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

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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.

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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.

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                            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

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                        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.

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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

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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

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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

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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

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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

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                                 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

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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

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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

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                                                    PRODUCT SHIPMENT

CD
SOLUTION PRODUCTION SOLID PRODUCTION r-

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/^^
AMMONIA

CARBON^
DIOXIDE


SECTION
^v _— -^\.
— ^ r ^
SOLUTION
PRODUCTION





SOLUTION
CONCENTRATION


SOLID
FORMATION



FINISHING




£
o
z
o







RECYCLE |


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cz
s
r~
O
>
z
o






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UKtA
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      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

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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

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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

-------
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

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        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

-------
                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

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              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

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                            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

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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

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                                                  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

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                               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

-------
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

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                           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

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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

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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

-------
                       REFERENCES
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Search, W. J. , and R. B. Reznik.  Source Assessment:  Urea
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Rawlings, G.  D. , and R. B. Reznik.  Source Assessment:
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Rawlings, G.  D. , and R. B. Reznik.  Source Assessment:
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Quartulli, O. J.  Stop  Wastes:  Reuse Process Condensate.
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Romero, C. J. , D. A. Brown, and J.  H. Mayes.  Treatment of
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Spangler, H.  D.  Repurif ication of  Process Condensate.   In:
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Quartulli, 0. J.  Review of Methods for  Handling Ammonia
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                            61

-------
10.  Fineran, J. A., and P. H. Whelchel.  Recovery and Reuse  of
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                                62

-------
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31.  Thurston, R. V., et al.   Aqueous  Ammonia Equilibrium Calcu-
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                                63

-------
33.  Reznik, R. B-, E. C. Eimutis, J. L. Delaney, T. J. Hoogheem,
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34.  Code of Federal Regulations, Title 40 - Protection of Envi-
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36.  Personal communication with T. W. Segar, N-ReN Corporation,
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37.  Smit, A. C. M., and P. U. C. Kaasenbrood.  Treatment of
     Urea-Plant Effluents.  Industrial Wastes, 22(5):44-47, 1976.

38.  Van Moorsel, W. H.  Method for Treatment of Urea Crystal-
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39.  Urea Makers Can Strip Away Waste Problems.  Chemical Week,
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40.  Mioduszewski, D.  Ammonia Removal - What's Best?  Water  &
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41.  Bingham, E. C., and R. C. Chopra.  A Closed Cycle Water
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42.  Brennan, J. F.  The Chem-Seps Nitrogen Recovery Process:
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     Washington, D.C.  pp. 217-249.

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.
                               64

-------
45.  Sloan, C. R., and A.  S.  McHone.   The  Effect of the Energy
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     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 Pro-
     cessing, 53(10):133-135, 1974.

48.  Current Industrial Reports, Inorganic Chemicals.  U.S.
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49.  Current Industrial Reports, Inorganic Fertilizer Materials
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50.  Current Industrial Reports, Inorganic Fertilizer Materials
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51.  Current Industrial Reports, Inorganic Fertilizer Materials
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52.  Water Resources Data for New York,  1975.  USGS/WRD/HD-76/029
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53.  Water Resources Data for Louisiana, 1975.  USGS/WRD/HD-76/
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     Division, Baton Rouge, Louisiana,  1975.   829  pp.

54.  Water Resources Data for Virginia,  1975.  USGS/WRD/HD-76/035
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55.  Water Resources Data for Kentucky, 1975.  USGS/WRD/HD-76/002
      (PB 251 853), U.S. Geological Survey, Water Resources Divi-
     sion, Louisville, Kentucky, 1976.   348  pp.

56.  Water Resources Data for Nebraska, 1975.   USGS/WRD/HD-76/30
      (PB 259 842), U.S. Geological Survey, Water  Resources Divi-
     sion, Lincoln,  Nebraska, 1976.  481 pp.

57.  Water Resources Data for Illinois, 1975.   PB 254  434,  U.S.
     Geological Survey, Water Resources Division,  Champaign,
     Illinois, 1976. 417 pp.
                                65

-------
58.  Water Resources Data for Arizona, 1975.  USGS/WRD/HD-76/036
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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
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61.  Water Resources Data for Texas, 1975.  Volume 1.  USGS/WRD/
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62.  Water Resources Data for Indiana, 1975.  USGS/WRD/HD-76/010
     (PB 251 859), U.S. Geological Survey, Water Resources Divi-
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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
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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

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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

-------
                 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

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                             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

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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

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             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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