution pro-
duced is sold as blending agent for other fertilizers or as a
raw material in the synthesis of other chemicals. The remaining
62% is solidified by either granulation or prilling. Granula-
tion is the most common method of solid urea production,
accounting for 85% of the solid product.
Nitric acid is produced in a three-step ammonia oxidation proc-
ess: 1) ammonia is oxidized to nitrogen oxide (NO) or nitrogen
(N2) in the presence of oxygen and a platinum catlyst, 2) NO is
further oxidized to nitrogen dioxide (N02)/ and 3) N02 reacts
with water to form nitric acid and NO. The resulting solution
stream is between 55% and 65% nitric acid.
-------
Effluents in a nitrogen fertilizer plant originate from both
point and nonpoint sources. Point sources exist at those plants
where process exhaust streams are condensed instead of being
released directly to the atmosphere. Condensates from evapora-
tors and concentrators fall into this category. Cooling tower
blowdown, crystallizer filtrate, and discharge from water treat-
ment units are other examples of effluent point sources.
Nonpoint sources may be either process specific or nonprocess
specific. Process specific nonpoint sources include valve and
pump leaks, cooling tower overflows, shipping areas, other random
spills and leaks, and plant washdowns. Nonprocess specific
sources result in an effluent that cannot be traced to a particu-
lar process or specific area. Typical examples of nonprocess
specific sources are general plant cleanup and runoff from pre-
cipitation. In addition, ammonia that is present in the air
around a plant may be absorbed by any water stream that is open
to the atmosphere.
The basic components in the effluent from a nitrogen fertilizer
plant are ammonia nitrogen (NH3-N), nitrate nitrogen (NO3--N),
and organic nitrogen (ORG-N). Ammonia exists in both the un-
ionized (NH3°-N) and ionized form (NH«+-N), and each one is
evaluated separately in terms of its potential environmental
impact. The organic nitrogen is primarily urea, but there may be
other organic nitrogen compounds in the stream, such as monoeth-
anolamine from ammonia manufacture. In addition to these basic
components there may be low concentration of methanol, carbon
dioxide, micronutrients, or cooling tower treatment compounds in
the plant effluent. These compounds are present in much lower
quantities than are the major nitrogen compounds. Average ef-
fluent factors for the major compounds are given in Table 2. A
compilation of effluent data from all reporting plants is given
in Appendix B.
TABLE 2. AVERAGE EFFLUENT FACTORS FROM
NITROGEN FERTILIZER PROCESSES
(g effluent component/kg product)
Process
Effluent
component
NH3-N
NO3-N
ORG-N
Ammonium nitrate
including ammonia
and nitric acid
0.862
0.471
0
Urea
including
ammonia
0.756
0
0.275
Composite
plants »b
0.809
0.236
0.138
For plant with equal ammonium nitrate and urea
capacities.
Plant includes ammonium nitrate, urea, ammonia and
nitric acid.
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In order to evaluate the potential impact of nitrogen fertilizer
plants on the environment, the source severity for the 22 plants
with adequate available data was calculated. Source severity
compares the concentration of a particular pollutant in a receiv-
ing stream as a result of discharge to an acceptable concentra-
tion (hazard factor). Severities were calculated based on the
mean river flow rate at each plant site, the average receiving
water pH of 7.6, and the average receiving water temperature of
16°C. Table 3 presents average severity values and ranges for
three plant types: plants producing ammonium nitrate (including
nitric acid and ammonia), plants producing urea (including
ammonia), and plants producing ammonium nitrate and urea (includ-
ing nitric acid and ammonia). Severities in terms of other
receiving water characteristics are presented in Section 4. The
wide range of severities reflects the wide range in individual
plant effluent rates and receiving stream flow rates. Effluent
rates vary with the degree of wastewater treatment and with the
level of water recycle and reuse.
TABLE 3. AVERAGE SOURCE SEVERITIES FOR NITROGEN FERTILIZER
PLANTS BASED ON MEAN RECEIVING BODY FLOW RATES
average receiving water pH = 7.6
average receiving water temperature = 16°C
Process
Ammonium nitrate,
including
acid and
Urea,
including
nitric
ammonia
ammonia
Effluent
species
NH3°
NH/*+
N03~
NH3°
NH*+
-N
-N
-N
-N
-N
ORG-N
Composite plant,
NH3°
-N
including ammonium +
nitrate, urea, nitric 4
acid, and
ammonia
N03~
-N
ORG-N
Average3
3
5
4
7
1
2
7
1
5
1
.0
.9
.4
.7
.5
.0
.4
.1
.1
.2
x ID-3
X ID"3
x 10-*
x 10~5
x 10~5
x IO-5
X 10~ 3
x 10"2
x ID" *
X ID"3
Severity
Range
0
0
0
1.2 x 10~5
2.3 x 10~5
4.9 x 10~6
1.4 x IO-5
2.8 x 10"5
<10~6
1.4 x 10~5
to
to
to
to
to
to
to
to
to
to
1.
2.
3.
1.
2.
4.
7.
42
80
3 x
1 x
2 x
5 x
24
10-1
10-*
10-*
io-5
13.5
1.
6.
3 x
5 x
io->
IO-2
Plants with low receiving stream flow rates (<1 m3/s) were excluded from
the average because they skew the data and give an inaccurate view of the
total industry-
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Effluent control in the nitrogen fertilizer industry is a
step process consisting of both containment and treatment. First
the many nonpoint sources must be gathered together before treat-
ment. Containment is used to some degree at almost every
nitrogen fertilizer plant, either to hold small pump leaks or to
drain an entire area. Newer plants are installing extensive
drainage systems and older plants are incorporating them in
remodeling plans.
Treatment itself varies with effluent and composition, and even
for a general treatment category there are many individual plant
modifications. Steam stripping is used extensively in the pro-
duction of ammonia to remove ammonia and methanol from waste
streams and to a limited extent in urea production. Air strip-
ping of ammonia has been tested but is only employed at one
ammonia plant to remove ammonia from process condensate. To
treat urea in waste streams, thermal hydrolysis is being promoted.
Several plants have installed and are operating thermal hydroly-
sis systems. Biological treatment of ammonium nitrate wastes is
practiced to a limited extent. Ion exchange under the name of
CHEM-SEPS® is currently in use or under installation in at least
10 plants. Some plants are using an ion exchange concept based
on an internally developed design.
Growth of ammonia, ammonium nitrate, and nitric acid production
has been fairly constant in recent years and is projected to
remain so. Urea, however, has experienced dramatic growth in-
creases in recent years. The annual growth rate for each indus-
try based on actual and predicted production from 1975 through
1980 is as follows:
Ammonia 5.2%
Ammonium nitrate 3.8%
Urea 9.7%
Nitric acid 1.0%
Effluent quality is expected to improve as this growth occurs for
two reasons: 1) government regulations will require older plants
to apply control technology, and 2) as growth occurs new plants
or plant expansions will integrate control technology into over-
all design. The exact effect this will have on effluent quality,
however, cannot be predicted.
-------
SECTION 3
SOURCE DESCRIPTION
NITROGEN FERTILIZER MATERIALS
A nitrogen fertilizer can be defined as any fertilizer whose main
nutrient contribution to the soil environment is nitrogen. Many
materials fall under this definition, but most of them arise from
three primary compounds: ammonium nitrate, urea, and ammonia.
These three chemicals are the focus of this report. In addition,
nitric acid is included as an essential part of nitrogen fertil-
izer materials because it is a precursor for ammonium nitrate
production. All other nitrogen fertilizers are formed by combi-
nations of or additions to these major chemicals.
Ammonium nitrate is a white crystalline material at normal tem-
peratures. Its major end use is as a fertilizer either in
liquid or solid form. Of the 7.6 x 106 metric tons3 produced in
1976, 6.3% was sold directly as a liquid, 27.7% was used as a
liquid in other fertilizers, 50.4% was sold as a solid fertilizer,
and 15.6% was consumed in other ways; e.g., in explosives (1).
Urea is a colorless crystal at normal temperatures. Its major
use is as a fertilizer with approximately 85% of production being
used in this capacity(2). The remaining 15% is used as an indus-
trial feedstock for urea-formaldehyde resins, melamine, or other
products (2). In 1975, 3.45 x 106 metric tons of urea were pro-
duced (as 100% urea) (2).
al metric ton equals 106 grams; conversion factors and metric
system prefixes are presented at the end of this report.
(1) Search, W. J., and R. B. Reznik. Source Assessment:
Ammonium Nitrate Production. EPA-600/2-77-107i, U.S. Envi-
ronmental Protection Agency, Research Triangle Park, North
Carolina, September 1977. 78 pp.
(2) Search, W. J., and R. B. Reznik. Source Assessment: Urea
Manufacture. EPA-600/2-77-107JI, U.S. Environmental Protec-
tion Agency, Research Triangle Park, North Carolina,
November 1977. 94 pp.
-------
In 1976, 15.2 x 106 metric tons of ammonia were produced in the
United States (3). Approximately 80% of this amount was used
either as a direct application fertilizer or in the production
of ammonium nitrate, urea, and ammonium phosphates for fertilizer
application (3). The remainder was used in nonfertilizer pro-
duction of ammonium nitrate, urea, nitric acid (which may in turn
go to fertilizer production), acrylonitrile, and amines (3).
In 1976, 7.16 x 106 metric tons of nitric acid were produced in
the United States (4). By material balance, approximately 84%
of this production was consumed in the production of ammonium
nitrate. The remainder was sold directly as nitric acid or used
in other applications.
NITROGEN FERTILIZER PLANTS
Nitrogen fertilizers are often made at a complex in which more
than one fertilizer product is manufactured. This type of ar-
rangement results from the potential interrelationships shown in
Figure 2. By taking advantage of these interrelationships and
judicious location of manufacturing lines, plant operators can
gain an economically favorable position. Cost savings are real-
ized from minimal external purchase and transportation of raw
materials and from energy savings obtained by interconnecting
heat exchangers. However, all or none of these interrelation-
ships may exist at any given plant.
Integration within the nitrogen fertilizer industry is illus-
trated in Figure 3 for ammonium nitrate, urea, and ammonia pro-
cesses. For example, 10% of the nitrogen fertilizer plants
contain only ammonia and urea production facilities. Ammonia,
ammonium nitrate, and urea production facilities are contained
in 23% of the plants. Nitric acid plants were assumed to exist
at all ammonium nitrate facilities. Data on the various plants
used in preparing Figure 3 are presented in Table A-l in
Appendix A.
This communal arrangement presents serious ramifications in the
water effluent area. Many plants have common outfalls; i.e., all
processes discharge their effluent into a single channel. Also
discharging into the channel may be groundwater runoff or plant
washdown. The problems posed by this situation will be discussed
at greater length in Appendix B.
(3) Rawlings, G. D. , and R. B. Reznik. Source Assessment:
Synthetic Ammonia Production. EPA-600/2-77-107m, U.S. Envi-
ronmental Protection Agency, Research Triangle Park, North
Carolina, November 1977. 83 pp.
(4) Current Industrial Reports, Inorganic Chemicals, 1976.
M28A(76)-14, U.S. Department of Commerce, Washington, D.C.,
August 1977. p. 16.
8
-------
SYNTHETIC AMMONIA PLANT
REFORMING &
CO? CONVERSION
Figure 2. Potential interrelationships of various manufacturing
lines at a nitrogen fertilizer plant.
Figure 3. Approximate percentage of nitrogen fertilizer
plants having single or specified combinations
of manufacturing processes.
-------
COMPONENT PROCESS DESCRIPTIONS
This section presents process descriptions for synthetic ammonia,
ammonium nitrate, urea, and nitric acid production. A more ex-
tensive discussion of each process, except nitric acid, is
available in the air source assessment documents (1-3) . An air
source assessment document has also been written on the bulk
blending of fertilizers (5). This operation can also occur at
nitrogen fertilizer plants. Air emissions from this process are
readily identifiable. However, water effluent only results from
the occasional washing down of trucks and blending equipment.
The composition of the resulting stream is highly random and its
flow is a small part of the overall plant effluent flow. There-
fore, bulk blending of fertilizers is not discussed separately
in this document.
A later section, entitled "Effluent Origins," discusses the ori-
gin of water effluents for each process in the nitrogen fertil-
izer plant.
Ammonia Industry
Synthetic ammonia in the United States is produced predominantly
(98% of total production) by the catalytic steam reforming of
natural gas. In this process hydrogen feedstock for ammonia
synthesis is obtained by reacting natural gas with steam. The
remaining 2% of production obtains hydrogen feedstock from
electrolysis cells in chlorine-caustic soda plants (3).
Six process steps are required to produce synthetic ammonia by
the catalytic steam reforming of natural gas method:
1. natural gas desulfurization
2. catalytic steam reforming
3. carbon monixide shift
4. carbon dioxide removal
5. methanation
6. ammonia synthesis
The first, third, fourth, and fifth steps are designed to remove
impurities such as sulfur, carbon monoxide (CO), carbon dioxide
(C02), and water from the feedstock, the hydrogen, and the syn-
thesis gas streams. In the second step, hydrogen is manufactured
and nitrogen is introduced into the process. The sixth step pro-
duces anhydrous ammonia from the synthesis gas:
N2 + 3H2 -* 2NH3 (1)
(5) Rawlings, G. D., and R. B. Reznik. Source Assessment:
Fertilizer Mixing Plants. EPA-600/2-76-032c, U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, March 1976. 187 pp.
10
-------
While all ammonia plants use this basic process, process details
such as pressures, temperatures, and quantities of feedstock vary
from plant to plant. A general process flow diagram of a typi-
cal synthetic ammonia plant using the catalytic steam reforming
process is shown in Figure 4 (3).
NATURAL GAS
AIR EMISSIONS DURING
REGENERATION OF TANK
AIR EMISSIONS
COMPRESSED A1
AIR EMISSIONS
PURGE GAS VENTED
TO PRIMARY REFORMER
FOR FUEL
Figure 4. General process flow diagram
of a typical ammonia plant (3) .
Natural Gas Desulfurization—
The sulfur content of natural gas feedstock must be reduced to as
low a level as is economically possible to prevent nickel cata-
lyst poisoning in the primary reformer. The total sulfur concen-
tration in pipeline grade natural gas ranges from 229 yg/m3 to
915 yg/m3, with an average value of 450 yg/m3 (3). The concen-
tration in the feedstock must be reduced to less than 280 yg/m3.
Over 95% of the ammonia plants use activated carbon fortified
with a metallic additive,.such as copper, for feedstock desulfuri-
zation. The remainder of the plants use a zinc oxide bed which
is replaced instead of being regenerated at the plant. Ammonia
plants using activated carbon for desulfurization employ a dual-
tank system so that one tank is always onstream while the other
is being regenerated.
Catalytic Steam Reforming—
Natural gas leaves the desulfurization tank containing less than
150 yg/m3 sulfur (3). This sweetened natural gas is mixed with
process steam and preheated to approximately 540°C in the heat
recovery section of the primary reformer. The steam-gas mixture
enters the vertically supported primary reformer tubes, which are
filled with a nickel-based reforming catalyst. The reforming
11
-------
reaction (Equation 2) is endothermic and requires a heat input of
227 kJ/mole:
CHij + H2O -> CO + 3H2 (2)
Radiant heat for the reforming reaction is normally supplied by
firing natural gas and purge gas (from the synthesis loop) on the
outside of the reformer tubes. Fuel oil is also used for heating.
Approximately 70% of the methane is converted to hydrogen and
carbon monoxide in the primary reformer. Process gas is sent to
the secondary reformer, where it is mixed with air that has been
compressed in a centrifugal compressor to approximately 3.4 MPa
and preheated to about 480°C in heat exchangers in the primary
reformer. Sufficient air is added to produce a final synthesis
gas having a hydrogen-to-nitrogen molar ratio of 3:1.
Carbon Monoxide Shift—
After cooling, the secondary reformer effluent gas (12.0% CO and
8.4% C02 on a dry weight basis) enters a high temperature (330°C
to 550°C) CO shift converter which is filled with an iron oxide
shift catalyst promoted with chromium oxide. Conversion of water
and carbon monoxide to carbon dioxide and hydrogen with the addi-
tion of steam is necessary for economical use of the raw synthe-
sis gas. The following reaction takes place in the CO shift
converter:
CO + H20 -> C02 + H2 (3)
Shift gas is cooled to approximately 200°C in a heat exchanger
and passes to the low temperature shift converter for further CO
removal. The final shift gas is cooled from approximately 200°C
to approximately 55°C and enters the carbon dioxide absorption
system. Unreacted steam is condensed and separated from the gas
in a knockout drum. This condensed steam is the source of more
than 90% of the wastewater generated at a synthetic ammonia plant.
A 544-metric ton/day ammonia plant produces 7.89 x 10"3 m3/s of
condensed steam (process condensate). A 900-metric ton/day plant
produces 1.39 x 10~2 m3/s of condensate. This water contains
approximately 600 g/m3 to 1,200 g/m3 ammonia, 200 g/m3 to 2,000
g/m3 methanol, and 200 g/m3 to 2,800 g/m3 carbon dioxide (6-9).
(6) Quartulli, 0. J. Stop Wastes: Reuse Process Condensate.
Hydrocarbon Processing, 54(10):94-99, 1975.
(7) Romero, C. J. , D. A. Brown, and J. H. Mayes. Treatment of
Ammonia Plant Process Condensate Effluent. EPA-600/2-77-200,
U.S. Environmental Protection Agency, Research Triangle Park'
North Carolina, September 1977. 85 pp.
12
-------
Ammonia in the process condensate is formed in the high tempera-
ture shift converter. It is present as ammonium bicarbonate
because the condensate is saturated with carbon dioxide. Methanol
is formed in the low temperature shift converter. The condensate
also contains small amounts (less than 1 g/m3) of sodium, iron,
copper, zinc, calcium, and aluminum, which enter the process
stream through contact with catalyst, internal refractory, vessel
walls, and piping (6, 10).
Process condensate is sent to a steam stripper to remove volatile
gases such as ammonia, methanol, and carbon dioxide. The concen-
tration of these materials in the effluent depends on the pH, the
amount of steam used, and the original concentration in the con-
densate. The ammonia content is generally reduced to 50 g/m3 or
less, the methanol concentration to under 100 g/m3, and the CO2
concentration to less than 50 g/m3 (6, 9). From 96 kg to 240 kg
of stripping steam are used per cubic meter of condensate (6).
Ion exchange units or molecular sieves are then used to further
purify the condensate before recycling it to the boilers. Steam
and volatile gases are vented to the atmosphere. Trace metals
remaining in the process condensate are removed by the ion
exchange unit.
Carbon Dioxide Removal—
The final shift gas contains CC>2 which must be removed. [About
1.22 metric tons (11) of C02 are produced per metric ton of
ammonia.] The removal of CC>2 depends on its acid-gas character;
i.e., its tendency to form carbonic acid in water:
C02 + H20 t H2C03 (4)
Carbonic acid can be absorbed by solutions of amines, for example:
2NH2CH2CH2OH + H2C03 ->• (NH2CH2CH2) 2C03 + 2H20 (5)
(8) Spangler, H. D. Repurification of Process Condensate. In:
Ammonia Plant Safety, Vol. 17, Chemical Engineering Progress
Technical Manual. American Institute of Chemical Engineers,
New York, New York, 1975. pp. 85-86.
(9) Quartulli, 0. J. Review of Methods for Handling Ammonia
Plant Process Condensate. In: Proceedings of the Fertil-
izer Institute Environmental Symposium (New Orleans,
Louisiana, January 13-16, 1976), The Fertilizer Institute,
Washington, D.C. pp. 25-44.
(10) Fineran, J. A., and P. H. Whelchel. Recovery and Reuse of
Aqueous Effluent from a Modern Ammonia Plant. In: Ammonia
Plant Safety, Vol. 13, Chemical Engineering Progress Tech-
nical Manual. American Institute of Chemical Engineers,
New York, New York, 1971. pp. 29-32.
(11) Strelzoff, S. Choosing the Optimum C02-Removal System.
Chemical Engineering, 82(19):115-120, 1975.
13
-------
or by solutions of alkaline salts, such as:
K2C03 + H2C03 -»• 2KHCO3 (6)
to form carbonates. These carbonates decompose into CO2 and the
amine or salt on heating, regenerating the absorption solution.
The CO2 scrubbing systems used in the United States today employ
either monoethanolamine or hot potassium carbonate as the scrub-
bing medium (11, 12) .
Methanation —
In commercial practice, all CO2 absorption methods leave a small
amount of CO and C02 (usually less than 1.0%) which must be re-
moved because it is a poison to most ammonia synthesis catalysts.
Residual C02 is removed by catalytic methanation. The reaction
is conducted over a nickel catalyst (nickel oxide on alumina) at
temperatures of 300 °C to 600 °C and pressures up to 3 MPa accord-
ing to the following reactions:
CO + 3H2 -> CHij + H20 (7)
C02 + H2 •*• CO + H20 (8)
C02 + 4H2 •* CHU + 2H20 (9)
The methanation reaction is the reverse of the catalytic steam
reforming of methane. Methanation is favored for its lower tem-
peratures and removal of excess water. The final synthesis gas
at 38°C and approximately 2.5 MPa has a 3:1 molar ratio of hydro-
gen to nitrogen and contains less than 1% methane and argon.
Ammonia Synthesis —
The purpose of the ammonia synthesis section is to fix the nitro-
gen with hydrogen as ammonia in the presence of a catalyst. The
arrangement and construction of equipment, the composition of
catalysts, and the temperatures and pressures used vary from
plant to plant.
The first step in the synthesis process is to compress the
synthesis gas from the methanation step. Condensed ammonia is
separated from the unconverted synthesis gas in a liquid-vapor
separator and sent to a let-down separator. The unconverted gas
is compressed and preheated to approximately 180°C before enter-
ing the synthesis converter.
Synthesis gas enters the converter and is radially dispersed
through the triply promoted iron oxide (Fe30i+) synthesis catalyst^
(12) Green, R. V. Synthetic Nitrogen Products. In: Riegel's
Handbook of Industrial Chemistry, Seventh Edition, J. A.
Kent, ed. Van Nostrand Reinhold Company, New York, New York,
1974. pp. 75-122.
14
-------
The exit gas from the converter contains approximately 15% ammo-
nia and approximately 14% inerts. This gas is then cooled from
approximately 370°C to about 38°C. The ammonia which condenses
is separated in a primary separator. A small portion of the over-
head gas is taken as a purge to prevent the buildup of inerts
such as argon in the circulating gas system (12). The purge gas
is cooled to -23°C in order to condense ammonia and minimize am-
monia loss, and is then used as fuel in the primary reformer (13).
Liquid ammonia from the primary, secondary, and purge separators
collects in the let-down separator where the ammonia is flashed
to 0.1 MPa at -33°C to remove impurities such as argon from the
liquid. The flash vapor is condensed in the let-down chiller.
Anhydrous ammonia product is drawn from the let-down separator
and may be stored in a low temperature (-33°C) atmospheric stor-
age tank or piped to other locations within the plant to produce
other products.
Ammonium Nitrate
Ammonium nitrate is produced by an exothermic reaction of ammonia
and nitric acid. When a 55% nitric acid feed stream is used, the
product of the reaction is an aqueous solution of ammonium ni-
trate (61%). In practice the heat of reaction (108.8 kJ) may be
used to drive off a portion of the water and concentrate the solu-
tion to 83% ammonium nitrate. Another major use is to preheat
the ammonia and nitric acid feed streams.
In the United States, there are four major solidification proc-
esses (see Figure 5) which utilize this basic chemistry to pro-
duce solid ammonium nitrate (1). Three of these (prilling,
graining, and granulation by spherodization) have the common
starting point described above. The fourth, the Stengel process,
differs in the method by which the feed reactants are mixed and
concentrated as well as in the solid formation method.
These differing processes give the breakdown in final product
state shown in Figure 6. This breakdown is based on actual pro-
duction and indicates that 92% of all solid product is formed by
prilling, 7% by granulation, and 1% by graining. Prilling is con-
sidered to be the main process and will be discussed further.
The remaining three processes are briefly described on page 19.
Prilling Processes—
Ammonium nitrate solution can be solidified in four major proc-
esses as mentioned previously. This assessment centers on the
(13) Haslam, A. A., and W. H. Isalski. Hydrogen from Ammonia
Plant Purge Gas. In: Ammonia Plant Safety, Vol. 17,
Chemical Engineering Progress Technical Manual. American
Institute of Chemical Engineers, New York, New York, 1975.
pp. 80-84.
15
-------
DIRECT SOLUTION SHIPMENT
STENGEL PROCESS
NES RECYCLE
Figure 5. Generalized flow sheet of ammonium
nitrate production processes.
PRODUCTION A SOLIDS (61%l
AAA
SOLIDS)
PERCENTAGES REFLECT WEIGHT PERCENT.
Figure 6. Physical states of ammonium nitrate products.
prilling process, because at least 92% of all solid ammonium
nitrate in the United States is produced by this method.
The basic prilling process (14) consists of spraying hot, concen-
trated ammonium nitrate solution from the top of a tower. In
descending countercurrent to a lower temperature airstrearn, the
droplets are formed into spherical particles between 84 pm and
2.38 mm in diameter. This basic procedure is actually only one
(14) Williams, L., L. F. Wright, and R. Hendricks. Process for
the Production of Ammonium Nitrate. U.S. Patent 2,402,192
(to Consolidated Mining and Smelting Co. of Canada, Ltd.),
June 18, 1946.
16
-------
step of what is termed the prilling process today, which includes
the following:
feed preparation and recycle
neutralizer and liquid storage
evaporation/concentration
• particle formation
• product preparation
• dust control
The above areas are distinguished as six sections on the general-
ized flow sheet in Figure 7 by dashed lines.
Figure 7. Prilling process flow diagram.
Section 1 in Figure 7 contains the feed pretreatment and the
recycle loops entering the main process stream before the neutral-
izer. Ammonia is heated to vaporization (approximately 66°C to
77°C) before being introduced under a liquid nitric acid head.
The nitric acid is heated in 85% of the plants to approximately
82°C.
A lump dissolving tank dissolves the over- and undersize material
recovered from the screening process. The material is then
recycled to the process as a weak (approximately 60% ammonium
nitrate) liquor.
Section 2 of Figure 7 contains the neutralizer and an adjusting
tank. The neutralizer is a vertical, cylindrical vessel in which
the reaction between ammonia and nitric acid takes place. A
hydrostatic head of ammonium nitrate is maintained by judicious
placement of the overflow pipe. The reaction takes place under
this head.
As a result of the highly exothermic reaction and the water con-
tent of the nitric acid feed, a steam exhaust exists. This
17
-------
stream may be used to preheat the ammonia and/or it may be
exhausted to the atmosphere or condensed.
The adjusting tank is used to store the 83% ammonium nitrate solu-
tion from the neutralizer, to receive overflow from a head tank
on the prilling tower, and to supply the evaporator/concentrator
on a demand basis. The actual ammonium nitrate concentration in
such tanks may therefore range from 81% to 83%.
Section 3 in Figure 7 consists of the evaporator/concentrator.
This portion of the process is responsible for concentrating the
81% to 83% solution to a 95% to 96% solution for low density
prill production or to a 99.5+% solution for high density prill
production.
Section 4 in Figure 7 includes the prilling tower, various sizing
screens, and the dryer and cooler. In the prilling tower, ammo-
nium nitrate is received from the evaporator/concentrator and con-
tained in a head tank at the top of the tower. The head tank
maintains a constant pressure on a spray device which sprays the
ammonium nitrate into the tower. Droplets are formed and fall
countercurrent to a rising airstream. The airstream acts as a
heat transfer mechanism that cools the ammonium nitrate below its
melting point and permits solidification of the droplet into a
spherical particle.
Two solid products can be made by the prilling process: low
density prills and high density prills. For the low density
prills, a 95% to 96% solution is used. As these droplets descend
in the tower, the prill cools, trapping the water. When the
prill is dried, the void space left results in a low density
prill with a bulk density of 770 kg/m3. Approximately 40% of all
prilled ammonium nitrate is low density. Because high density
prilling utilizes a more concentrated ammonium nitrate solution,
the resulting voids are fewer and a prill with bulk density of
860 kg/m3 results.
After .solidifying, prills are screened to remove oversize and
undersize material. Low density prills then go to a two-stage
drying process to drive off excess water, followed by cooling and
additional screening. High density prills do not require the
drying step and go directly to cooling followed by screening.
Low density prills which are not used as an onsite intermediate
(e.g., in explosive manufacturing or fertilizer mixing) are
coated with diatomaceous earth or other material as a water
barrier. High density prills are generally not coated (approxi-
mately 3% are coated); instead they are made with an additive
that enhances shelf life.
The final product may be stored in warehouses (for a short period
of time), shipped in bulk in railroad cars or bulk trucks, or
bagged in 23-kg or 45-kg quantities.
18
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Other Processes—
Three processes other than prilling were identified in Figure 5.
The basic differences in the products are crystal structure and
particle strength.
The graining process employs feed streams and a neutralizer simi-
lar to those used in the prilling process. The stream then goes
through an evaporation step to produce a 98% ammonium nitrate
solution. This stream is discharged to graining kettles where
the mix is stirred by large plows until it cools.
The SPHERODIZER® granulation process, developed by C&I Girdler
Inc. (15-17), utilizes a neutralizer and evaporator/concentrator
as described previously. The method by which the solids are
formed, however, differs greatly. The 99.5% ammonium nitrate is
sprayed through nozzles into a rolling bed of particles in the
rotating granulation drum (18). A dam in the drum retains the
particles a sufficient length of time to permit several layers to
build up on each granule. The granules then pass over the dam
into the cooling section where they are screened and cooled; then
they are coated and bagged.
The Stengel process uses the special reactor shown in Figure 8
(19, 20). Preheated nitric acid and ammonia are continuously fed
to the reactor. The heat of reaction vaporizes the water in the
nitric acid feed. A solution of 98% ammonium nitrate and trace
ammonia flows from the reactor to a centrifugal separator which
removes the ammonium nitrate and runs it through an air stripper
that reduces the moisture content to approximately 0.2%.
(15) Smith, B. G. Process for Production of Fertilizer Pellets.
U.S. Patent 2,926,079 (to C&I Girdler Inc.), February 23,
1970.
(16) Tyler, F. J., and T. D. Striggles. Process for Pelletizing
a Water Soluble Material. U.S. Patent 3,227,789 (to C&I
Girdler Inc.), January 4, 1966.
(17) Tyler, F. J., and T. D. Striggles. Apparatus for Making
Spherical Pellets of Water Soluble Substances. U.S. Patent
3,333,297 (to C&I Girdler Inc.), August 1, 1967.
(18) Reed, R. M., and J. C. Reynolds. The Spherodizer Granula-
tion Process. Chemical Engineering Progress, 99(2):62-66,
1976.
(19) Hester, A. S-, J. J. Dorsey, Jr., and J. T. Kaufman.
Stengel Process Ammonium Nitrate. Industrial and Engineer-
ing Chemistry, 46(4):622-632, 1954.
(20) Stengel, L. A. Process for Producing Ammonium Nitrate.
U.S. Patent 2,568,901 (to Commercial Solvents Corp.),
September 25, 1951.
19
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AMMONIA GAS
STEAM
NITRIC ACID
MOLTEN
AMMONIUM
NITRATE
Figure 8. Stengel reactor (20) .
The molten ammonium nitrate flows into a weir box for distribu-
tion onto an endless, stainless steel, water-cooled (Sandvik)
belt. Solid ammonium nitrate is removed from the belt by a
doctor blade. This material is fed to grinders, then screened,
coated, and bagged. The oversize material is recycled to the
grinder and the fines are returned to the process. Particle form-
ation may also be accomplished using a prill tower, as described
previously.
Urea Manufacture
Urea [CO(NH2)2] is produced by the reaction of ammonia and carbon
dioxide to form ammonium carbamate (NH2C02NHif) which is then
dehydrated to form urea and water. There are over 15 production
methods by which this reaction is carried out. All processes,
however, follow the basic scheme shown in Figure 9 (2). The reac-
tion of liquid ammonia and carbon dioxide gas takes place at
approximately 175°C to 200°C and 19.2 MPa to 23.2 MPa. The ammo-
nium carbamate formed is dehydrated to form urea. The resulting
urea stream goes to various solution concentration, solidifica-
tion, and packaging steps before leaving the plant.
Solution Production—
While process chemistry remains constant, there are variations in
vessel design, operating conditions, and type and quantity of
unreacted material recycle. These variations result in three
major classes of urea processes (for solution formation), based
on the type or quantity of recycle: once-through processes,
partial recycle processes, and total recycle processes.
In once-through processes, there is no recycle of unreacted
material. The reactants enter the reactor, achieve 40% to 45%
conversion to urea, and then proceed to a decomposer. Here
unreacted carbamate is decomposed to ammonia and carbon dioxide
20
-------
PRODUCT SHIPMENT
CD
SOLUTION PRODUCTION SOLID PRODUCTION r-
--—-— ^
/^^
AMMONIA
CARBON^
DIOXIDE
SECTION
^v _— -^\.
— ^ r ^
SOLUTION
PRODUCTION
SOLUTION
CONCENTRATION
SOLID
FORMATION
FINISHING
£
o
z
o
RECYCLE |
CD
cz
s
r~
O
>
z
o
MDCA
UKtA
SHIPMENT
Figure 9. Block diagram of urea production process.
which is then separated from the urea and water. The aqueous
urea goes for further processing. The mixed gas stream goes
directly to another fertilizer manufacturing facility as a feed
stream.
In the partial recycle process, the reactants are fed to the
reactor with approximately 200% excess ammonia versus the 2:1 to
3:1 ammonia-to-carbon dioxide molar ratio in the once-through
process. This excess has been shown to give a urea equilibrium
yield of at least 80%. Before going to a decomposer and proceed-
ing as described above, the reactor effluent passes through an
excess ammonia separator. The ammonia recovered is recycled to
the reactor.
Figure 10 is an extreme simplification of the basic process dif-
ferences in the three total recycle systems available from
various contractors (2). Each recycles all unreacted material to
the reactor. In the gas recycle system, the reactor effluent is
decomposed in the manner described for the once-through process.
The decomposed gases are then separated and recycled. In the
liquid recycle system, the separated carbamate solution is
recycled to the reactor. In the gas/liquid recycle system, ammo-
nia is recycled basically as a gas and carbon dioxide (with a
stoichiometric amount of ammonia) is recycled as a carbamate
slurry.
Solid Urea Production—
Figure 11 is a flowsheet of the entire urea solidification proc-
ess (2) . The formation of solid urea requires a critical balance
between temperature, retention time, and airflow due to several
physical characteristics: melting point, heat of crystallization,
and decomposition properties. These factors lead to careful
21
-------
FEED
UREA
" SOLUTION
A. Basic gas recycle process
CARBAMATE RECYCLE
M REACTOR
MAJ
i
CONDENSER
1 GASES
SEPARATOR
ADDITIONAL
LIQUID
UREA
SOLUTION
FEED-
B. Basic liquid recycle process
FEED i
NH3 RECYCLE
K7\ REACJOR
$
1
SEPARATOR
»
DECOMPOSER
UREA
" SOLUIION
Figure 10.
CARBAIVIATE RECYCLE
C. Basic gas/ liquid recycle process
PRODUCT-CONTAINING STREAMS
RECYCLE. FEED,OR OTHER ANCILLARY STREAMS
Total recycle urea processes
AQUEOUS UREA SOLUTION
COOLING, SCREENING & COATING
Figure 11. Solidification of urea (2).
22
-------
control and at times adaptation of established techniques depend-
ing upon the environment in which the material is produced.
Solution concentration is achieved by either a crystallizer or
evaporator. The purpose of both is to achieve a more concen-
trated stream while maintaining a low biuret (H2NCONHCONH2)
content (a contaminant that can result from heat exposure) . When
a crystallizer is used, the crystals must be dried and melted
before going to solid formation. Water effluents result from
these operations directly from crystallization, and from off-gas
condensation in evaporators.
Solid product can be formed by two methods, prilling and granula-
tion. The Spherodizer granulation process accounts for approxi-
mately 85% of all the solid urea that is produced domestically.
In this process, urea melt enters a granulation drum through a
spray bar which distributes the melt on a tumbling bed of parti-
cles. Particles of appropriate diameter exit the drum by passing
over a retaining dam and go through a cooling section.
The second method of solid formation is prilling. In this proc-
ess, concentrated urea solution is pumped to the top of a tower
30.5 m to 33.5 m high and forced through a spray device in a
method similar to that previously described for ammonium nitrate.
Final product preparation may include cooling of the material,
screening of the final product, coating for preservation purposes,
and possibly bagging.
Nitric Acid Production
In the United States, nitric acid is manufactured commercially by
the ammonia oxidation process. A series of three reactions is
required to convert ammonia, the feed substance, to nitric acid.
In the first reaction, ammonia is oxidized to either NO or N2 in
the presence of oxygen (02) and a platinum catalyst as follows:
4H3 + 502 •> 4NO + 6H20 (10)
or
4NH3+ 302 -»• 2N2 + 6H2O (11)
Both reactions are rapid, complete, and highly exothermic (AH
equals -226 kJ/mole and -317 kJ/mole, respectively), with higher
operating temperatures and gas velocities favoring higher yields
of NO, the desired product. Operating pressure has some effect
on yield, and this fact is exploited in the dual pressure proc-
ess. Industrial experience has shown that a 96% yield of NO can
23
-------
be expected at 800 kPa and 900°C while a yield of 98% can be
expected at atmospheric pressure (100 kPa) and 850 °C (21) .
In the second reaction, NO and 02 react slowly, compared to the
first pair of reactions, to yield nitrogen dioxide by the follow
ing exothermic (AH equals -114 kJ/mole) reaction:
2ND + 02 t 2N02
Lower temperature and higher pressure favor the formation of NO2.
An equilibrium is achieved between N02 and nitrogen tetraoxide
(N2Oit) in the following exothermic reaction:
2N02 "t ®2Ok (13)
In this case lower temperatures and higher pressures favor the
formation of N20it (21) .
In the third reaction, nitrogen dioxide combines with water to
form nitric acid as follows:
3N02(g) + H20(£) t 2HNO3(aq) + N0(g) (14)
This reaction is also exothermic (AH equals -136 kJ/mole) , and
lower temperature and higher operating pressure favor the forma-
tion of HN03 (aq) .
In practice, operating gage pressures of the ammonia oxidation
process fall within three ranges: atmospheric (0 kPa to 70 kPa) ,
intermediate (140 kPa to 410 kPa) , and high pressure (550 kPa to
830 kPa) . As noted, higher pressures are advantageous to the
formation of the desired products in reactions 12 and 14 . There-
fore 91% of the nitric acid produced in the United States is
produced within the high pressure range of operating pressures
(22) . A typical process flowsheet common to a high pressure
system is presented in Figure 12 (23) .
In the dual pressure process, which is more common in Europe than
in the United States, advantage is taken of the conversion of
(21) Strelzoff, S-, and D. J. Newman. Nitric Acid. In: Kirk-
Othmer Encyclopedia of Chemical Technology, Second Edition,
Vol. 13. John Wiley & Sons, Inc., New York, New York, 1967,
pp. 796-814.
(22) Spencer, E. F., Jr. Pollution Control in the Chemical
Industry. In: Industrial Pollution Control Handbook,
H. F. Lund, ed. McGraw-Hill, Inc., New York, New York,
1971. pp. 14-4 to 14-6.
(23) Mandelik, B. G. , and W. Turner. Selective Oxidation in
Sulfuric and Nitric Acid Plants: Current Practices.
Chemical Engineering, 84(9):127-130, 1977.
24
-------
NITRIC ACID PRODUCT
BOILER
FEEDWATER
HEATER;
PLATINUM \
DUST FILTER
NHj-AIR MIXER
COOLING
WATER
NHj
OXIDATION
REACTOR
AIR EXPANDER
COMPRESSOR
Figure 12. Typical pressure system flowsheet (23).
NH3 to NO (Reaction 10) at lower pressures. This process util-
izes low pressure ammonia oxidation followed by high pressure
absorption of N02 in water.
In all of the processes ammonia is first vaporized by steam, then
mixed with excess compressed air. This mixture is passed through
the platinum catalyst (which may also contain less than or equal
to 10% rhodium to increase catalyst strength) in the ammonia oxi-
dation reactor. An operating temperature of approximately 900°C
is typically used (23). As mentioned earlier, 95% to 98% of the
feed NH3 is converted to NO (21, 23).
Temperature in the reactor is controlled by cooling water that
circulates through the reactor shell. Some cooling occurs when
tail gas is circulated through the heater below the reactor as
shown in Figure 12.
The gas containing NO is cooled following the ammonia oxidation
reactor. As shown in Figure 12, the heat can be recovered to
produce steam which can be used for various purposes including
1) powering the air compressor drive turbine, 2) vaporizing the
ammonia at the head end of the process, and 3) exporting for use
in other processes in the fertilizer plant.
25
-------
Additional cooling takes place in the condenser. The steam con-
denses to form weak nitric acid. This liquid fraction enters the
side of the absorption tower while the gaseous fraction enters the
bottom. The two fractions flow countercurrent in the tower.
Cooling water or liquid ammonia are also applied to the tower to
lower and control the temperature of the exothermic reactions and
to induce additional condensation of the steam. Additional
"bleacher" air is supplied to the absorption tower to ensure more
complete formation of NO2 from NO originating both from incomplete
oxidation prior to the absorption tower and formation as a bypro-
duct of the absorption reaction.
Tail gas exits the top of the absorption tower, and typically
contains 0.2% to 0.3% nitrogen oxides by volume (21). The gas
can be circulated as shown in Figure 12 to provide cooling and to
supply power to the air compressor by means of a gas expander.
Tail gas treatment can be achieved by various catalytic systems
which convert the NOX to NO which can be discharged (24). Other
processes, for example, extended absorption or caustic scrubbing
result in cleaner off-gases because they do not produce a stream
with NOX in the exhaust.
Concentration processes are not normally used in nitric acid pro-
duction for fertilizer manufacture. The fertilizer industry uses
dilute acid (55% to 65%) which can typically be produced by the
ammonia oxidation process discussed above without concentration.
Energy recovery from the exothermic reactions as discussed above
provides sufficient energy so that some nitric acid plants can
operate without auxiliary power (21) .
EFFLUENT ORIGINS
Two basic effluent source types exist in a nitrogen fertilizer
plant—point and nonpoint. Point sources are those which origi-
nate as a definite wastewater stream from a particular process.
Nonpoint sources originate from random leaks or from large areas
within a plant. In the following sections, point sources for
each of the four basic processes will be discussed, followed by
a general discussion of nonpoint sources for the entire plant.
Point Sources
Ammonia—
Effluent from the production of ammonia can result from conden-
sate from the steam stripper exhaust or from spent regenerant
used in the ion exchange purification of the recycled condensate.
Condensate must be purified to remove ammonia and other ions
before it can be used as boiler feedwater.
(24) Chemical Week, 98(8):85, 1966,
26
-------
Ammonium Nitrate—
Point sources of wastewater in the ammonium nitrate manufacturing
process may include condensate from the neutralizer and the evap-
orator exhausts and solutions from air pollution control equip-
ment used on the cooler and/or dryer. Less than 50% of the
ammonium nitrate plants condense the exhausts from the neutral-
izer and evaporator. It is estimated that over one-half of these
plants either recycle the material or sell/use it as a dilute
fertilizer solution. Thus less than an estimated 25% of the ammo-
nium nitrate plants release process condensate to a receiving
body or send it into a treatment unit. Effluent from air pollu-
tion control equipment may be blended into fertilizer solutions
where markets exist.
Urea—
Point sources in the manufacture of urea are condensate of the
evaporator exhaust and filtrate from the concentration of urea
solution when a crystallizer is used. Plants using a vacuum
evaporator (^50%) condense the exhaust so that they can recover
the nitrogen value in the stream as a dilute fertilizer (1).
When airswept evaporators are used the exhaust is scrubbed and
vented to the atmosphere, and the scrubbing liquid may be re-
covered as a dilute fertilizer solution. Less than 25% of the
plants use crystallizers (1).
Nitric Acid—
In general there are no point sources of water effluent from the
actual nitric acid manufacturing line (25). There may be efflu-
ent from the cooling towers or spills, and these are covered in
the following sections.
Cooling Towers—
Manufacture of ammonia, urea, and nitric acid requires a cooling
system for temperature control during certain processing steps.
Closed loop cooling towers are generally used, although older
plants may still use once-through or single-pass cooling towers.
The designs of these cooling towers are the same as those of
towers used in other industrial operations.
Closed loop cooling systems require a periodic tower blowdown.
This blowdown is discharged to a receiving body or to a treatment
system. Although the cooling system is a noncontact process, the
blowdown (or discharge in the case of a single-pass system) may
still contain NH3 or nitrate (N03) from two sources. The first
of these is absorption of ammonia from the ambient air (25) .
(25) Train, R. E., A. Cywin, E. E. Martin, and R. Strelow.
Development Document for Effluent Limitations Guidelines and
New Source Performance Standards for the Basic Fertilizer
Chemicals Segment of the Fertilizer Manufacturing Point
Source Category. EPA-440/l-74-011-a, U.S. Environmental Pro-
tection Agency, Washington, D.C., March 1974 168 pp.
27
-------
This complication is especially acute at a nitrogen fertilizer
plant considering the elevated (compared with other ambient
levels) levels of ammonia present. Rainfall in open areas (i.e.,
farmland) has been shown to contain as much as 1.6 ± 0.5 g/m NHs
(26) , and the levels that can be achieved from ambient pickup at
a nitrogen fertilizer plant may be significant. Ammonia will
also be converted to nitrate as a result of bacterial action es-
pecially in hot weather.
A second source of NHs or NO3 is small leaks into the cooling
system from process streams. Even slight leaks may lead to appre-
ciable concentrations of NHs or NO3 in the cooling water. Such
a source occurs in the inlet hot gas line on the nitric acid
plant where flashing causes extreme corrosion. This corrosion
results in leaks to the cooling system.
Other potential pollutants are any inhibitors added to the cool-
ing tower water to prevent corrosion (27). Chemicals such as
copper, chromium, or zinc compounds will definitely show up in
any blowdown in minute amounts. Other compounds used for boiler
feedwater treatment can also appear in the cooling water if the
boiler blows down to the cooling tower.
Nonpoint Sources
In nitrogen fertilizer plants, there are various nonpoint sources
that can contribute a major portion of the water effluent.
Leaks and Spills—
In any plant, a certain number of valve and pump leaks as well as
random spills can be expected. In the nitrogen fertilizer plant,
these leaks can become a major contributor due to the sometimes
corrosive character of the material (25). For example, the carba-
mate recycle is a highly corrosive slurry, and pump seals on such
recycle lines must be replaced frequently. Spills also often
occur at shipping facilities.
Plant and Equipment Cleanup—
Spills are often not cleaned up until there is a general plant
cleanup, unless they are large enough to require immediate atten-
tion. These spills generally occur around loading operations and
are hosed down periodically.
(26) Taylor, A. W., W. D. Edwards, and E. C. Simpson. Nutrients
in Stream Draining Woodland and Farmland near Coshocton,
Ohio.• Water Resources Research, 7(l):81-89, 1971.
(27) Patton, T. H., Jr., W. C. Wood, and R. C. Chopra. Develop-
ment of a Water Management Plan for an Acid Manufacturing
Plant. In: Proceedings of the 28th Industrial Waste Con-
ference, Purdue University, Lafayette, Indiana, 1973.
pp. 1032-1046.
28
-------
Equipment cleanup generally involves the flushing of railroad
cars or trucks. This normally occurs in a specified area with
proper drainage designed specifically for this use.
Other cleanup sources may result when process vessels must be
evacuated and flushed for maintenance and personnel entry.
Additive Filter Cake Back Wash—
The use of additives in the manufacture of high density ammonium
nitrate requires filtration to remove raw material insolubles.
Periodic renewal of the filter cake results in back washing
entrapped nitrate solutions to the sewer.
Runoff—
Rainfall runoff from a plant can be a significant contributor to
a plant's total nitrogen loading because it collects ammonia and
nitrate from the air and washes down the ground and buildings on
which solid fertilizer material may have settled (25).
29
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SECTION 4
EFFLUENT PARAMETERS
As discussed in Section 3, wastewater from the manufacture of
nitrogen fertilizer materials originates from many point and non-
point sources. The quality and characteristics of a given plant
effluent are dependent on the types of processes present at the
complex, plant to plant variations in process design and opera-
tion, equipment age, level of maintenance, plant drainage and
collection, and wastewater treatment methods. These varying
parameters cause the effluents from nitrogen fertilizer plants to
vary significantly from plant to plant. As a result, it is
difficult to define average effluent parameters that are truly
representative of the industry as a whole. The approach that has
been taken in this study is to present the range encountered for
the parameters of concern as well as average values.
EFFLUENT CHARACTERIZATION
Three basic nitrogen pollutant materials occur in wastewater from
nitrogen fertilizer production: ammonia nitrogen (NHa-N) , nitrate
nitrogen (N03~-N), and organic nitrogen (ORG-N). Ammonia nitro-
gen (NH3-N) can exist in either the un-ionized (NH3°-N) or ionized
(NHi,+-N) form depending upon the pH and temperature of the waste-
water. These two forms of ammonia will be treated as separate
species in Section 4. In addition, contaminants other than
nitrogen compounds may be present for a particular unit process.
In the sections following, effluent parameters for each basic
process will be discussed.
Synthetic Ammonia Production
Effluent from the manufacture of ammonia arises when the ammonia
synthesis gas is cooled following the low temperature shift con-
version. As discussed in the process description, the resulting
condensate is routinely steam stripped because EPA regulations
require the industry to reduce ammonia discharged in the water.
The water stream exiting the condensate stripper is suitable for
discharge or recycle as boiler feed water for low pressure
boilers.
Typical concentrations of potential pollutants in the steam strip-
per condensate stream are <50 g/m3 ammonia, <100 g/m3 methanol,
<50 g/m3 carbon dioxide, and minor concentrations of metals
30
-------
.ActUai concentrations vary from unit to unit depending
n* f ? ^rxpper operating parameters (e.g., initial pollu-
tant levels, PH and amount of steam used for stripping) . A
544-metnc ton/day ammonia plant produces about 7.9 x 10~3 m3/s
ofnnf^o JiPPer condensate- S<^ce test data concerning emis-
sions from the condensate steam stripper are reported in I re-
^?^r?^GUlf.S?Ut? Research institute in which the authors
evaluated different techniques for handling steam stripper over-
heads at a typical ammonia plant (7). Complete material balances
were calculated around a 10-m-tall steam stripper at a 900-metric
ton/day ammonia plant generating 1.26 x 10~2 m*/s of process
condensate. The condensate stripper system is shown in Figure 13.
PROCESS
CONDENSATE
OVERHEAD
EFFLUENT
-STEAM
Figure 13. Process condensate steam stripper.
In order to calculate ammonia and methanol effluent factors, a
total of 65 individual source test measurements from Reference 7
were used. The average material balance is shown in Table 4.
TABLE 4. MASS BALANCE AROUND THE CONDENSATE STEAM
STRIPPER—RESULT OF 65 TEST MEASUREMENTS
(kg/hr)
(7)
Stream
Process condensate
Steam
Overhead
Effluent
Stream
flow
rates
80,500
7,980
8,680
81,200
Mass flow rate
Ammonia
39.2
0
41.2
0.57
Methanol
21.1
0
22.7
0.28
Note.—Mass entering the stripper does not exactly
equal mass exiting since these values are
the averages from 65 test measurements.
Effluent factors for ammonia and methanol from this 900-metric
ton/day ammonia plant are shown in Table 5. Average effluent
31
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concentrations were 7 g/m3 for ammonia and 3.4 g/m3 for methanol,
indicating high removal efficiencies ,for this stripper. Less
efficient strippers could have final effluent concentrations ana
effluent factors higher by up to a factor of ten.
TABLE 5. EFFLUENT DISCHARGE FACTORS FOR A
CONDENSATE STEAM STRIPPER (7)
(mg/kg)
Effluent species Effluent discharge factor
Ammonia 15 ± 105%
Methanol 7.5 ± 97%
Note.—Uncertainty values were calculated
using the "Student t" test for 95% confidence
limits.
Concentrations of trace metals in the process condensate, strip-
per overheads, and stripper effluents were measured at six ammo-
nia plants (7). Results of the analyses are presented in Table 6.
For companies 100 and 200, metals were analyzed by flame atomic
absorption spectrophotometry, while samples from companies 400,
500, 600, and 700 were analyzed by graphite furnace atomic
absorption spectrophotometry.
TABLE 6 TRACE METAL CONCENTRATIONS IN PROCESS CONDENSATE (7)
(g/m3)
Company
No.
100
200
400
500
600
700
Average
Chromium
<0.5
<0.5
<0.2
<0.2
<0-2
<0.2
<0-3
Metal
Copper
<0.5
<0.5
<0.02
<0.02
<0.02
0.045
<0.2
concentration
Iron
<0.3
<0.3
<0. 1
<0. 1
<0. 1
-------
TABLE 7. TRACE METAL EFFLUENT DISCHARGE FACTORS
FROM A CONDENSATE STEAM STRIPPER (7)
Average concentration,Effluent discharge factor,
Metal g/m3 g/kg
Chromium
Copper
Iron
Nickel
Zinc
<0. 3
<0.2
<0.2
<0.3
<0. 3
<6
<4
<4
<6
<6
X
X
X
X
X
io-5
io-5
IO-5
io-5
io-5
Effluent factors in Tables 5 and 7 are characteristic of steam
stripper condensate discharged directly to a receiving stream.
If condensate is recycled, the only effluent arises when the
deionization unit used to further purify the condensate is regen-
erated. In such a case, the metal concentrations and short-term
effluent factors will be higher, but material balance considera-
tions show that long-term effluent factors can be no higher than
in the case of direct discharge.
Ammonium Nitrate
Effluent data reported to the Effluent Guidelines Division of the
EPA by the nitrogen fertilizer industry were used as a basis for
setting effluent standards.3 These data are compiled and evalu-
ated in Appendix B. Industry data were supplied for ammonium
nitrate plants, urea plants, and plants manufacturing ammonium
nitrate and urea. Separate data were not reported for effluents
from ammonia and nitric acid production because these processes
were treated as part of ammonium nitrate and urea production.
Effluent from the ammonium nitrate process contained any waste-
water from associated ammonia and nitric acid operations.
Ammonia nitrogen and nitrate nitrogen were found to be the basic
constituents of the wastewater stream from an ammonium nitrate
facility. Average effluent parameters are given in Table 8. The
methodology used in deriving these averages is presented in
Appendix B. In cases where sampling measurements were taken on a
combined ammonium nitrate/urea plant outfall, a proportioning
method was used to arrive at ammonium nitrate effluent factors.
Three ammonium nitrate plants also reported organic nitrogen in
their wastewater at levels of 8.9 g/m*, 14.2 g/m3, and 69.9 g/m* .
This could result from some monoethanolamine from the ammonia
unit or from crossover from the urea plant (all three plants make
ammonium nitrate, ammonia, and urea). Under normal circumstances,
9Data on file at the Effluent Guidelines Division, U.S. Environ-
mental Protection Agency, Washington, D.C., 1977.
33
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organic nitrogen would not be expected in ammonium nitrate
wastewater.
TABLE 8. AVERAGE EFFLUENT PARAMETERS FOR
NITROGEN FERTILIZER PLANTS
Parameter Ammonium nitrate3
Wastewater effluent flow rate, m3/s 0.0327 0.0399
0.862 0.756
N03-N 0.471 . 0
ORG-N 0 0.275
Effluent concentration, g/m3:
NHa-N 482 120
NO?--N 121 0
ORG-N 0 90
aAn average plant produces 386 metric tons/day of ammonium
nitrate.
An average plant produces 342 metric tons/day of urea.
Urea
Ammonia nitrogen and organic nitrogen were found to be the basic
constituents, of the wastewater stream from a urea facility.
Their average effluent factors are derived in Appendix B and
shown in Table 8. As in the case of ammonium nitrate, some
plants reported data for a combined plant outfall. A proportion-
ing method, described in Appendix B, was used to calculate urea
effluent factors.
Three urea plants reported nitrate nitrogen in their wastewater
at levels of 6.3 g/m3, 6.9 g/m3, and 23.6 g/m3. This is probably
caused by crossover in the drainage systems or by drift of ammo-
nium nitrate material in the air into the urea drainage system,
since all three plants also produced ammonium nitrate. Nitrate
could also result from the conversion of ammonia or urea to
nitrate by biological action, but it was not reported by any
plant manufacturing only urea.
Nitric Acid
Effluent data are not available for wastewater originating solely
from a modern nitric acid plant with a recirculating cooling
system. Aggregated data are reported in the section on ammonium
nitrate effluents. Values of effluent parameters for two nitric
34
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acid plants equipped with single-pass cooling systems are pre-
sented in Table 9 (28, 29). These data are not typical of the
industry where the only point source effluent from nitric acid
production is cooling tower blowdown.
TABLE 9. EFFLUENT FROM NITRIC ACID PLANTS
WITH SINGLE-PASS COOLING SYSTEMS
Production,
Parameter
metric tons/day (100% HNOs)
Plant A
180
Plant B
51
Effluent concentration, g/m3 :
NH3-N
N03~-N
ORG-N
Effluent flow rate, m3/day
pH
Reference
0.03
5.0
0.02
34,900
3.1
28
0.3
0.8
_a
4,040
7.7
29
Data not reported.
POTENTIAL ENVIRONMENTAL EFFECTS
Factors that bear on the evaluation of the potential environ-
mental effects of a particular wastewater discharge include the
hazard potential of the waste, discharge quantities, and type of
receiving body. In this section, these parameters are quantified
and then combined to determine another parameter called the
source severity, which is used to measure the potential impact
of a wastewater discharge on a receiving stream.
As mentioned previously, there are three types of nitrogen mater-
ials released in the effluent from nitrogen fertilizer plants:
ammonia nitrogen, nitrate nitrogen, and organic nitrogen. Other
minor contaminants, such as trace metals and water treatment com-
pounds, are also present but more difficult to characterize
because they are lower in concentration and dependent on individ-
ual plant design and operation.
(28) Patterson, J. W., J. Brown, W. Duckert, J. Poison, and
N. I. Shapira. State of the Art: Military Explosives and
Propellants Production Industry. Volume II, Wastewater
Characterization. EPA-600/2-76-213b, U.S. Environmental
Protection Agency, Cincinnati, Ohio, August 1976. 273 pp.
(29) Fairall, J. M. Tennessee Valley Authority, Wilson Dam,
Alabama--Nos. 1 and 2 Nitric Acid Units, Tennessee River.
U.S. Department of the Interior, Tennessee Valley Authority
- and Federal Water Pollution Control Administration,
Cincinnati, Ohio, May 1966. 12 pp.
35
-------
Hazard Potential
Hazard potentials were arrived at by determining acceptable
concentrations for each species in receiving streams. This con-
centration was then termed the hazard factor because higher con-
centrations may pose a potential hazard to aquatic life in the
stream or to people who drink the water.
Established water quality criteria were used as hazard factors
whenever possible, but in the absence of such criteria other
data on health or toxic effects were used to determine estimated
acceptable concentrations.
In general, the health effects data base is incomplete and the
hazard factors include a safety factor to allow for more sensi-
tive species. As more data become available, the hazard factors
used in this report may be revised upward because the margin of
safety is greater than necessary.
Ammonia Nitrogen—
When ammonia is present in water, a chemical equilibrium exists
between un-ionized ammonia, ionized ammonia, and hydroxide ions
as shown in Equation 15 (30).
NH3° + H20 t NH3.H20 J NH<,+ + OH~ (15)
At a given temperature, the percentage of un-ionized ammonia in
solution can be found on Figure 14 (31).
Un-ionized ammonia (NH3°) is the most toxic form of ammonia. A
water quality criterion of 0.02 g/m3, based on fish toxicity
and including a ten-fold safety factor, has been assigned to un-
ionized ammonia nitrogen (30). Thus 0.02 g/m3 was chosen as the
hazard factor for un-ionized ammonia nitrogen. At least one
investigator has found the ionized form of ammonia (NH^+) to be
toxic, but at levels much higher than those for NH3. He esti-
mates the toxicity of NH*+ to be less than 1/50 that of NH3° (30).
On this basis, a value of 1.00 g/m3 was selected as a hazard
factor for ionized ammonia nitrogen.
Nitrate Nitrogen—
The toxicity of nitrate nitrogen (N03--N) in waters is due to its
potential conversion to nitrite, which has been shown to be high-
ly detrimental to the blood stream (30) . A value of 10 g/m3 has
(30) Quality Criteria for Water. EPA-440/9-76-023, U.S. Environ-
mental Protection Agency, Washington, D.C., July 1976
501 pp.
(31) Thurston, R. V., et al. Aqueous Ammonia Equilibrium Calcu-
lations. Fisheries Bioassay Laboratory Technical Report
No. 74, Montana State University, Bozeman, Montana, 1974
18 pp.
36
-------
10.0
Figure 14. Percent un-ionized ammonia in aqueous
ammonia solutions of zero salinity.
been established as a water quality criterion for nitrate nitro-
gen in domestic water supplies (30), and hazard factor of 10 g/m3
was therefore used for nitrate nitrogen.
Organic Nitrogen
The predominant form of organic nitrogen (ORG-N) in the waste-
water stream from a nitrogen fertilizer plant is urea. Other
forms (e.g., amines or amides) of organic nitrogen may be present,
as discussed previously, but will be considered negligible in
light of the larger concentrations of urea.
An LD50 (lethal dose for a 50% kill of rabbits when dosed sub-
cutaneously) of 3,000 mg/kg has been established for urea (32).
The following equation has been derived to convert LD50 values
for animals other than rats to hazard factors (33):
(32) Registry of Toxic Effects of Chemical Substances, 1975
Edition. CDC-99-74-92, National Institute for Occupational
Safety and Health, Rockville, Maryland, June 1975. 1296 pp.
(33) Reznik, R. B., E. C. Eimutis, J. L. Delaney, T. J. Hoogheem,
S. R. Archer, J. C. Ochsner, W. R. McCurley, and T. W.
Hughes. Source Assessment: Prioritization of Stationary
Water Pollution Sources. EPA-600/2-77-107p, U.S. Environ-
mental Protection Agency, Research Triangle Park, North
Carolina, December 1977. 137 pp.
37
-------
Hazard factor = 2.25 x 10~3 x LD50
(16)
From this equation and the LD50 of 3,000 mg/kg, the hazard factor
for urea in the effluent is calculated to be 6.75 g/m3. This is
equivalent to a measurement of 3.17 g/m3 organic nitrogen (6.75
g/m3 x 47 g N/100 g urea) .
Discharge Quantities
Discharge quantities are determined by multiplying wastewater
effluent flow rates and effluent concentrations. This gives a
mass quantity for use in evaluation purposes, and does not con-
sider the impact of in-plant dilution.
Receiving Body
Potential environmental effects are strongly dependent upon the
type of receiving body into which plant effluent is discharged.
Types of receiving bodies include sewers, dry ditches, canals,
tributaries, large rivers, and lakes. In this report, the receiv-
ing body is defined to have a volumetric flow rate equal to the
flow rate of the receiving body upstream of the plant plus the
flow rate of the plant discharge. In many cases, the correction
introduced by the flow rate of the plant discharge will prove
negligible; however, it is an important consideration for dis-
charge into a dry bed or small stream.
Probable receiving bodies for nitrogen fertilizer plants are
listed in Appendix A, Table A-2. Sewers and lakes do not appear
on the list and will not be considered further. Table A-3 lists
the available data on pH and temperature for the receiving
streams identified in Table A-2. Stream pH varied from 6 . 2 to
8.8 with an average of 7.6; temperatures ranged from 0°C to 33°C
with an average of 16 °C.
Source Severity
Source severity compares the concentration of a given pollutant
in the receiving water as a result of discharge to the minimum
concentration of the pollutant determined to be hazardous (hazard
factor) . In determining the source severity of a plant, the dis-
charge quantity is compared to the receiving body flow rate times
the hazard factor according to Equation 17.
S
"
V
R
38
-------
where S = source severity for a particular pollutant
VD = wastewater effluent flow rate, m3/s
CD = concentration of particular pollutant, g/ra3
VR = volumetric flow rate of receiving body above plant
discharge, m3/s
F = hazard factor for particular pollutant, g/m3
Source severities were calculated for plants producing either
ammonium nitrate or urea based on available data (Tables B-l and
B-2, Appendix B) , and the results are presented in Tables 10 and
11. Nitrate nitrogen, organic nitrogen, and the two forms of
ammonia, un-ionized (NH3°-N) and ionized (NHi4+-N), were the pol-
lutant species considered in the source severity calculations.
Receiving water pH and temperature are important parameters in
determining the species of ammonia present. Therefore, severi-
ties were calculated at two receiving water pH levels, pH 7.6
and pH 9.0. These pH levels correspond to the average and maxi-
mum receiving water pH. The average receiving water temperature
of 16 °C was used in source severity calculations.
Source severities at each plant were calculated for each pollut-
ant species based on the low and mean receiving body flow rates
at the plant. The low flow rate represents a worst case example
because it gives the smallest denominator in Equation 17, result-
ing in the largest source severity. The mean receiving body flow
rate is indicative of average river flow conditions.
Source severities were also calculated for plants producing both
urea and ammonium nitrate. In order to estimate these severities,
Equation 17 was modified to Equation 18.
+ (V°u)
s
"
where V = volumetric flow rate from ammonium nitrate plant,
AN m3/s
V = volumetric flow rate from urea plant, m3/s
U
V = volumetric flow rate of receiving body, m3/s
R.
C = concentration of given pollutant in ammonium
DAN nitrate discharge, g/m3
C = concentration of given pollutant in urea discharge,
DU g/m3
F = hazard factor for particular pollutant, g/m3
S = source severity for particular pollutant
39
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TABLE 10. CALCULATED SOURCE SEVERITIES FOR PLANTS PRODUCING
AMMONIUM NITRATE (INCLUDING NITRIC ACID AND AMMONIA)
Source severity
Plant
code
sa
X
z
BB
FP
Average
Standard
Produc-
tion,
metric
tons/day
147
309
336
342
241
654
deviation
Receiving
body
flow rate,
n>3/s
Low Mean
0.50 0.57
71 1,020
81 317
76.5 377
303 3,210
41 415
NH3°-N NH«+-N
Low receiving
body flow rate
at pH 7.6
1.62
4.9 x ID"2
2.1 x ID"2
0
4.4 x ID"3
2.7 x lO-2
2.5 x lO-2
1.8 x lO-2
at pH 9.0
35.5
10.3
4.7 x 10— '
0
9.5 x 10-2
6.0 x 10~1
5.5 x 10—"
3.8 x 10~1
Mean receiving
body flow rate
at pH 7.6
1.42
3.4 x ID"3
5.5 x ID"3
0
4.2 x 10~*
2.7 x lO-3
3.0 x lO-3
2.1 x 10-3
at pH 9.0
31.1
7.2 x 10-2
1.2 x 10— '
0
9.0 x 10~3
5.9 x 10-2
6.5 x lO-2
4.6 x 10-2
Low receiving Mean receiving
body flow rate body flow rate
at pH 7.6 at pH 9.0 at pH 7.6 at
3.19 2.50 2.80
9.5 x lO-2 7.5 x i0-2 6.6 x 10-3 5.
4.2 x 10-2 3.3 x 10-2 1.1 x 10-2 8.
000
8.6 x lO-3 6.8 x 10-3 8.2 x IQ-* 6.
5.4 x lO-2 4.2 x 10-2 5.3 x IQ-S 4.
5.0 x lO-2 3.9 x 10-2 5.9 x io-3 4.
3.6 x 10-2 2.8 x iQ-2 4.2 x i0-3 3.
pH 9.0
2.19
2 x lO-3
6 x 10~3
0
4 x 10-*
2 x lO-3
3 x lO-3
3 x 10~3
N03-
Low
receiving
body
flow rate
3.8 x 10— '
7.6 x 10-3
3.5 x ID-3
0
8.2 x lO"3
3.3 x lO-3
5.6 x lO-3
2.6 x 10~3
-N
Mean
receiving
body
flow rate
3.3
5.0
9.0
5.0
3.2
4.4
3.6
x 10"1
x 10-*
x 10~*
0
x 10~s
x 10~*
x 10-*
x 10-*
Excluded from average to prevent low river flow rate «1 m3/s) from skewing the data.
Excluded from average because plant is practicing zero discharge.
TABLE 11. CALCULATED SOURCE SEVERITIES FOR PLANTS
PRODUCING UREA (INCLUDING AMMONIA)
Receiving water temperature equals 16°C
Source severity
Plant
code
Production
metric
tons/day
Receiving
body
NH39-N NHu+-N
flow rate. Low receiving
m3/s body flow rate
Low Mean at ph 7.6
at pH 9.0
Mean receiving
body flow rate
at pH 7.6
at pH 9.0
Low receiving
body flow rate
at pH 7.6
at pH 9.0
Mean receiving
body flow rate
at pH 7.6
at pH 9.0
ORG-N
Low Mean
receiving receiving
body body
flow rate flow rate
C 1,083 5,975 17,896 3.5 x 10~5 7.6 x 10~* 1.2 x IQ-' 2.5 x 10~* 6.8 x 10~5 5.4 x 10~s 2.3 x 10~5 1.8 x 10~s 1.5 x 10~5 4.9 x 10~6
F 161 498 1,986 4.3 x 10~* 9.5 x 10 ~3 1.1 x 10~* 2.4 x 10~3 8.6 x 10~* 6.7 x 10~* 2.2 x 10~* 1.7 x 10~» 1.3 x 10~* 4.5 x 10~5
L 701 5,975 17,896 3.4 x 10~* 7.5 x 10 ~3 1.1 x 10 ~* 2.5 x 10~3 6.7 x 10~* 5.3 x 10~* 2.2 x 10~* 1.8 x 10~* 3.2 x 10~5 1.1 x 10~s
Average 2.7 x 10"* 5.9 x 10~3 7.7 x 10~5 1.7 x 10~3 5.3 x 10~* 4.2 x 10~* 1.5 x 10~* 1.2 x 10~* 5.9 x 1Q-S 2.0 x 10~5
Standard deviation 2.1 x 10~* 4.6 x 10~3 5.6 x 10~s 1.3 x KT3 4.1 x 10~* 3.2 x 10~» 1.1 x 10~* 9.0 x 10~s 6.2 x 10~5 2.2 x 10~8
-------
Input data for calculating source severities from composite
plants are presented in Tables B-l and B-2 and are summarized in
Table 12. Source severity values for the composite plants for
which adequate data are available are presented in Table 13.
Average source severity values are also presented in Tables 10,
11, and 13. Plants with low river flow rates (<1 m3/s) are ex-
cluded from these averages in order not to skew the data and give
an inaccurate view of the total industry. Because the river
flow rate appears in the denominator of the source severity
equation, low value can bias a set of data. Flow rate data
listed in Table A-2 in Appendix A show that M.0% of the plants
in the industry discharge to rivers with mean flow rates of
under 1 m3/s.
Effluent data tabulated in Appendix B was supplied by industry
to EPA as a basis for setting the effluent guideline standards as
given in Table 14 (34) . Standards for best practicable technol-
ogy (BPT) are based on average effluent data from all plants
within an industry category. Standards for best available tech-
nology (BAT) are based on those plants with the lowest effluent
values. For the plants reporting data, 13 out of 31 ammonium
nitrate plants and 12 out of 22 urea plants met the BPT stand-
ards. For BAT, 6 out of 31 ammonium nitrate plants and 10 out
of 22 urea plants met the guidelines. It is expected that those
plants that exceeded the guidelines have taken or are taking
steps to reduce their effluent loading and come into compliance
with the regulations.
Effluent guideline standards specify a certain effluent quality
that must be achieved by plants within an industry. However,
there are no restrictions in terms of the type of controls that
must be used to meet the standards. Each plant may choose what-
ever control option is best suited to operating practices at its
location, provided that final effluent quality is within the
guidelines. In the case of ammonium nitrate manufacture, ion
exchange technology is named as one example of BAT, but that is
not intended to limit plants from using alternative control
strategies if they wish.
Source severities can also be calculated for individual ammonia
plants (34% of the nitrogen fertilizer plants) based on effluent
data presented earlier in this section for pilot testing of a
condensate steam stripper. Based upon the data presented in
(34) Code of Federal Regulations, Title 40 - Protection of Envi-
ronment, Chapter I - Environmental Protection Agency, Sub-
chapter N - Effluent Guidelines and Standards, Part 418 -
Fertilizer Manufacturing Point Source Category. Ammended
regulations published in Federal Register 43(81):17821-17828,
1978.
41
-------
to
TABLE 12. INPUT VALUES OF VD, CD, AND VR USED TO CALCULATE SOURCE
SEVERITY FOR COMPOSITE NITROGEN FERTILIZER PLANTS
Receiving water temperature equals 16°C
Plant
code
B
G
H
I
J
M
N
P
R
S
T
U
V
m3/s
0.000441
0.1108
0.0016
0.0736
0.0045
0.0074
0.002
0.0193
0.2174
0 . 0515
0.0193
0.00907
0.0213
Urea
CD(NH3-N),
g/m3
68
18
1,030
5
83
241
198
308
92
291
222
112
495
Ammonium nitrate
CD(ORG-N),
g/m3
a
1
82
11
104
455
3,640,
a
17
16
160
112
1,169
VD,
m3/s
0.00195
0.1211
0.0009
0.00286
0.0263
0.00113
0.0007
0.0205
0.252
0.0840
0.0034
0.0507
0.0591
CD(NH3-N),
g/m3
65
17.8
9,111
141
83.1
2,110
0.1
229
17.5
291
5,200
149
495
CD (N03 -N) ,
72
3.7
951
92.9
71.6
2,900
0.1
229
19.0
75.3
780
89
148
Receiving body
flow T"at** - Tn3/e2
VR(LO)
377
5
0.05
0.5
205
50
518
227
317
5,975
498
156
6,400
VR(Mean)
1,305
90
0.68
4
448
177
1,420
1,005
1,190
17,896
1,986
331
19,930
Not available.
-------
u>
TABLE 13. CALCULATED SOURCE SEVERITIES FOR PLANTS PRODUCING AMMONIUM
NITRATE AND UREA (INCLUDING NITRIC ACID AND AMMONIA)
Source severity
NHa'-N NH»+-N HOa'-N ORG-N
Low receiving
Plant
code
B
G
HK
r*
J
M
K
P
R
S
T
U
V
Average
Sd
body flow rate
at pH 7.6
2.1 x 10-*
4.0 x 10-1
98.5
6.7 x 10-1
6.2 x 10-3
4.2 x 10-2
3.8 x 10-*
2.3 x lO-2
3.8 x lO-2
3.3 x lO-3
2.2 x ID"2
2.7 x 10-2
3.1 x lO-3
5.1 x 10-2
1.2 x 10-1
at pH 9.0
4.6 x 10-3
8.74
2,167
14.8
1.4 x 10-1
9.2 x 10-1
8.4 x 10"**
5.1 x 10-1
8.4 x 10-1
7.2 x 10-=
4.8 x 10-'
6.0 x 10-1
6.8 x 10-=
1.12
2.55
Mean receiving
body flow rate
at pH 7.6
6.0 x 10~s
2.3 x 10-2
7.24
9.4 x lO-2
2.9 x 10-3
1.2 x 10-2
1.4 x 10~s
5.3 x 10-3
1.0 x ID"2
1.1 x lO-3
5.5 x 10-3
1.3 x ID"2
1.1 x lO-3
6.7 x lO-3
7.2 x lO-3
at pH 9.0
1.3 x ID"3
5.1 x 10-1
Low receiving
body flow rate
at pH 7.6
4.1 x 10-"
7.9 x 10-1
159 184
2.00 1.
6.3 x 10-2
2.6 x 10-1
3.1 x 10-*
1.2 x 10-1
2.2 x 10-1
2.4 x lO-3
1.2 x 10-1
2.8 x 10-1
2.2 x lO-2
1.5 x 10-1
1.6 x 10— '
33
1.2 x lO-2
8.2 x lO-2
7.6 x 10-=
4.6 x lO-2
7.6 x 10-2
6.5 x lO-3
4.4 X 10-2
5.4 x 10-2
6.2 x lO-3
1.0 x 10-'
2.3 X 10-"
at PH 9.0
3.2 x 10-*
6.2 x 10-1
145
1.05
9.7 x 10-3
6.5 x 10-2
6.0 x 10~s
3.6 x 10-2
6.0 x 10~2
5.1 x lO-3
3.5 x 10-2
4.3 x 10-2
4.8 x lO-3
8.0 x 10-2
1.8 x 10-1
Mean receiving
body flow rate
at pH 7.6
1.2 x 10~*
4.6 x 10-2
13.5
1.9 x 10-1
5.7 x lO-3
2.3 x 10-a
2.8 x 10-5
1.1 x 10-2
2.0 x lO-2
2.2 x 10-3
1.1 X 10-2
2.6 x 10-2
2.0 x 10-3
1.3 x lO-2
1.4 x 10-2
at pH 9.0
9.4 x 10~s
3.6 x 10-2
10.7
1.5 x 10-1
4.4 x 10-3
1.8 x lO-2
2.2 x 10~5
8.2 x lO-3
1.6 x lO-2
1.7 x 10-3
8.6 x 10-2
2.0 x 10-2
1.6 x lO-3
1.0 x lO-2
1.1 x 10-2
Low
receiving
body
flow rate
1.2 x 10-*
8.6 x 10-3
1.71
5.3 x ID"2
9.2 x 10-"
6.6 x ID"3
-------
TABLE 14. EFFLUENT GUIDELINES (34)
Effluent guideline, q/kq
Product
Urea (solutions)
Effluent
species
NH3-N
ORG-N
Best practicable
technology
Daily Monthly
maximum average
0.95 0.48
0.61 0.33
Best available
technology
Daily Monthly
maximum average
0.53 0.27
0.45 0.24
Urea (prilled or
granulated)
Ammonium nitrate
NH3-N
ORG-N
NH3-N
N03-N
1.
1.
0.
0.
18
48
73
67
0
0
0
0
.59
.80
.39
.37
0
0
0
0
.53
.86
.08
.12
0.
0.
0.
0.
27
46
04
07
Table 4 and low and mean receiving body flow rates of 6 6 m3/s
and 18 m3/s, respectively, source severities for ammonia NH3°)
and ammonium (NH4+) were calculated and are presented in Table 15,
Plants with less efficient steam strippers could have source
severities higher by up to a factor of ten under the same condi-
tions (i.e., same size plant and same receiving stream).
TABLE 15. CALCULATED SOURCE SEVERITIES FOR A CONDENSATE
STEAM STRIPPER OF AN AMMONIA PLANT
Receiving water temperature equals 16°C
Source severity
Low receiving water flow rate:
Receiving water pH = 7.6
Receiving water pH = 9
Mean receiving water flow rate;
Receiving water pH = 7.6
Receiving water pH = 9
NH3°-N
1.13 x ID"2
2.76 x 10-1
3.77 x 10-3
9.21 x ID-2
2.61 x ID-2
2.08 x ID-2
8.71 x lO-3
6.94 x ID-3
For those plants that recycle process condensate rather than dis-
charge it, the source severities should still be similar, because
the condensate must be purified before use as boiler feedwater.
In this case spent regenerant from the ion exchange units used
for purification becomes the discharge stream. However, material
44
-------
balance considerations show that the discharge stream must con-
tain the same amount of NH3-N as the condensate from the steam
stripper.
Other Considerations
In applying the source severity equation (Equation 18), it is
assumed that the greatest impact occurs where the discharge is
mixed with the receiving stream. In reality, the situation may
be different when considering NH3-N and urea. Urea and ammonia
put an oxygen demand on the stream some distance downstream as
NH3 and urea are naturally oxidized by nitrifying bacteria to
NOz"/ NO3~, and CO2. If the receiving stream is low in dissolved
oxygen and has a low capacity to reoxygenate, toxicity to aquatic
life in the stream may be caused by an oxygen depletion some dis-
tance downstream from the discharge rather than by ammonia or
urea toxicity near the discharge point.
To determine the potential effect due to oxygen depletion by
urea and ammonia, the following assumptions are made:
• No reaeration of the receiving body takes place while NH3
and urea are being oxidized.
• All of the entering NH3 and urea is completely oxidized
to COa and N03~ by the oxygen in the receiving body.
• 2 moles of oxygen are required to oxidize 1 mole of NH3,
or 3.76 g of Qz per gram of NH3.
• 7 moles of oxygen are required to oxidize 1 mole of
urea, or 8 g of Oz per gram of ORG^N.
In addition, the following average flow characteristics describ-
ing the wastewater from a composite ammonium nitrate urea plant,
as shown in Tables B-5 and B-6, are used to determine the worst
case flow conditions:
• Flow rate of the discharge stream originating from the
urea plant is 0.0399 m3/s; it contains 120 g/m3 NH3-N
and 90 g/m3 ORG-N.
• Flow rate of the discharge stream originating from the
ammonium nitrate plant is 0.0327 m3/s; it contains
482 g/m3 NH3-N.
• Flow rate of the receiving stream is 771 m3/s.
With the above conditions, the oxygen demand can be calculated
as follows:
45
-------
oxygen
de and = ^(pollutant discharge rate)(molar ratio)
aemana receiving body flow rate
|[(482) (0.0327)1 + [ (120) (0.0399)] \3.76 + \[ (90) (0.0399)318
771 + .0327
=0.14 g/m3 O2
Considering that this approximates a worst case situation, the
oxygen concentration demand is not significant when compared to
normal oxygen concentrations (^10 g/m3), and toxicities are con-
sidered more important parameters in evaluating the impact of
effluent discharge on stream quality.
Wastewater constituents other than nitrogen derivatives were
reported by some plants, and they are listed in Table 16. As can
be seen, there are no other significant constituents discharged
by ammonium nitrate plants, urea plants, or nitrogen fertilizer
complexes. Source severities were therefore not calculated for
these minor constituents.
TABLE 16. MINOR CONSTITUENTS PRESENT
IN PLANT EFFLUENTS
Plants producing both
Ammonium nitrate plants Urea plants urea and ammonium nitrate
Parameter
pH
Temperature , °C
Total suspended solids, g/m3
Total dissolved solids, g/m3
Chemical oxygen demand, g/m3
R x z jj ii a
7.2 7.7 6.3 7.6 6.3 7.1
13 13
29 11 1.5
18
67 29
R B E G K N
7.5 8.2 7.2 8.4 7.4 8.3
34 32 4 10
100 74 12
P Q
7.6 8.0
7
5-Day biochemical oxygen demand, g/m3 8
Total hardness as CaCOa, g/m3 8
Calcium hardness as CaCOa, g/m3
Magnesium hardness as CaCOa, g/m3 10
Total alkalinity as CaCOa, g/m3
Sulfate (S0»), g/m3 2
Chloride (Cl), g/m3 4
Sodium (Ha), g/m3 3
Total iron (Fe), g/m3
Total phosphate (PO»), g/m3 0.7
Manganese (Mn), g/m3 0.1
Copper (Cu), g/m3 0.12
Chromate (Cr), g/m3 0
Silica (SiOa), g/m3
Oil and grease, g/m3
nickel (Ni), g/ma
Zinc (Zn), g/m3 0
Cyanide (Cn~), g/m3 0.12
Residual C12, g/m3 3.6
<3
16
0
16
0
3
5
0.03
0.7
0
0.12
0.02
0.3
0.52
1.1
0.7
Note.—Blanks indicate data not available, and dashes indicate reported plant intake concentration greater than
reported effluent concentration.
46
-------
SECTION 5
CONTROL TECHNOLOGY
Control technology as applied to the wastewater effluent from
nitrogen fertilizer plants is used basically to control the
following primary contaminants: ammonia nitrogen, organic
nitrogen and nitrate nitrogen. Control technologies may focus
on a particular process discharge or may be applicable to an
entire plant complex.
TYPES OF CONTROL
Containment
Containment is used basically to control effluents from nonpoint
sources such as pump seal leaks, spills, and plant washdowns. It
is achieved by using a small dike or by proper drainage design.
If the area is not drained but simply enclosed by a dike (usually
less than 0.15 m high), evaporation controls the effluent level
and no discharge occurs. If the area is drained, however,
additional control technology is needed just as if the effluent
were from a point source.
Containment is used to some degree at almost every nitrogen
fertilizer plant. The degree of application may range from a
simple dike around a couple of pumps to entire areas drained by
an underground system. Newer plants are anticipated to have an
increasing amount of containment as an awareness of the level of
nonpoint source effluents increases. In addition, older plants
often incorporate a containment system in newly installed control
systems.
In any situation where wastewaters are contained in ponds or be-
hind dikes, there is the possibility that materials can leach or
percolate through the soil into underground water supplies.
Nothing is presently known about whether this may be a potential
problem at nitrogen fertilizer plants.
Steam Stripping
Steam stripping is used on process condensate from nitrogen
fertilizer plants for the removal of ammonia, carbon dioxide and
methanol. The condensate stripper in its simplest form passes
low pressure steam countercurrent to the condensate in a packed
or tray tower. Overhead product from the stripper is vented
directly to the atmosphere or recovered for the value of its
47
-------
ammonia content. Stripping occurs at a pressure adapted to the
pressure of the recirculation section if offgases are to be
recovered. The content of ammonia in the stripped condensate
ranges from 5 g/m3 to 100 g/m3 and is highly dependent on the
amount of steam and the pH of the contaminated feed condensate
(25) . In neutral solutions ammonia exists mainly as the ammonium
ion while at higher pH (11 to 12) ammonia exists as dissolved
gas. Residual methanol in stripped condensate varies but usually
is in the range of 20 g/m3 to 100 g/m3 (9) . Stripped condensate
is either discharged into a receiving stream or used as cooling
water makeup or as boiler feedwater.
The ammonia concentration of the effluent is lowered by increas-
ing the amount of stripping steam. However, increasing steam
usage will dilute the overhead product and may adversely affect
the water balance of the recirculation system. Addition of a
refluxing system can be used in producing a concentrated overhead
product from dilute (approximately 1,000 g/m3) condensate streams.
The more concentrated overhead may then be recycled. Either one
of these modifications may be uneconomical or produce a stream
incompatible with present operation.
Under a grant awarded through the U.S. Environmental Protection
Agency (EPA), the Louisiana Chemical Association (LCA) partici-
pated in the study and development of a reflux system (35) . A
schematic diagram of the pilot steam stripper used is shown in
Figure 15 (35). The stripper was operated as a fractionator, as
overhead would be totally condensed and reflux provided. The
pilot stripper achieved 98% and 99.8% removal of ammonia and
methanol, respectively. Maximum overhead ammonia concentration
was 6% (60,000 g/m3) with a minimum bottoms concentration of
20 g/m3 (35). Process condensate with an average concentration
in the range of 1,000 g/m3 ammonia and 600 g/m3 methanol was used
in the process. In this study the overhead condensate was sent
to the primary reformer and incinerated. The overhead may also
be recycled as feedstock, but this alternative requires more
energy.
Air Stripping
Air stripping of ammonia from wastewater has in the past been
focused primarily in the municipal wastewater treatment area.
Its potential application to nitrogen fertilizer plant effluent
is direct because in both cases the objective is to remove
(35) Romero, C. U., and F. H. Yocum. Treatment of Ammonia Plant
Process Condensate. In: Proceedings of the Fertilizer
Institute Environmental Symposium (New Orleans, Louisiana
January 13-16, 1976), The Fertilizer Institute, WashingtoA,
D.C. pp. 45-89. 3 '
48
-------
CONDENSER-
FEED
' MANOMETER
Figure 15. Model of pilot steam stripper (35).
ammonia. Currently at least one ammonia plant practices air
stripping to remove ammonia from process condensate (36) .
Some testing has been done on air stripping ammonium nitrate
effluent. These tests have shown that the ammonia concentrations
in the stripping air did not exceed 10 mg/m3 (25) . Information
on the percent removal of ammonia in the effluent stream as a
function of operating parameters is not available. Some of the
critical parameters are bed depth, transfer medium, surface
loading rate, and proper pH. Disadvantages to air stripping are
the decrease in efficiency due to cold weather operation and the
deposition of calcium carbonate scale from the water on the
column packing or internals resulting in plugging (25). Figure 16
is a schematic of a tower used for ammonia air stripping.
Urea Hydrolysis
This treatment system is designed to process condensate contain-
ing urea by converting the urea through a series of intermediate
products back to ammonia and carbon dioxide. The ammonia and
C02 are then driven off with steam.
Decomposition of urea into its basic components may be effected
in two methods: biological conversion or thermal hydrolysis.
In the biological process, urease enzyme produced by Bacillus
Pasteuri acts to decompose the urea into NH3 and CO2 (37) . This
(36) Personal communication with T. W. Segar, N-ReN Corporation,
Cincinnati, Ohio, June 1978.
(37) Smit, A. C. M., and P. U. C. Kaasenbrood. Treatment of
Urea-Plant Effluents. Industrial Wastes, 22(5):44-47, 1976.
49
-------
WA1EHW DISTRIBUTION
1 BASIN
- TYPICAL FILL
.BAFFLE (TYPICAL)
Figure 16. Ammonia/condensate air stripping (25).
decomposition takes place on a fixed carbon bed that serves as
a support for the aerobic bacteria. Oxygen and nutrients needed
by the bacteria are added, because they are not supplied in the
process condensate feed. Major drawbacks of this biological
treatment system are the following:
• Air supplied to support bacterial growth must be
washed free of ammonia.
• The biological process is very sensitive to
fluctuations in the feed streams.
• Much time is needed to achieve optimum column performance.
As a result of these major drawbacks, no biological conversion
systems are currently in operation.
In the thermal hydrolysis process, a single tower is used for
both hydrolysis and desorption. Heated urea process condensate
is fed directly to the stripper tower where dissolved urea is
hydrolyzed to ammonium carbamate, and ammonium carbamate is
decomposed to gaseous ammonia and C02, which exit overhead. This
process is carried out at temperatures above 100°C and under pres-
sures of up to 1.8 MPa (25). . Overhead vapors containing the ammo-
nia and C02 have a relatively low concentration of water vapor
and can be returned to the urea plant for recovery without affect-
ing the reactor water balance or increasing steam consumption in
the ammonium carbamate recycle loop.
50
-------
A somewhat modified hydrolysis stripping unit has been developed
by CF Industries and is shown diagramatically in Figure 17 (38) .
In this operation, the condensate enters a low pressure boiler
operating at 57 kPa and 85°C. The condensate is evaporated and
the urea in the stream is hydrolyzed to ammonia and C02. Approx-
imately 93% of the vapor goes through the condenser to the top of
the stripping column. The remainder is discharged to the lower
section. Approximately 7% of the condensate water containing
about 86% of the ammonia and carbon dioxide are recycled to the
process through a condenser (38).
The bottom stream containing the remainder of the water, ammonia,
and CC>2 goes to a deaerator operating at 448 kPa and 148°C for
removal of approximately 85% of the residual contaminants. The
bottom stream from this unit is of sufficient quality to go to a
high pressure boiler (38).
RECYCLE TO
PROCESS
FROM
CRYSTALLIZER-
CONDENSER
LOW PRESSURE
BOILER
STRIPPING
COLUMN
EXHAUST
I
DEAERATOR
HIGH PRESSURE
BOILER
Figure 17.
Method for Treatment of Urea
Crystallizer Condensate (38).
Condensate. U.S.
November 25, 1975.
51
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A number of hydrolysis stripper units are now in operation and
more are expected as urea producers strive to meet plant effluent
standards for 1977 and 1983. Three Technip SD Plants hydrolyzer
strippers already are operating in the United States. The newest
is at Atlas Powder's 272-metric ton/day plant in Joplin, Missouri,
which started up earlier in 1977. It uses a 14-m high tower that
is 1.14 m in diameter to handle waste flows with ammonia levels
up to 15% and urea up to 3% by weight. An ammonia stripper at
the 236-metric ton/day Cooperative Farm Chemicals Assn. urea plant
in Lawrence, Kansas went on stream in 1972 (39). These two units
are retrofits to existing plants. Technip SD Plants' units will
reduce effluent urea and ammonia to 20 g/m3 (39). Vistron's only
operating unit is at its own 635-metric ton/day urea plant in
Lima, Ohio, but the Vistron system will be used in the 907-metric
ton/day urea plant being built in Kenai, Alaska, as a joint ven-
ture of Union Oil's Collier Carbon & Chemicals Corp. subsidiary
and Mitsubishi Gas Chemical (39). Vistron's hydrolysis unit can
handle 15% or more ammonia and up to 3% by weight of urea and
bring effluent levels down to 60 g/m3 of urea and 30 g/m3 of NHs
(39) . CF Industries has two of their own systems installed as
retrofits to existing plants. Agrico has one unit in service.
Biological Treatment
A possible treatment mechanism for the removal of ammonia and
ammonium nitrate from process condensate involves biological
nitrification and denitrif ication. This process, applied for
years in the treatment of municipal wastes, is based on the
reaction of ammonia nitrogen with oxygen in an aerated pond or
basin to form nitrates via biological oxidation. The nitrates
are in turn reacted in an anaerobic environment in the presence
of a biodegradable carbon compound to form elemental nitrogen.
In the nitrification process, ammonia is oxidized aerobically to
nitrite (NOa) and then to nitrate (NO 3) . The following equations
apply :
2NH3 + 3O2 -> 2N02 + 2H+ + 2H20 (19)
+ 02 •> 2NOg (20)
In addition to requiring an adequate supply of oxygen and warm
temperatures, the rate of nitrification is strongly pH dependent.
The maximum nitrification rate is attained at a pH of 8.0. This
falls to 90% of maximum at pH's of 7.8 and 9.0, and only 50% at a
(39) Urea Makers Can Strip Away Waste Problems. Chemical Week
120(14):33-34, 1976.
52
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pH of 7.0 (40) . Because the production of acidity is part of the
biological metabolism, alkalinity must be supplied to maintain
an operable system.
In the denitrification process, nitrate is anaerobically con-
verted to nitrogen gas. Anaerobic micro-organisms cause the
nitrates and available carbon to be broken down into nitrogen
gas and CO2 . Methanol has been the most successful carbon source
used, but work has also been done using sugar, acetic acid,
methane, sewage sludge, and raw wastewater as the source. Using
methanol the pertinent equation is:
6N03~ + 5CH3OH -»• 3N2t + 5C02t + 7H20 + 60H~ (21)
Because effluents from nitrogen fertilizer plants do not normally
contain a carbon source for the microorganisms, additional carbon
would have to be supplied. This could introduce another environ-
mental problem not originally present.
Ion Exchange
Figure 18 is a schematic diagram of the Chemical Separations
Corporation continuous ion exchange process. In this process,
ammonium nitrate bearing fertilizer wastes flow to a strongly
acidic cation exchange unit where the ammonium ion combines with
the resin while the H+ ion combines with the nitrate ion to form
nitric acid. The wastewater then flows to an anion unit where
the nitrate ion combines with the resin and water is formed.
The following equations apply (25) :
Cation: NHijNOa + R2H -> R2NHi( + HNO3 (22)
Anion: HN03 -I- R2OH -»• R2N03 + H20 (23)
The resulting water stream can be discharged to a receiving body
or used as boiler feed water or cooling tower makeup. A repre-
sentative feed and treated water effluent analysis is shown in
Table 17 (41) .
The CHEM-SEPS® ion exchange system is operated in a continuous
manner. Ion exchange resins, pulsed hydraulically through a
closed loop, are divided into three sections for simultaneous
demineralization of wastewater, washing of resin, and regenera-
tion. To regenerate the cation and anion resin beds, 22% nitric
(40) Mioduszewski, D. Ammonia Removal - What's Best? Water &
Wastes Engineering, 12(7):34-46, 1975.
(41) Bingham, E. C., and R. C. Chopra. A Closed Cycle Water
System for Ammonium Nitrate Products. Brochure, Chemical
Separations Corporation, Oak Ridge, Tennessee, 1971. 11 pp.
53
-------
FROM PLANT POND
DILUTION
WATER
NITRIC ACID
TANK
-ET
PRODUCT
AMMONIUM DEM|NERALIZERU
NITRATE WATER
Figure 18. Continuous ion exchange process (25) .
TABLE 17. REPRESENTATIVE WASTE AND TREATED WATER
ANALYSIS FROM ION EXCHANGE (41)
Component
Ammonia (NH3)
Magnesium (Mg++)
Calcium (Ca++)
Sodium (Na+)
Nitrate (N03~)
Chloride (Cl~)
Sulfate (SO^")
PH
Silica (Si02)
Influent,
g/m3
340
4.8
60
0
1,240
53
72
5 to 9
15
Effluent,
g/m3
2 to 3
-
_
—
7 to 11
—
_
5.9 to 6.4
15
Ammonium nitrate removal is 99.4%.
54
-------
acid (HN03) and 7% NH3 solutions are used, respectively. The
rf SVi^ing streams wil1 contain an amminium nitrate concentration
of 10% to 20%. The application of the Chem-Seps process is
limited to those manufacturers who have an outlet for this re-
covered ammonium nitrate solution. Many manufacturers feel that
there are certain materials in the receovered solution that would
prohibit evaporating this recovered solution to dryness because
of their sensitizing qualities (i.e., they render the solid prod-
uct more susceptible to explosions) . This is of particular con-
cern to those manufacturers who use some or all of their ammonium
nitrate in the manufacture of explosives.
Ion exchange appears to be the growing technique by which ammon-
ium nitrate plant effluents are being treated and is named as the
best available technology for these plants in the amended efflu-
ent date guidelines of 1978 (34). As of January 1976, 10 major
ammonium nitrate plants had decided to utilize the Chem-Seps
process (Table 18) (42) .
TABLE 18. PLANT LOCATIONS USING ION EXCHANGE (42)
Plant Location
Hercules, Inc. Louisiana, MO
Mississippi Chemical Co. Yazoo City, MS
American Cyanamid Co. Hannibal, MO
Indiana Army Ammunition
Plant (ICI America) Charleston, IN
Standard Oil Co. of Ohio
Vistron Division Lima, OH
W. R. Grace & Co. Wilmington, NC
Joliet Army Ammunition Plant Joliet, IL
Illinois Nitrogen Corp. Marseilles, IL
CF Industries, Inc. Chattanooga, TN
CF Industries, Inc. Tunis, NC
Condensate Reuse
A potential control technology involves the direct recycle of
neutralizer condensate as a feed stream. The effluent stream
from the condensed neutralizer exhaust at an ammonium nitrate
plant, for example, could potentially be used as a feed to the
absorption column in the adjacent nitric acid plant. The value
of the nitrate content in the wastewater would then be realized.
Figure 19 is an example of ammonium nitrate effluent utilization.
(42) Brennan, J. P. The Chem-Seps Nitrogen Recovery Process:
A Pollution Solution that Works. In: Proceedings of The
Fertilizer Institute Environmental Symposium (New Orleans,
Louisiana, January 13-16, 1976), The Fertilizer Institute,
Washington, D.C. pp. 217-249.
55
-------
fe TAILGAS
TO VENT SCRUBBER
NITRIC ACID
AMMONIA
I
rV-
CONDENSER
r*
I
COOLING WATER
^••I^^MBIMMtfimMIIII
•J
1 '
1
'If
REACTOR
PRC
RE(
fr TO
COOLING WATER
CONDENSED
^•REACTOR VAPOR
WATER
MAKE UP ACID
_ FOR —
NITRIC ACID
ABSORPTION
COLUMN
TO CONCENTRATOR
GAS FROM CONVERTER
AND HEAT EXCHANGERS*
COOLING
WATER
FOR ABSORBER
PRODUCT
' NITRIC ACID
AMMONIUM NITRATE PLANT
NITRIC ACID PLANT
Figure 19. Ammonium nitrate effluent utilization (9).
DEGREE OF APPLICATION
Production of nitrogen fertilizers often occurs in a complex of
several manufacturing lines. The effluent is therefore composed
of the individual effluents originating with each component
process. As a result it is difficult to compose an exact list-
ing of control techniques applied on a plant-by-plant basis.
Table 19 provides estimates of the degree of utilization of
various nitrogen control technologies by industry segments. Air
stripping of ammonia, condensate reuse and biological treatment
of effluents are not included in Table 19 as they are now rarely
applied to effluent control.
TABLE 19. DEGREE OF UTILIZATION OF NITROGEN CONTROL
TECHNOLOGIES BY INDUSTRY SEGMENT
Product
Steam Ion
stripping exchange Hydrolysis Containment
Ammonium nitrate
Urea
Ammonia
M
M3
H
L
M
H
NA
L NA
NA M
NA NA
- low utilization
- medium utilization
- high utilization
- not applicable
M
M
M
aSteam stripping is often used in conjunction with urea hydrol-
ysis at a urea plant.
56
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SECTION 6
GROWTH AND NATURE OF THE INDUSTRY
PRESENT TECHNOLOGY
The technology utilized in the production of various major
nitrogen-based fertilizers or components; i.e., ammonia,
ammonium nitrate, urea, and nitric acid, is well established.
For example,there have been no major breakthroughs in the pro-
duction of ammonium nitrate since high density prilling was
begun in the early 1960's. Nitric acid and urea production
have followed a similar pattern of no major change in produc-
tion technology.
Ammonia production further illustrates the static aspects of
technology development when one considers that in the United
States, 98% of the synthetic ammonia is produced by steam
reforming natural gas. Six plants representing less than 2%
of domestic production use hydrogen feedstock obtained from
salt water electrolysis plants. Foreign processes for ammonia
production include: use of naphtha and other light hydrocar-
bons for feedstock, partial oxidation of heavier hydrocarbons
(petroleum oil or distillates), cryogenic recovery of hydrogen
from petroleum refinery gases, and gasification of coal or
coke. These production techniques are not used in the United
States because of their high capital and operating costs com-
pared to the low prices and availability of natural gas in this
country.
EMERGING TECHNOLOGY
Ammonia Manufacturing
As long as natural gas is available and cheaper than oil, plants
in the United States will continue to use the catalytic steam
reforming process. However, because of the uncertainty in
natural gas supply and prices, several companies are considering
other production techniques.
Because of natural gas curtailments, about 50% of the plants are
beginning to fire No. 2 fuel oil in the radiant heat section of
57
-------
the primary reformer during winter months (43-45). If gas
supplies continue to dwindle, this practice probably will be
extended to full annual.operation.
In terms of feedstock substitution, estimates indicate that con-
version from natural gas to naphtha would cost 50% to 100% of
the original expense of a new plant (46, 47). For example, a
new 900-metric ton/day ammonia plant built to use naphtha would
cost 15% more than one built to operate on natural gas because
additional desulfurization and carbon removal equipment would
have to be installed to treat the dirtier feedstock (46).
Ammonium Nitrate
Changes in neutralizer operation and construction are among the
most significant developments which may affect effluent quality.
Different designs have been proposed for the control of air
emissions (1).
Urea
Several new processes are being developed for the production of
urea (2). Each of these, however, is concerned with the solu-
tion production stage, not the solidification stage. Since water
effluents arise from the evaporation of excess water in the
solidification stage, the impact of these new processes on efflu-
ent quality is minimal.
Nitric Acid
Improvements in the basic nitric acid process previously
described lie in the area of catalysts. Costs of the standard
platinum catalyst are high, and efforts are always underway to
recover as much as possible or to develop alternate, cheaper
catalysts (23). These process changes have little or no effect
on water effluent quality.
(43) Personal communication with J. C. Barber, Tennessee Valley
Authority, Muscle Shoals, Alabama, June 1976.
(44) Personal communication with J. H. Mayes, Gulf South Research
Institute, Baton Rouge, Louisiana, July 1976.
(45) Sloan, C. R., and A. S. McHone. The Effect of the Energy
Crisis on Ammonia Producers. In: Ammonia Plant Safety,
Volume 15, Chemical Engineering Progress Technical Manual.
American Institute of Chemical Engineers, New York, New York
1973. pp. 91-95.
(46) Ammonia Plants Seek Routes to Better Gas Mileage. Chemical
Week, 116 (8):29, 1975.
(47) Strelzoff, S. Make Ammonia from Coal. Hydrocarbon Process-
ing, 53(10):133-135, 1974.
58
-------
INDUSTRY GROWTH TRENDS
48 S?
3, 48-51).
industry is shown in
growth m production of ammonium
100
1960 196Z 1964 1966 1968 1970 1972 1974 1976 1978 1980
YEAR
Figure 20. Growth factors for nitrogen-based fertilizers.
nitrate, ammonia, and nitric acid has been fairly level in recent
years and in current projections to 1980. Urea, on the other
hand, has experienced dramatic increases in recent years and has
a projected growth of almost 1.5 times 1976 production for 1980.
This growth is the result of use of urea in nonfertilizer areas,
in forest fertilization, and in increased export of prilled urea.
(48) Current Industrial Reports, Inorganic Chemicals. U.S.
Department of Commerce, Washington, D.C. M28A(72)-14,
December 1972. p. 14.
(49) Current Industrial Reports, Inorganic Fertilizer Materials
and Related Products. M28B(75)-4, U.S. Department of
Commerce, Washington, D.C., June 1975. p. 1.
(50) Current Industrial Reports, Inorganic Fertilizer Materials
and Related Products. M28B(76)-1, U.S. Department of
Commerce, Washington, D.C., March 1976. p. 1.
(51) Current Industrial Reports, Inorganic Fertilizer Materials
and Related Products. M28B(77)-1, U.S. Department of
Commerce, Washington, D.C., March 1977. p. 1.
59
-------
The respective annual growth rate for each of the industries
based on actual and predicted production for 1975 through 1980
is as follows:
Ammonia 5.2%
Ammonium nitrate 3.8%
Urea 9.7%
Nitric acid 1.0%
A significant factor influencing the growth of the fertilizer
industry is economics. The fertilizer industry is capital inten-
sive; therefore any expansions or new plants are affected by the
supply of capital. Also, the industry is highly depenedent on
the customer. It is therefore subject to seasonal demand, cyclic
oversupply, "commodity type" sales price, and customer's ability
to purchase. All of these factors combine to inhibit or acceler-
ate the growth of nitrogen fertilizers.
POTENTIAL IMPACT OF CONTROLS
In the ammonia industry, the potential impact of increased utili-
zation of controls is not too large. Already the condensate
stripper, used in virtually all ammonia plants, reduces contami-
nants to acceptable levels. Therefore the growth of pollutants
is expected to parallel the growth of the industry.
Both urea and ammonium nitrate production could possibly increase
the use of already existing controls to reduce the growth of
pollutants.
60
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64
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65
-------
58. Water Resources Data for Arizona, 1975. USGS/WRD/HD-76/036
(PB 259 326), U.S. Geological Survey, Water Resources Divi-
sion, Tucson, Arizona, 1976. 452 pp.
59. Water Resources Data for Idaho, 1975. USGS/WRD/HD-76/034
(PB 263 998), U.S. Geological Survey, Water Resources Divi-
sion, Boise, Idaho, 1976. 698 pp.
60. Water Resources Data for New Mexico, 1975. USGS/WRD/HD-76/
051 (PB 263 548), U.S. Geological Survey, Water Resources
Division, Albuquerque, New Mexico, 1976. 616 pp.
61. Water Resources Data for Texas, 1975. Volume 1. USGS/WRD/
HD-76/025 (PB 257 081), U.S. Geological Survey, Water
Resources Division, Austin, Texas, 1976. 579 pp.
62. Water Resources Data for Indiana, 1975. USGS/WRD/HD-76/010
(PB 251 859), U.S. Geological Survey, Water Resources Divi-
sion, Indianapolis, Indiana, 1976. 368 pp.
63. Water Resources Data for Tennessee, 1975. USGS/WRD/HD-76/
005 (PB 254 462), U.S. Geological Survey, Water Resources
Division, Nashville, Tennessee, 1976. 467 pp.
64. Water Resources Data for Texas, 1975. Volume 2. USGS/WRD/
HD-76/026 (PB 257 082), U.S. Geological Survey, Water
Resources Division, Austin, Texas, 1976. 447 pp.
65. Water Resources Data for Wyoming, 1975. USGS/WRD/HD-76/038
(PB 259 841), U.S. Geological Survey, Water Resources Divi-
sion, Cheyenne, Wyoming, 1976. 664 pp.
66. Water Resources Data for Georgia, 1975. USGS/WRD/HD-76/006
(PB 251 856), U.S. Geological Survey, Water Resources Divi-
sion, Doraville, Georgia, 1976. 378 pp.
67. Water Resources Data for Colorado, 1975. USGS/WRD/HD-76/053
(PB 262 771), U.S. Geological Survey, Water Resources Divi-
sion, Lakewood, Colorado, 1976. 274 pp.
68. Water Resources Data for Texas, 1975. Volume 3. USGS/WRD/
HD-76/025 (PB 257 083), U.S. Geological Survey, Water
Resources Division, Austin, Texas, 1976. 523 pp.
69. Water Resources Data for West Virginia, 1975. USGS/WRD/HD-
76/052 (PB 262 742), U.S. Geological Survey, Water Resources
Division, Charleston, West Virginia, 1976. 299 pp.
70. Water Resources Data for Kansas, 1975. USGS/WRD/HD-76/008
(PB 251 857), U.S. Geological Survey, Water Resources Divi-
sion, Lawrence, Kansas, 1976. 401 pp.
66
-------
71. Water Resources Data for Iowa, 1975. USGS/WRD/HD-76/009
(PB 251 858), U.S. Geological Survey, Water Resources Divi-
sion, Iowa City, Iowa, 1976. 303 pp.
72. Water Resources Data for Pennsylvania, 1975. Volume 1.
USGS/WRD/HD-76/047 (PB 261 436), U.S. Geological Survey,
Water Resources Division, Harrisburg, Pennsylvania, 1976.
399 pp.
73. Water Resources Data for Missouri, 1975. USGS/WRD/HD-76/031
(PB 256 765), U.S. Geological Survey, Water Resources Divi-
sion, Rolla, Missouri, 1976. 378 pp.
74. Water Resources Data for Pennsylvania, 1975. Volume 3. USGS/
WRD/HD-76/049 (PB 261 438), U. S. Geological Survey, Water
Resources Division, Harrisburg, Pennsylvania, 1976. 209 pp.
75. Water Resources Data for Washington, 1975. USGS/WRD/HD-76/
033 (PB 259 197), U.S. Geological Survey, Water Resources
Division, Tacoma, Washington, 1976. 700 pp.
76. Water Resources Data for California, 1975. Volume 3. USGS/
WRD/HD-76/043, (PB 264 476), U.S. Geological Survey, Water
Resources Division, Menlo Park, California, 1976. 411 pp.
77. Water Resources Data for Oregon, 1975. USGS/WRD/HD-76/017
(PB 257 153), U.S. Geological Survey, Water Resources Divi-
sion, Portland, Oregon, 1976. 607 pp.
78. Water Resources Data for Minnesota, 1975. USGS/WRD/HD-76/
039 (PB 259 952), U.S. Geological Survey, Water Resources
Division, St. Paul, Minnesota, 1976. 523 pp.
79. Water Resources Data for Ohio, 1975. Volume 2. USGS/WRD/
HD-76/042 (PB 261 783), U.S. Geological Survey, Water
Resources Division, Columbus, Ohio, 1976. 249 pp.
80. Water Resources Data for Alabama, 1975. USGS/WRD/HD-76/003
(PB 251 854), U.S. Geological Survey, Water Resources Divi-
sion, University, Alabama, 1976. 391 pp.
81. Water Resources Data for California, 1975. volume 1. USGS/
WRD/HD-76/059 (PB 264 474), U.S. Geological Survey, Water
Resources Division, Menlo Park, California, 1976. 563 pp.
82. Standard Methods for the Examination of Water and Wastewater.
Thirteenth Edition. American Public Health Association,
New York, New York, 1971. 874 pp.
83. Standard for Metric Practice. ANSI/ASTM Designation
E 380-76e, IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976.
37 pp.
67
-------
APPENDIX A
RAW DATA
Plant parameters and data on receiving streams that were used in
this report are compiled in Appendix A. Table A-l gives a list-
ing of nitrogen fertilizer plants, plant locations, and plant
capacities. Tables A-2 and A-3 present data on the receiving
streams into which plants discharge. In most cases receiving
streams were identified by using an atlas to locate the river
closest to a plant site. However, because smaller streams were
not given in the atlas, and because some plants may discharge to
municipal treatment systems, the listing of rivers in these
tables may not be completely accurate.
68
-------
TABLE A-l. NITROGEN FERTILIZER PLANTS, LOCATIONS, AND CAPACITIES
Annual capacity,
103 metric tons
Company
Agway, Inc.
Air Products and Chemicals, Inc.
Allied Chemical Corp.
'•'*
American Cyanamid Co.
Apache Powder Co.
Beker Industries, Inc.
Borden , Inc .
California Oil Purification Co.
Camex, Inc.
CF Industries, Inc.
Cherokee Nitrogen Co.
(N-ReN Corp.)
Coastal States Gas Corp.
Columbia Nitrogen Corp.
Cominco American, Inc.
Commercial Solvents Corp.
Diamond Shamrock Corp.
Dow Chemical Co.
DuFont Co.
El Paso Natural Gas Co.
Ensearch Corp., Nipak, (subsidiary)
(Lone Star Gas Co.)
Esmark, Inc.
FMC Corp.
Farmers National Chemical Co.
Farmland Industries, Inc.
Cooperative Farm chemicals Assoc.
(CPCA)
Felmont Oil Corp.
First Mississippi Corp.
Gardinier, Inc.
General American Oil of Texas
Goodpasture, Inc.
W. R. Grace & Co.
Green Valley Chemical Corp.
Gulf Oil Corp.
Gulf and Western Industries, Inc.
Bercules, Inc.
City/state
Clean, NX
New Orleans, CA
Pensacola, FL
Geismar, LA
Hopewell, VA
South Point, OH
Omaha, NE
Hannibal, HO
New Orleans, LA
Benson, AZ
Conda, ID
Carlsbad, MM
Geismar, LA
Ventura, CA
Borger, TX
Donaldsonville, LA
Fremont, NE
Terre Haute, IN
Tyner, TN
Tunis, NC
Olean, NY
Pryor , OK
Plainview, TX
Cheyenne, WY
Augusta , GA
Beatrice, NE
Sterlington, LA
Dumas, TX
Freeport, TX
Beaumont, TX
Belle, HV
Gibbstown, NJ
Seneca , IL
Victoria, TX
Odessa, TX
Kerens , TX
Pryor, OK
Beaumont, TX
South Charleston, HV
Plainview, TX
Dodge City, KS
Lawrence, KS
Ft. Dodge, IA
Hastings, NE
Enid, OK
Plainview, TX
Olean, NY
Ft. Madison, IA
Tampa, FL
Helena, AR
Pasadena, TX
Dimmitt, TX
Wilmington, SC
Memphis, TN
Big Spring, TX
Creston, IA
Donaldsonville, LA
Pittsburg, KS
Palmer ton, PA
Bessemer, AL
Carthage, MO
Donora , PA
Hercules, CA
Louisiana, MO
Ammonia
190
68
308
308
290
180
308
14
127
190
258
363
616
43
122
149
190
166
118
308
145
104
308
308
90
104
113
95
22
54
181
308
18
127
362
24
77
308
118
77
300
113
32
308
36
—
63
63
Ammonium •
nitrate
64
182
102
272
123
30
141
116
363
77
73
212
154
-
45
182
65
73
417
95
30
197
326
23
1 "tK
LJv
73
459
Urea
21
222
63
127
132
145
200
120
329
16
30
150
68
16
41
35
63
170
45
58
244
61
85
21
• 4 f\
44Z
36
86
Note.—Blanks indicate that the product is not produced and dashes indicate that the
amount produced is unknown.
69
-------
TABLE A-l (continued)
10 3 metric tons
Hooker Chemical Corp.
IMC Corp.
Illinois Nitrogen Co.
Kaiser Aluminum s Chemicals Corp.
Mississippi Chemical Corp.
Mobil Oil Corp.
Monsanto Co.
Nitram, Inc.
Occidental Petroleum Corp.
Olin
PPG Industries, Inc.
Pennwalt Chemicals Corp.
Phillips Pacific Chemical Co.
Phillips Petroleum Co.
Reichhold Chemical, Inc.
Rohm and Haas Co.
St. Paul Ammonia Products, Inc.
J. R. Simplot Co.
Standard Oil of California
Chevron Chem. Co., (subsidiary)
Standard Oil of Indiana
Standard Oil of Kentucky
Standard Oil Co. of Ohio
(Vistron Corp.)
Solar Nitrogen Chemicals, Inc.
Skelly Oil Co.
Hawkeye chemical Co., (subsidiary)
Tenneco, Inc.
TVA
Terra Chemicals International, Inc.
Tipperary Corp.
Triad Chemical
Tyler Corp.
(Atlas Powder Co.)
Union oil Co. of California
Collier Carbon & Chemical Corp.,
(subsidiary)
United States Steel Corp.
USS Agri-Chemicals
Valley Nitrogen Producers, Inc.
Vulcan Materials Co.
The Williams Companies
(Agrico Chemicals)
City/state
Tacoma, WA
Sterlington, LA
Marseilles, IL
Bainbridge, GA
North Bend, OH
Savannah, GA
Tampa, FL
Pascagoula, MS
Yazoo City, MS
Beaumont, TX
Luling, IA
El Dorado, AR
Tampa, FL
Lathrop , CA
Plainview, TX
Hanf ord , CA
Lake Charles, LA
New Martinsville, HV
Portland, OR
Finley (Kennewick), WA
Beatrice, NE
Pasadena, TX
Etter, TX
St. Helens, OR
Deer Park, TX
E. Dubugue, IL
St. Paul, MN
Pocatello, ID
Fort Madison, IA
El Segundo, CA
Richmond, CA
Kennewick , WA
Texas City, TX
Pascagoula, MS
Lima, OR
Joplin, MO
Clinton, IA
Houston, TX
Muscle Shoals, AL
Sioux City, IA
(Port Neal)
Loving ton, MM
Donaldsonville , LA
Joplin, MO
Tamaque , PA
Brea, CA
Kenai, AK
Cherokee, AL
Crystal City, MO
Geneva, UT
Clairton, PA
El Centre, CA
Helm, CA
Chandler, AZ
Wichita, KS
Henderson, KY
Verdigris , OK
Donaldsonville, LA
Tulsa, OK
Blytheville, AR
Ammonia
20
136
159
358
236
408
87
47
435
45
8
141
190
209
81
45
190
100
95
12
118
655
463
522
23
123
190
81
190
90
345
236
463
160
63
363
190
160
32
36
308
386
308
Ammonium
nitrate
170
136
55
93
229
50
788
177
322
254
136
33
50
64
168
23
208
18
77
95
58
136
39
136
146
14
55
91
91
91
41
69
91
239
Urea
73
127
150
34
45
62
77
14
200
55
55
145
426
67
109
308
23
17
53
190
181
299
70
-------
TABLE A-2. NITROGEN FERTILIZER PLANTS, LOCATIONS, AND WASTEWATER RECEIVING BODIES
Plow,8 m3/s
Company
Agway, Inc.
Air Products and Chemicals, Inc.
Allied Chemical Corp.
American Cyanamid Co.
Apache Powder Co.
Beker Industries , Inc .
Borden, Inc.
California Oil Purification Co.
Camex, Inc.
CF Industries, Inc.
Cherokee Nitrogen Co.
(N-ReN Corp.)
Coastal States Gas Corp.
Columbia Nitrogen Corp.
Cominco American, Inc.
Commercial Solvents Corp.
Diamond Shamrock Corp.
Dow Chemical Co.
DuPont Co.
City/state
Olean, NY
New Orleans, LA
Pensacola, FL
Geismar, LA
Hopewell, VA
South Point, OH
Omaha, NE
Hannibal, HO
New Orleans, LA
Benson, AZ
Conda, ID
Carlsbad, NM
Geismar, LA
Ventura, CA
Borger, TX
Donaldsonville, LA
Fremont, NE
Terre Haute, IN
Tyner , TN
Tunis, NC
Olean, NY
Pryor , OK
Plainview, TX
Cheyenne , WY
Augusta, GA
Beatrice, NE
Sterlington, LA
Dumas, TX
Freeport, TX
Beaumont, TX
Belle, WV
DuPont, WA
Gibbstown, NJ
Louviers, CO
Seneca, IL
Victoria, TX
Receiving body
Allegheny River
Mississippi River
Pensacola Bay
Mississippi River
James River
Ohio River
Missouri River
Mississippi River
Mississippi River
San Pedro River
Bear River
Pecos River
Mississippi River
Pacific Ocean
Canadian River
Mississippi River
Platte River
Wabash River
Tennessee River
Chowan River
Allegheny River
Neosho River
Running Hater Draw
Crow River
Savannah River
Big Blue River
Ouachita River
South Palo Duru River
Brazos River
Neches River
Kanawah River
Sequalitchen Creek
Delaware River
South Platte River
Illinois River
Guadalupe River
Max
711
33,131b
h
33,131
3,540
11,300
2,060
9,460
33,131b
57
43
300
33,131b
26
33,131b
d
1,410
4,050
d
710
e
0.48
7.6
1,243
_d
1,890
63.2
1,725
560
3,200
d
"d
44
1,286
821
Min
5
5,925b
h
5,925
32
303
317
844.
5,975b
oc
4.5
0.02
5,975b
0.01
5,975b
d
76.5
377
d
I
e
oc
0.05
156
d
71b
oc
47
50
67
d
"d
2.6
81
32
Mean
90
17,896b
h
17,896
246
3,210
1,190
3,310
17,896b
0.5
21 •
3
17,896b
1.7
17,896
d
377
1,305
d
90
e
0.02
0.68
331
_d
1,020
0.50
397
280
562
d
"d
11
317
99
Measuring station
location
Salamanca, NY
Talbert Landing, MS
(below Vicksburg)
Talbert Landing, MS
Near Richmond, VA
Greenup Dam, KY
Nebraska City, NE
Alton, IL
Talbert Landing, MS
Near Benson, AZ
Soda Springs, ID
Below Dark Canyon at
Carlsbad, NM
Talbert Landing, MS
Near Canadian, TX
Talbert Landing, MS
Terre Haute, IN
Chattanooga, TN
Salamanca, NY
Plainview, TX
Near Tipperary, WY
Augusta, GA
Monroe , LA
Near Spearman, TX
Near Rosharon, TX
Evadale, TX
Charleston, WV
South Platte, CO
Marseilles, IL
Victoria, TX
Reference
52
53
53
54
55
56
57
53
58
59
60
53
61
53
62
63
52
64
65
66
53
61
62
61
69
67
57
68
See footnotes at end of table, p. 73.
-------
TABLE A-2 (continued)
Flow, m3/s
Company
El Paso Natural Gas Co.
Ensearch Corp., Nipak, subsidiary
. (Lone Star Gas Co.)
Esmark, Inc.
FMC Corp.
Fanners National Chemical Co.
Farmland Industries, Inc.
Cooperative Farm Chemicals
Association (CFCA)
Felmont Oil Corp.
First Mississippi Corp.
Gardinier, Inc.
General American Oil of Texas
Goodpasture, Inc.
W. R. Grace fi Co.
Green Valley Chemical Corp.
Gulf Oil Corp.
Gulf and Western Industries, Inc.
Hercules , Inc .
Hooker Chemical Corp.
IMC Corp.
Illinois Nitrogen Co.
City/state
Odessa, TX
Kerens , TX
Pryor, OK
Beaumont, TX
South Charleston, WV
Plainview, TX
Dodge City, KS
Lawrence, KS
Fort Dodger IA
Hastings , NE
Enid, OK
Plainview, TX
Olean, NY
Fort Madison, IA
Tampa, FL
Helena, AR
Pasadena, TX
Dimmitt, TX
Wilmington, NC
Memphis, TO
Big Spring, TX
Creston, I A
Donaldsonville, LA
Pittsburg, KS
Palmerton, PA
Bessemer , AL
Carthage, MO
Donora, PA
Hercules , CA
Louisiana, MO
Tacoma, WA
Sterlington, LA
Marseilles, IL
Receiving body
Johnson River
Chambers River
Neosho River
Neches River
Kanawha River
Running Water Draw
Arkansas River
Kansas River
Des Moines River
_g
Turkey River
Running Water Draw
Allegheny River
Mississippi River
Tampa Bay
Mississippi River
Houston Ship Channel
_9
Atlantic Ocean
Mississippi River
Beals Creek
Platte River
Mississippi River
_g
Lehigh River
_g
Spring River
Monongahela River
San Francisco Bay
Mississippi River
Puyallup River
Ouachita River
Illinois River
Max
_d
634
_f
560
3,200
0.48
1.6
1,360
334
f
0.48
710
7,140
42,200
_d
42,200
5.2
66
33,131
310
170
2,165
9,460
785
l,890b
1,286
Min
_d
0.02
_f
50
67
oc
0
50
2
f
0
5
637
6,400
_d
6,400
0
0.03
5,975b
14
3
20
844
15
71b
81
Mean
_d
28
_f
280
562
0.02
0.35
177
38
f
0.02
90
2,100
19,930
d
19,930
0.3
2.2
17,896
64
18
314
3,305
103
l,020b
317
Measuring station
location
Near Corsicana, TX
Evadale, TX
Charleston, WV
Plainview, TX
Dodge City, KS
Desoto, KS
Fort Dodge, IA
Plainview, TX
Salamanca, NY
Keokuk, IA
Memphis , TN
Memphis, TN
Above Big Spring, TX
Near Diagonal, IA
Talbert Landing, MS
Walnutport, PA
Carthage, MO
Charleroi, PA
Alton, IL
Payallup, WA
Monroe, IA
Marseilles, IL
Reference
61
61
69
64
70
70
71
64
52
71
63
63
68
71
53
72
73
74
57
75
53
57
See footnotes at end of table, p. 73.
-------
TABLE A-2 (continued)
Company
Kaiser Aluminum & Chemicals Corp.
Mississippi Chemical Corp.
Mobil Oil Corp.
Monsanto Co.
Nitram, Inc.
Occidental Petroleum Corp.
Olin
PPG Industries, Inc.
Pennwalt Chemicals Corp.
Phillips Pacific Chemical Co.
Phillips Petroleum Co.
Reichhold Chemical, Inc.
Rohm and Haas Co.
St. Paul Ammonia Products, Inc.
J. R. Simplot Co.
Standard Oil of California
Chevron Chemical Co. (subsidiary)
Standard Oil of Indiana
Standard Oil of Kentucky
Standard Oil Co. of Ohio
(Vistron Corp.)
Solar Nitrogen Chemicals, Inc.
City/state
Bainbridge , GA
North Bend, OH
Savannah, GA
Tampa , FL
Pascagoula, MS
Yazoo City, MS
Beaumont, TX
Luling, LA
El Dorado, AR
Tampa, FL
Lathrop, CA
Plainview, TX
Hanf ord , CA
Lake Charles, LA
New Martinsville, WV
Portland, OR
Finley (Kennewick) , WA
Beatrice, NE
Pasadena, TX
Etter, TX
St. Helens, OR
Deer Park, TX
East Dubuque, IL
St. Paul, MS
Pocatello, ID
Fort Madison, IA
El Segundo, CA
Richmond, CA
Kennewick, WA
Texas City, TX
Pascagoula, MS
Lima, OH
Joplin, MO
Receiving body
Flint River
Dark Hollow Run
Pipemaker Canal
Sixmile River
Gulf of Mexico
Martin Creek
Heches River
Mississippi River
Ouachita River
Hillsborough River
San Joaquin River
Running Water Draw
Lakeland Canal
Beckwith River
Ohio River
Willamette River
Columbia River
Big Blue River
Houston Ship Channel
South Palo Duru
Columbia , River
Galveston Bay
Mississippi River
Mississippi River
Portneuf River
Mississippi River
Pacific Ocean
Pacific Ocean
Columbia River
Gulf of Mexico
Gulf of Mexico
Ottawa River
Shoal River
Flow,3 m3/
Max Min
0.76 0.50
f f
"f "f
~f ~f
_f _f
561 50
33,131 5,975
_d _d
_f _f
250 38
0.48 Oc
_d _d
68 0.13
9,460 156
3,400 175
6,004 1,240
_d _d
63 0
_d _d
6,060 518
2,212 41
43 3.6
7,140 637
6,000 1,240
115 0.5
414 4
s Measuring station
Mean location
0.57 Bainbridge, GA
f
"f
~f
_f
281 Evadale, TX
17,896b Talbert Landing, MS
_d
_f
110 Near Vernalis, CA
0.02 Plainview, TX
_d
8 Near DeQuincy, LA
1,966 Belleville Dam, WV
994 Portland, OR
3,350 Below Priest Rapids
Dam, HA
_d
0.50 Near Spearman, TX
_d
1,420 Clinton, IA
415 St. Paul, MN
13 Pocatello, ID
2,100 Keokuk, IA
3,350 Below Priest Rapids
Dam, HA
4 Allentown, OH
20 Above Joplin, MO
Reference
66
61
53
76
64
53
69
77
75
61
71
78
59
71
75
79
73
See footnotes at end of table, p. 73.
-------
TABLE A-2 (continued)
Flow,8 m3/s
Company
Skelly Oil Co.
Hawkeye Chemical Co. (subsidiary)
Tenneco, Inc.
TVA
Terra Chemicals International) Inc.
Tipperary Corp.
Triad Chemical
Tyler Corp.
(Atlas Powder Co.)
Union Oil Co. of California
Collier Carbon & Chemical Corp.
(subsidiary)
United States Steel Corp.
USS Agri-Chemicals
Valley Nitrogen Producers, Inc.
Vulcan Materials Co.
The Williams Companies
(Agrico Chemicals)
City/state
Clinton, IA
Houston, TX
Muscle Shoals, AL
Sioux City, IA
(Port Neal)
Lovington, NM
Donaldsonville, LA
Joplin, MO
Tamaque, PA
Brea, CA
Kenai, AK
Cherokee , AL
Crystal City, MO
Geneva, UT
Clairton, PA
El Centre, CA
Helm, CA
Chandler, AZ
Wichita, KS
Henderson, KY
Verdigris, OK
Donaldsonville , LA
Tulsa, OK
Blytheville, AR
Receiving body
Mississippi River
Houston Ship Channel
Tennessee River
Missouri River
_g
Mississippi River
Shoal River
Schuylkill River
h
Cook Inlet
Tennessee River
Mississippi River
e
~e
Alamo River
Fresno Slough
_3
Arkansas River
Ohio River
Verdigris River
Mississippi River
Verdigris River
_g
Max
6,060
_d
8,694
1,818
33,131b
414
31
8,694
_d
48
_d
300
14,560
33,131b
_f
Min
518
_d
498
227
5,975b
4
0.5
498
_d
14
_d
7
370
5,9750
_f
Mean
1,420
_d
1,986
1,005
17,896b
20
3
1,986
_d
26
_d
29
4,600
f
17,896"b
_f
Measuring station
location
Clinton, IA
Florence , AL
Sioux City, IA
Talbert Landing, MS
Above Joplin, MO
Tamaque , PA
Florence , AL
Near Niland, CA
Wichita, KS
Louisville, KY
Talbert Landing, MS
Reference
71
80
71
53
73
72
80
81
.70
55'
S3
Maximum, minimum, and mean of daily averages for the 1975 water year (October 1974 to September 1975).
Value for 1974 water year.
NO flow for a portion of the year.
Measurements not readily available.
Could not locate city on road atlas.
Water Resources Data not available in microfiche file.
®No river noted within a 16.1-km (10-mi) radius of city.
Discharge into an underground sewer line which connects to a large sanitation district central treating plant.
-------
TABLE A-3. NITROGEN FERTILIZER PLANTS AND RECEIVING STREAM PARAMETERS
a
ui
Company
Agway, Inc.
Air Products and Chemicals, Inc.
Allied Chemical Corp.
American Cyanamid Co.
Apache Powder Co.
Beker Industries, Inc.
Borden, Inc.
California Oil Purification Co.
Camex, Inc.
CF Industries, Inc.
(Central Farmers Fertilizer Co.)
Cherokee Nitrogen Co.
(N-ReN Corp.)
Coastal States Gas Corp.
Columbia Nitrogen Corp.
Cominco American, Inc.
Commercial Solvents Corp.
Diamond Shamrock Corp.
Dow Chemical Co.
DuPont Co .
City/state
Olean, NY
New Orleans, LA
Pensacola , FL
Geismar, LA
Hopewell, VA
South Point, OH
Omaha , NE
Hannibal, MO
New Orleans, LA
Benson, AZ
Conda, ID
Carlsbad, MM
Geismar, LA
Ventura , CA
Borger , TX
Donaldsonville , LA
Fremont, NE
Terre Haute, IN
Tyner , TN
Tunis, NC
Olean, NY
Pryor, OK
Plainview, TX
Cheyenne , WY
Augusta , GA
Beatrice, NE
Sterlington, LA
Dumas , TX
Freeport , TX
Beaumont, TX
Belle, WV
DuPont , WA
Gibbstown, NJ
Louviers, CO
Seneca , IL
Victoria, TX
Receiving body
Allegheny River
Mississippi River
Pensacola Bay
Mississippi River
James River
Ohio River
Missouri River
Mississippi River
Mississippi River
San Pedro River
Bear River
Pecos River
Mississippi River
Pacific Ocean
Canadian River
Mississippi River
Platte River
Wabash River
Tennessee River
Chowan River
Allegheny River
Neosho River
Running Water Draw
Crow River
Savannah River
Big Blue River
Ouachita River
South Palo Duru River
Brazos River
Heches River
Kanav;ah River
Sequalitchen Creek
Delaware River
South Platte River
Illinois River
Guadalupe River
Water
pH, temperature, °C
Max Min Mean Max Min Mean
7.6 6.8 7.2 28.0 4.5 15.9
30.0 0
18.0 7.5 12.9
8.5 7.5 8.1 32.0 2.0 15.3
,
7.0 6.2 6.6 29'.0 8.0 19.0
8.5 7.6 7.9 25.0 15.0 20.0
7.9 6.3 7.0 29.0 10.0 20.8
7.1 6.3 6.7 29.5 11.0 20.4
33.0 4.0
7.9 7.1 7.5 30.0 4.0 15.5
8.0 7.7 7.8 30.0 14.0 22.9
See footnotes at end of table, p. 77.
-------
TABLE A-3 (continued)
a\
Water
pH, temperature.
Company
El Paso Natural Gas Co.
Ehsearch Corp., Nipak, subsidiary
(Lone Star Gas Co.)
Esmark , inc .
FMC Corp.
Farmers National Chemical Co.
Farmland Industries, Inc.
Cooperative Farm Chemicals
Association (CFCA)
Felmont Oil Corp.
First Mississippi Corp.
Gardinier, Inc.
General American Oil of Texas
Goodpasture, Inc.
W. R. Grace & Co.
Green Valley Chemical Corp.
Gulf Oil Corp.
Hercules, Inc.
Hooker Chemical Corp.
IMC Corp.
Illinois Nitrogen Co.
City/state
Odessa, TX
Kerens , TX
Pryor , OK
Beaumont, TX
South Charleston, WV
Plainview, TX
Dodge City, KS
Lawrence , KS
Fort Dodge, IA
Hastings, NE
Enid, OK
Plainview, TX
Olean, NY
Fort Madison, IA
Tampa , FL
Helena, AR
Pasadena, TX
Dimmitt, TX
Wilmington, NC
Memphis, TN
Big Spring, TX
Creston, IA
Donaldsonville, LA
Pittsburg, KS
Bessemer, AL
Carthage , MO
Donora , PA
Hercules, CA
Louisiana, MO
Tacoma , WA
Sterlington, LA
Marseilles, IL
Receiving body
Johnson River
Chambers River
Neosho River
Heches River
Kanawha River
Running Water Draw
Arkansas River
Kansas River
Des Moines River
_b
Turkey River
Running Water Draw
Allegheny River
Mississippi River
Tampa Bay
Mississippi River
Houston Ship Channel
-b
Atlantic Ocean
Mississippi River
Seals Creek
Platte River
Mississippi River
_b
_b
Spring River
Monongahela River
San Francisco Bay
Mississippi River
Puyallup River
Ouachita River
Illinois River
Max Min Mean Max
8.3 7.4 7.8 27.5
7.1 6.3 6.7 29.5
33.0
8.7 7.0 7.9 32.0
8.6 7.9 8.2 25.0
8.6 7.8 8.4 30.0
8.2 6.9 7.5 25.5
30.0
7.6 6.9 7.3 16.3
7.0 6.2 6.6 29.0
7.9 7.1 7.5 30.0
Min
7.0
11.0
4.0
0.5
1.5
0
5.0
0
3.4
8.0
4.0
"C
Mean
18.6
20.4
14.8
14.9
15.9
17.5
10.0
19.0
15.5
See footnotes at end of table, p. 77.
-------
TABLE A-3 (continued)
Company
Kaiser Aluminum & Chemicals Corp.
Mississippi Chemical Corp.
Mobil Oil Corp.
Monsanto Co.
Nit ram, Inc.
Occidental Petroleum Corp.
Olin
Pennwalt Chemicals Corp.
Phillips Pacific Chemical Co.
Phillips Petroleum Co.
City/state
Bainbridge, GA
North Bend, OH
Savannah , GA
Tampa, FL
Pascagoula, MS
Yazoo City, MS
Beaumont, TX
Luling, LA
El Dorado, AR
Tampa , FL
Lathrop, CA
Plainview, TX
Hanford , CA
Lake Charles, LA
Portland, OR
Finley (Kennewick), WA
Beatrice, NE
Pasadena, TX
Etter, TX
Receiving body
Flint River
Dark Hollow Run
Pipemaker Canal
Sixmile River
Gulf of Mexico
Martin Creek
Heches River
Mississippi River
Ouachita River
Hillsborough River
San Joaguin River
Running Water Draw
Lakeland Canal
Beckwith River
Willamette River
Columbia River
Big Blue River
Houston Ship Channel
South Palo Duru
Water
SH, temperature, °C
n Mean Max Min Mean
7.1 6.3 6.7 29.5 11.0 20.4
8.3 7.4 7.9 23.5 10.5 15. .8
8.5 7.0 7.9 20.1 5.5 11.7
-
Reichhold Chemical, Inc.
Rohm and Haas Co.
St. Paul Ammonia Products, Inc.
J. R. Simplot Co.
Standard Oil of California
Chevron Chemical Co. (subsidiary)
Standard Oil of Indiana
Standard Oil of Kentucky
Standard Oil Co. of Ohio
(Vistron Corp.)
Solar Nitrogen Chemicals, Inc.
St. Helens, OR
Deer Park, TX
East Dubuque, IL
St. Paul, MN
Pocatello, ID
Fort Madison, IA
El Segundo, CA
Richmond, CA
Kennewick, WA
Texas City, TX
Pascagoula, MS
Lima, OH
Joplin, MO
Columbia, River
Galveston Bay
Mississippi River
Mississippi River
Portneuf River
Mississippi River
Pacific Ocean
Pacific Ocean
Columbia River
Gulf of Mexico
Gulf of Mexico
Ottawa River
Shoal River
8.8 7.8 8.5
8.6 7.9 8.2
8.6 7.8 8.4
29.0
25.5
20.0
30.0
0
0.5
1.0
0
13.6
10.5
8.1
15.9
See footnotes at end of table, p.
77.
-------
TABLE A-3 (continued)
-j
CO
Company
Skelly Oil Co.
Hawkeye Chemical Co. (subsidiary)
Tenneco, Inc.
TVA
Terra Chemicals International, Inc.
Tipper ary Corp.
Triad Chemical
Tyler Corp
(Atlas Powder Co.)
Union Oil Co. of California
Collier Carbon & Chemical Corp.
(subsidiary)
United States Steel Corp.
USS Agri-Chemicals
Valley Nitrogen Producers, Inc.
Vulcan Materials Co.
The Williams Companies
(Agrico Chemicals)
City/state
Clinton, IA
Houston, TX
Muscle Shoals, AL
Sioux City, IA
(Port Neal)
Lovington, NM
Donaldsonville, LA
Joplin, MO
Tamague , PA
Brea, CA
Kenai, AK
Cherokee, AL
Crystal City, MO
Geneva , UT
Clairton, PA
El Centro, CA
Helm, CA
Chandler, AZ
Wichita, KS
Henderson, KY
Verdigris, OK
Donaldsonville, LA
Tulsa, OK
Blytheville, AR
Receiving body
Mississippi River
Houston Ship Channel
Tennessee River
Missouri River
_b
Mississippi River
Shoal River
Schuylkill River
c
Cook Inlet
Tennessee River
Mississippi River
a
~d
Alamo River
Fresno Slough
b
Arkansas River
Ohio River
Verdigris River
Mississippi River
Verdigris River
b
Water
pH, temperature, °C
Max Min Mean Max Min Mean
8.8 7.8 8.5 29.0 0 13.6
7.8 6.9 7.4 28.0 7,5 17.3
8.8 7.6 8.1 26.0 0 9.3
7.8 6.9 7.4 28.0 7.5 17.3
aBlanks indicate data not available.
bNo river noted within a 16.1-km (10-mi) radius of city.
CDischarge into an underground sewer line which connects to a large sanitation district central treating plant.
dCould not locate city on road atlas.
-------
APPENDIX B
CALCULATION OF EFFLUENT PARAMETERS
Effluent parameters used to characterize wastewater streams from
the production of ammonium nitrate and urea were calculated from
data supplied to the EPA by industry. A cross section of com-
panies producing ammonium nitrate and/or urea responded to an EPA
request for effluent data to enable them to formulate meaningful
effluent guidelines for the nitrogen fertilizer industry. The
dataQreceived were compiled and are listed in Tables B-l and
B-2. Table B-l presents compiled data characterizing effluents
from ammonium nitrate production, while Table B-2 presents com-
piled data characterizing effluents from urea production.
Difficulties occurred in reducing the original data to a form
useful in calculating source severities. The original data pro-
vided to EPA were often incomplete. Generally, data character-
ized the total discharge from an entire nitrogen fertilizer
plant, thus combining discharges from ammonium nitrate, urea,
ammonia, and nitric acid production. The nature of the nitrogen
fertilizer plants sampled and sampling techniques used varied
drastically. In addition, observed variations in discharge
characteristics could be attributed to variations in the:
• Size of the nitrogen fertilizer plants.
• Age of the nitrogen fertilizer plants.
• Configuration of the plants (location of nitric acid and
ammonia plant in the sewerage system).
• Type of cooling systems used: closed loop or single pass.
• Type of product: prilled or solution.
• Techniques of handling process off-gases: condensing or
venting.
• Plant maintenance procedures.
. Occurrence -of significant spills while effluent sampling
was conducted.
. Inclusion of land surrounding the nitrogen fertilizer
plant in the sewage system leading to the final discharge.
aData on file at the Effluent Guidelines Division, U.S. Environ-
mental Protection Agency, Washington, D.C., 1977.
79
-------
TABLE B-l.
oo
o
LISTING OF COMPILED RAW DATA CHARACTERIZING THE
WASTEWATER STREAMS FROM AMMONIUM NITRATE PLANTS
Plant
aa,b
B
od
Ea
Ga
fid
i .
ja.d
K?
M
jj8,b
pa
Q3
R
sa
Td
ua»b
va
wd
x
yd
Z
Aft
BB
CC
DE>d
Efid
ppd
GGd
HHd
Production , Wastewater
metric flow,
Product . ton/day m3/s
P(55%)-S
P(56%)-S
P(75%)-S
S
S
S
S
P(45%)-S
S
P(85%)-S
P(56%)-S
P(34%)-S
P
S
S
P(75%)-S
P(50%)-S
P(60*)-S
P
Solid (90%) -S
S
P(30%)-S
Pe(75%)-sf
S
S
P(94%)-S
P(56%)-S
P(95%)-S
P(86%)-S
G9
717
1,004
204
67
155
194
160
914
61
1,111
360
390
295
286
804
283
531
242
411
309
147
336
342
241
133
401
560
654
228
391
6.8 x 10~3
1.95 x ID"3
5 x 10-"
3.2 x 10~3
1.211 x 10-1
9 x 10-11
2.86 x ID"2
2.63 x 10~2
2.437 x 10— '
1.13 x ID-3
7 x 10-"
2.05 x 10~2
1.414 x 10-1
2.52 x 10-1
8.40 x 10~2
3.4 x ID"3
5.07 x ID"2
5.91 x 10~2
4.71 x 10~2
3.2 x ID-2
2.1 x 10~3
7.100 x 10-1
0
7.7 x 10-3
2.2 x ID"3
1.44 x ID"2
3.4 x 10~3
2.74 X 10~2
2.42 x 10-2
6.2 x ID"3
Wastewater
flow/product
produced ,
Nitrogen
g/metric ton
m3/metric ton NH3-N
0.82
0.17
0.21
4.13
67.5
0.40
15.4
2.49
345
0.09
0.17
4.54
41.4
76.1
9.03
1.04
8.24
21.1
9.90
8.95
1.23
183
0
2.76
1.43
3.10
0.52
3.62
9.17
1.37
10
11
585
75
1,200
3,652
2,173
207
70
185
7
1,038
1,880
1,330
2,630
5,400
1,230
10,440
1,080
1,900
947 •
895
0
948
352
96
30
294
153
24
NO3 -N
12
12
120
66
251
381
1,434
178
379
255
6
110
346
1,450
680
810
737
3,130
1,940
1,500
1,125
734
0
577
408
198
22
178
52
75
Nitrogen
g/day
NH3-N
7,170
11,044
119,340
5,025
186,000
708,488
347,680
188,784
4,270
205,535
2,520
404,820
554,600
380,380
2,114,520
1,528,200
653,130
2,526,480
443,880
587,100
139,209
300,720
0
228,468
46,816
38,496
16 ,800
192,276
34,884
9,384
NO3~-N
8,604
12,048
24,480
4,422
38,905
73,914
229,440
162,692
23,119
283,304
2,160
42,900
102,070
414,700
546,720
229,230
391,347
757,460
797,340
463,500
165,375
246,624
0
139,057
54,264
79,398
12,320
116,412
11,856
29,325
Nitrogen
concentration ,
g/n>3
NH3-N
<0.1
65
2,760
18.2
17.8
9,111
141
83.1
0.2
2,110
0.1
229
45.4
17.5
291
5,200
149
495
109
212
767
4.9
0
343
246
30.9
0.1
81.2
16.7
17.5
NO^-N
<0.1
72
567
16.1
3.7
951
92.9
71.6
1.1
2,900
0.1
24.2
8.4
19.0
75.3
780
89
148
196
168
911
4.0
0
209
285
63.8
0.1
49.2
5.7
54.7
Receiving water
flow, m3/s
1-yr Low
MAC
377
NA
NA
5
0.05
0.5
205
NA
50
518
227
NA
317
5,975
498
156
6,400
NA
71
0.50
81
.76.5
303
NA
NA
Ocean
41
NA
NA
1-yr Mean
NA
1,305
NA
NA
90
0.68
4
448
NA
177
1,420
1,005
NA
1,190
17,896
1,986
331
19,930
NA
1,020
0.57
317
377
3,210
NA
NA
Ocean
415
NA
NA
Data reported as one discharge from both ammonium nitrate
and urea production, proportioning method used to assign
values to each process.
Data reported as TKM, proportioning method used to assign
appropriate values of NH3-N and ORG-N.
CNot available.
Summary sheets used, original data not available.
e
'Prilled.
Solution.
q
3Granular.
-------
TABLE B-2.
CO
LISTING OF COMPILED RAW DATA CHARACTERIZING
WASTEWATER STREAMS FROM UREA PLANTS
Production
metric tons/day
Plant
aa,b
B
c
O^
EB
F
Ge
H6
I, „
J
K3
L
M
N
O
g^
R
sa,e
Te .
oa'b
va»e
a
Data
Product (as 100% urea)
sc
s
P
s
s
s
P(40%)-S
P(75%)-S
P(17%)-S
S
P(80%)-S
G9
G(70%)-S
S
P
P(46%)-S
P
S
S
s
s
P(40%)-S
__ _ — ^— — — — — — —
reported as one
269
322
1,083
45
51
161
191
142
550
210
168
701
596
114
1,000
494
155
337
661
60
95
117
Wastewater
Wastewater Nitrogen,
flow/ g/metric ton
flow, product produced, urea produced Nitrogen g/day
m3/s
1.89 x 10"3
4.41 x lO"1*
1.64 x 10"2
7 x ID'1*
1.8 x 10'3
2.4 x 10" 3
1.108 x 10"1
1.6 x 10"3
7.36 x 10"2
4.5 x 10"3
5.11 x 10"1
6.67 x 10~2
7.4 x 10~3
2 X lO"1*
2.63 x 10" 2
1.93 x 10~2
5.54 X 10~2
2.174 x 10"1
5.15 x 10~2
1.93 x 10~2
9.07 x 10"3
2.13 x 10~2
mVmetric
0.61
0.12
1.30
1.34
3'. 05
1.29
50.1
0.97
11.6
1.85
263
8.22
1.07
0.15
2.27
3.38
30.9
55.7
6.73
27.8
83.9
15.7
• — • • —
discharge from both ammonium nitrate
production, proportioning method
Data
reported as TKN
values of NH3-N and
used to assign
, proportioning method used
ORG-N.
values to
to assign
ton NH^-N
8
8
33
152
56
231
900
1,003
57
154
54
501
258
30
183
1,038
.1,490
5,140
1,960
6,180
920
7,780
and urea
each process.
appropriate
ORG-N NH^-N
8 2,152
NA 2,576
22 35,739
30 6,840
39 2,856
54 37,191
63 171,900
80 142,426
129 31,350
193 32,340
224 9,072
310 351,201
488 153,768
552 3,420
68 183,000
NA 512,772
877 230,950
960 1,732,180
110 1,295,560
4,460 370,800
920 87,400
18,380 910,260 2,
Solution.
Not available.
e
Summary sheets
^Prilled.
q
^Granular.
ORG-N
2,152
NA
23,826
1,350
1,989
8,694
12,033
11,360
70,950
40,530
37,632
217,310
290,848
62,928
68,000
NA
135,935
323,520
72,710
267,600
87,400
150,460
Nitrogen Receiving
concentration, water flow,
g/m3
mVs
NHj-N ORG-N 1-yr Low
13
68
25
113
18
179
18
1,030
5
83
0.
61
241
198
81
308
48
92
291
222
112
495
used, original
13
NA
17
22
13
42
1
82
11
104
2 0.
38
455
3,640
30
NA
28
17
16
160
112
1,169
data not
NAd
377
5,975
NA
NA
498
5
0.05
0.5
205
9 NA
5,975
50
518
Ocean
227
NA
317
5,975
498
156
6,400
available.
1-Yr Mean
NA
1,305
17,896
NA
NA
1,986
90
0.68
4
448
NA
17,896
177
1,420
Ocean
1,005
NA
1,190
17,896
1,986
331
19,930
•••••••• • m , , Ml , ,i ^
-------
• Occurrence of precipitation while sampling was performed.
• Detention times in sewage systems (these affect extent
of ammonia absorption or stripping, ammonia or urea
oxidation by microorganisms in aerobic conditions, and
nitrate reduction by microorganisms in anaerobic
conditions).
• pH of the sewages (high pH enhances NH3 stripping).
• Extent of water recycle in the complexes.
• Occurrence and extent of effluent treatment.
Because some of the reporting plants supplied data characterizing
the total effluent from a nitrogen fertilizer complex producing
both urea and ammonium nitrate, certain effluent parameters had
to be segregated as those emanating from ammonium nitrate pro-
duction and those emanating from urea production. An alternate
solution would have been to assign all of the reported effluent
parameters to both ammonium nitrate and urea production, but this
would have amounted to double counting.
A series of assumptions were made in segregating the parameters
to ammonium nitrate and urea production. First of all, it was
assumed that nitrate nitrogen appearing in the total discharge
originated entirely from ammonium nitrate production, while
organic nitrogen appearing in the total discharge originated
entirely from urea production. An approximation was used to
segregate the wastewater flow and ammonia nitrogen discharge to
urea and ammonium nitrate production. It was assumed that the
amount of wastewater generated by each plant (urea or ammonium
nitrate) and the amount of ammonia nitrogen discharged by each
plant were roughly proportional to the amount of nitrogen (in the
form of product ammonium nitrate or urea) each plant in a given
nitrogen fertilizer complex produces. The following series of
equations represents the stated assumptions and was used to
compute the wastewater flow and ammonia nitrogen contribution
from urea and ammonium nitrate production to the total discharge
of the nitrogen fertilizer complex:
PAN X CAN * PNAN
-------
tonl/dlyi9ht °f Pr°duct nitr°9en per time, metric
PN
' Ti Tkf
AN
NH3-NT * NH3-NA (B-4)
PNU
X NH3-NT = NHa-Ny (B-5)
PN
PN^ X % - VDD (B-7)
where NH3-NT = total discharged ammonia nitrogen, metric
tons/day
NHa~NAN = ammon;'-a nitrogen discharged from the ammonium
nitrate plant, metric tons/day
NHa-Ny = ammonia nitrogen discharged from the urea
plant, metric tons/day
VD = volumetric flow rate from total plant, m3/s
T
Vn = volumetric flow rate from ammonium nitrate
AN plant, m3/s
Vn = volumetric flow rate from urea plant, m3/s
U m3/s
In a few cases, nitrogen content of the discharge stream was
reported in terms of total Kjeldahl nitrogen (TKN) . The TKN test
measures ammonia-nitrogen and organic nitrogen, but not nitrate
nitrogen (82) . Therefore, in order to segregate nitrogen to
ammonia nitrogen and organic nitrogen in the case of urea pro-
duction discharge, it was assumed that the ratio of ammonia
nitrogen to organic nitrogen present in the discharge was 1:1.
The following series of equations represents these stated assump-
tions and was used when TKN was the effluent parameter reported.
X [(TKN) - (ORG-N )] = NH3-NAN (B-8)
(82) standard Methods for the Examination of Water and Waste
water. Thirteenth Edition. American Public Health
Association, New York, New York, 1971. 874 pp.
83
-------
PN
x [(TKN) - (ORG-Ny)] = NH3-ND
where
= ORG-N
U
(B-9)
(B-10)
TKN = total Kjeldahl nitrogen, metric tons/day
N = organic nitrogen discharge from the urea plant,
metric tons/day
The segregation of effluent characteristics in the case of a
composite waste stream from a nitrogen fertilizer complex, and
the segregation of TKN to ammonia nitrogen and organic nitrogen
in the case of urea production, were the only modifications to
the original data as submitted to the EPA. Modifications due to
other effects listed previously were not made due to lack of suf-
ficient data and desire to preserve the actual range of effluent
parameters occurring within the industry.
Various statistical parameters were computed using the data
listed in Tables B-l and B-2 to derive effluent parameters repre-
sentative of all urea or ammonium nitrate plants. These computed
values are presented in Tables B-3 through B-6.
TABLE B-3.
CALCULATED STATISTICAL PARAMETERS CHARACTERIZING
WASTEWATER STREAMS FROM AMMONIUM NITRATE PLANTS
Minimum Maximum
Mean
Standard
deviation Median
Al 1 x . ' s , nonweighted :
Production rate, metric tons/day (as 100% ammonium nitrate)
Wastewater flow, m3/s
Ratio of wastewater flow to production rate, m3/metric ton
Waste NHj-N:
g nitrogen/metric ton
g nitrogen/day
Waste NOj-N:
g nitrogen/metric ton
g nitrogen/day
Wastewater concentration, g nitrogen/m3 :
NH3-N
N03-N
1-Yr receiving water flow, m^/s:
Low
Mean
Two extreme x. 's eliminated, nonweighted:
Production rate, metric tons/day (as 100* ammonium nitrate)
Wastewater flow, m3/s
Ratio of wastewater flow to production rate, m3/metric ton
Waste NH3-N:
g nitrogen/metric ton
g nitrogen/day
Waste NOJ-N:
g nitrogen/metric ton
g nitrogen/day
Wastewater concentration, g nitrogen/m^ :
NH3-N
NOJ-N
1-Yr receiving water flow,
Low
Mean
3/s
36
0
0
61
0.001
0.1
1,111
0.71
345
386
0.063
30.0
278
0.136
70.5
1,004 373
0.252 0.043
183 20.1
9,920 1,320
245
0.067
40.6
2,060
309
0.021
3.6
0 10,400 1,570 2,600 895
0 2,530,000 398,000 604,000 192,000
0
0
0
0
0.05
0.57
5,180
797,000
9,111
2,900
6,400
19,930
721
182,000
731
252
805
2,694
1,090
217,000
1,890
559
1,905
5,782
346
102,000
83.1
63.8
156
448
309
0.021
3.6
895
2,520 2,110,000 338,000 469,000 192,000
6
2,160
0.1
0.1
0.5
4
3,130
758,000
5,200
951
5,975
17,896
592
167,000
467
170
524
1,839
719
189,000
1,100
273
1,415
4,220
346
102,000
83.1
63.8
156
448
84
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TABLE B-4.
CALCULATED STATISTICAL PARAMETERS CHARACTERIZING
WASTEWATER STREAMS FROM UREA PLANTS
oo
Ul
-
All x.'s, nonweighted:
Production rate, metric tons/day (as 100% ammonium nitrate)
Wastewater flow, m3/s
Ratio of wastewater flow to production rate, m3/metric ton
Waste NH3-N:
g nitrogen/metric ton
g nitrogen/day
Waste ORG-N:
g nitrogen/metric ton
g nitrogen/day
Wastewater concentration, g nitrogen/m3:
NH3-N
ORG-N
1-Yr receiving water flow, m3/s:
Low
Mean
Two extreme x.'s eliminated, nonweighted:
Production rate, metric tons/day (as 100% ammonium nitrate)
Wastewater flow, m3/s
Ratio of wastewater flow to production rate, m3/metric ton
Waste NH3-N:
g nitrogen/metric ton
g nitrogen/day
Waste ORG-N:
g nitrogen/metric ton
g nitrogen/day
Wastewater concentration, g nitrogen/m3 :
NH3-N
ORG-N
1-Yr receiving water flow, m3/s:
Low
Mean
Minimum
45
0.0002
0.12
8
2,150
8
1,350
0.2
0.9
0.05
4
51
0*0004
0.15
8
2,580
22
1,990
5
1
0.5
68
Maximum
1,083
0.511
263
7,780
1,730,000
18,400
2,150,000
1,030
3,640
6,400
19,930
1,000
0.2174
83.9
6,180
1,300,000
4,460
3,240,000
495
1,170
5,975
17,896
Mean
342
0.0554
26.0
1,280
287,000
1,400
190,000
168
299
1,698
5,227
320
0.0354
14.0
1,020
229,000
532
92 , 000
134
129
1,484
4,549
Standard
deviation
304
0.1136
57.4
2,180
458,000
4,120
473,000
239
830
2,621
7,896
261
0.0525
19.1
1,690
337,000
1,032
108,000
127
280
2,440
7,261
Median
201
0.0179
3.22
245
115,000
161
51,700
88
29
347
1,248
201
0.0179
3.22
245
115,000
161
517,000
88
29
347
1,248
-------
TABLE 5. CALCULATED STATISTICAL PARAMETERS CHARACTERIZING
WASTEWATER STREAMS FROM AMMONIUM NITRATE PLANTS
All x-^'s, weighted:
Wastewater flow, m3/s
Waste NH3-N:
g nitrogen/metric ton
g nitrogen/day
Waste N03-N:
g nitrogen/metric ton
g nitrogen/day
Wastewater concentration, g nitrogen/m3 :
NH3-N
N03-N '
1-Yr receiving water flow, mvs:
Low
Mean
Two extreme x. 's eliminated, weighted:
Wastewater flow, m3/s
Waste NH3-N:
g nitrogen/metric ton
g nitrogen/day
Waste N03-N:
g nitrogen/metric ton
g nitrogen/day
Wastewater concentration, g nitrogen/m3:
NH3-N
N03-N
1-Yr receiving water flow, mj/s:
Low
Mean
Mean
0.0508
1,030
410,000
472
197,000
608
376
914
2,922
0.0327
862
377,000
471
181,000
482
121
771
1,985
Standard
deviation
0.115
1,560
827,000
563
290,000
1,460
1,490
2,667
7,515
0.0482
1,190
809,000
556
270,000
1,270
157
2,564
7,628
TABLE B-6.
CALCULATED STATISTICAL PARAMETERS CHARACTERIZING
WASTEWATER STREAMS FROM UREA PLANTS
Mean
Standard
deviation
All x^'s, weighted:
Wastewater flow, m3/s 0.0499 0.0727
Waste NH3-N:
g nitrogen/metric ton 838 1,340
g nitrogen/day 334,000 629,000
Waste ORG-N:
g nitrogen/metric ton 580 1,410
g nitrogen/day 139,000 211,000
Wastewater concentration, g nitrogen/in3 :
NH3-N 135 171
ORG-N 148 320
1-Yr receiving water flow, m3/s :
Low 2,735 5,472
Mean 8,273 16,356
Two extreme x.'s eliminated, weighted:
Wastewater flow, m3/s 0.0399 0.0560
Waste NH3-N:
g nitrogen/metric ton 756 1,270
g nitrogen/day 279,000 567,000
Waste ORG-N:
g nitrogen/metric ton 275 301
g nitrogen/day 104,000 148,000
Wastewater concentration, g nitrogen/m3:
NH3-N 120 155
ORG-N 90 188
1-Yr receiving water flow, m3/s:
2,728 5,688
8,889 18,394
Mean
86
-------
A maximum, minimum, mean, standard deviation, and median were
generated for each column appearing in Tables B-l and B-2. In
addition, the same statistical parameters were derived after
eliminating the minimum and maximum in each column of data.
These statistical parameters are listed in Tables B-3 and B-4.
Weighted statistical parameters were also generated for each
column using the fraction of the total production rate of all
plants considered as the weighing factor. Using the statistical
method, values associated with the largest plants would have a
greater impact on the derivation of the statistical parameter.
The following equations were used to calculate weighted means
and weighted standard deviations:
n
E
(B-ll)
s =
n
w. \
-^riN(n)
V> W-; I v '
- x
n-1
(B-12)
where
x =
s =
n =
wi =
Wj =
X,- =
arithmetic mean
standard deviation
number of samples
plant output corresponding with
plant output, metric tons/day
individual of the column for which the statistical
parameter is being calculated
metric tons/day
Units for x^ are given in Table B-7.
in Tables B-5 and B-6.
87
-------
TABLE B-7. UNITS FOR
Parameter
Units
Wastewater flow
m
3/s
Nitrogen waste flow
NH3-N g NOa-N g Org-tJ
day ' day ' day
Concentration
NHs-N
m3
NO^-N g Org-N
m
Flow/output ratio
m
metric ton
88
-------
GLOSSARY
air stripping: Wastewater treatment process in which, as applied
to nitrogen fertilizer effluents, air is passed counter-
current to a wastewater stream in a column or stripping
tower to remove ammonia.
biological treatment: Wastewater treatment process which, as
applied to nitrogen fertilizer effluent, employs biological
nitrification to aerobically oxidize ammonia to nitrate,
and biological denitrification to anaerobically reduce
nitrate to nitrogen gas.
carbon monoxide shift: High and low temperature catalytic
reaction in which steam is added to transform carbon
monoxide to carbon dioxide and hydrogen in the production
of synthetic ammonia.
containment: Wastewater control technology in which effluent
is collected, held, and may or may not be drained.
desulfurization: Removal of hydrogen sulfide from natural gas
feedstock, prior to reforming, by use of an activated
carbon or zinc oxide bed in the production of synthetic
ammonia.
graining: Process in which concentrated solution is solidified
by placing it in a steam jacket-heated kettle and mixing
until the water evaporates.
granulation: Process in which concentrated solution is solidi-
fied by spraying it on a falling curtain or rolling bed of
seed particles to build a larger particle.
hazard factor: Concentration of a particular pollutant in
water which has been determined to be hazardous to aquatic
life.
high density prills: Prills formed using a 99.5+% solution that
lowers the number of void spaces formed to create a more
dense prill.
89
-------
ion exchange: Wastewater treatment process by which an ion in
the wastewater is exchanged for a more desirable counterion
on a resin in a column or bed.
low density prill: Prills formed using a 95% to 96% solution
that allows more voids in the final product, giving a less
dense prill.
methanation: Catalytic reaction in which hydrogen in process
gas converts trace amounts of carbon monoxide and carbon
dioxide to methane and water in the production of synthetic
ammonia.
prill: Spherical particle formed by the solidification of
solution droplet.
prilling: Process in which concentrated solution is solidified
by spraying it in a tower so that the drops formed fall
countercurrent to a stream of cooling air.
primary reformer: Set of catalyst-filled tubes in which natural
gas (methane) reacts with steam to form carbon monoxide
and hydrogen in the production of synthetic ammonia.
secondary reformer: Catalytic reactor in which compressed air
is mixed with process gas from primary reformer to produce
a synthesis gas with a hydrogen-to-nitrogen mole ratio of
3:1 in the production of synthetic ammonia.
source severity: Ratio of the concentration of a given pollutant
in the receiving water as a result of discharge to the mini-
mum concentration of the pollutant determined to be hazard-
ous (hazard factor).
steam stripping: Process in which process condensate flows
down a column countercurrent to steam which extracts
ammonia and methanol from condensate.
urea hydrolysis: Process in which urea in condensate is con-
verted through a series of intermediate products back to
ammonia and carbon dioxide, which are then driven off with
steam.
90
-------
CONVERSION FACTORS AND METRIC PREFIXES (83)
CONVERSION FACTORS
To convert from
Degree Celsius (°C)
Gram (g)
Joule (J)
Kilogram (kg)
Kilogram (kg)
Kilogram/meter3 (kg/m3)
Kilometer2 (km2)
Meter (m)
Meter3 (m3)
Meter3
Meter3/second (m3/s)
Metric ton
Pascal (Pa)
Pascal (Pa)
Second (s)
To
Degree Fahrenheit (°F)
Pound-mass
British thermal unit (Btu)
Pound-mass (avoirdupoi s)
Ton (short, 2,000 Ib mass)
Pound-mass/gallon (Ib-m/gal)
Mile2
Foot
Foot3
Liter
Gallon/minute (gpm)
Ton (short, 2,000 Ib mass)
Atmosphere
Pound-force/inch2 (psi)
Minute
Multiply by
t_ = 1.8 t
32
.c
2.205 x 10~3
9.479 x 10-lf
2.205
1.102 x 10~3
8.348 x 10~3
3.861 x 10
-1
281
103
3
3.531 x 10
1.000 x 10
1.585 x 10k
1.102
9.869 x 10~6
1.450 x 10-1*
1.667 x 10
~2
Prefix Symbol
Mega
Kilo
Milli
Micro
M
k
m
V
METRIC PREFIXES
Multiplication factor
106
TO
io~3
Example
10
-6
5 MPa = 5 x 10b pascals
5 kg
5 mg
5 lag
5 x 103 grams
5
x 10~3 gram
= 5 x 10
-6
gram
(83) Standard for Metric Practice. ANSI/ASTM Designation
E 380-76e, IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976.
37 pp.
91
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO.
EPA- 600/2 -79-019b
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
SOURCE ASSESSMENT: Nitrogen Fertilizer Industry
Water Effluents
S. REPORT DATE
January 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
W.J.Search, J.R.Klieve, G.D.Rawlings,
J.M.Nyers, and R. B. Reznik
8. PERFORMING ORGANIZATION REPORT NO.
MRC-DA-869
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45407
10. PROGRAM ELEMENT NO.
1AB015
11. CONTRACT/GRANT NO.
68-02-1874
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final: 8/77 - 10/78
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTESJERL.RTP project officer is Ronald A. Venezia, MD-62, 919-541-
2547. Earlier Source Assessment reports are in the EPA-600/2-76-032, -77-107,
and -78-004 series.
16. ABSTRACTIJ.^ report describes a study of waterborne pollutants from the manufacture
of nitrogen fertilizers. It includes an evaluation of the ammonia, ammonium nitrate,
urea, and nitric acid manufacturing processes. Water effluents in a nitrogen fertil-
izer plant originate from a variety of point and nonpoint sources. Major components
in the effluents are ammonia nitrogen, nitrate nitrogen, and organic nitrogen. The
potential environmental impact of nitrogen fertilizer effluents was evaluated by com-
paring the concentration of a particular pollutant in a receiving stream as a result
of discharge to an acceptable concentration (hazard factor). The ratio of these two
values is the source severity. At a mean receiving water flow rate and the average
stream pH of 7.6, all severities were below 0.05. Control technologies, available
and in use at some nitrogen fertilizer plants, include containment, steam and air
stripping, urea hydrolysis, biological treatment, ion exchange, and condensate
reuse.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a.
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
Pollution
Assessments
Fertilizers
Ammonia
Ammonium Nitrate
Urea
Biological Treatment
Nitric Acid
Containment
Stripping
Hydrolysis
Ion Exchanging
Condensates
Circulation
Pollution Control
Stationary Sources
Nitrogen Fertilizers
Steam Stripping
Air Stripping
Condensate Reuse
13B
14B
02A
07 B
07C
06A
07A,13H
07D
8. DISTRIBUTION STATEMEN1
Unlimited
19. SECURITY CLASS (ThisReport)'
Unclassified
20. SECURITY CLASS (Thispage)
Unclassified
21. NO. OF PAGES
103
22. PRICE
EPA Form 2220-1 (9-73)
92
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