EPA
Group I, Phase II
Development Document for
Effluent Limitations Guidelines and
New Source Performance Standards
for the
FORMULATED FERTILIZER
Segment of the
FERTILIZER MANUFACTURING
Point Source Category
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
JANUARY 1975
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DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES
and
NEW SOURCE PERFORMANCE STANDARDS
for the
FORMULATED FERTILIZER SEGMENT
of the
FERTILIZER MANUFACTURING
POINT SOURCE CATEGORY
Russell E. Train
Administrator
James L. Agee
Assistant Administrator for
Water and Hazardous Materials
Allen Cywin
Director, Effluent Guidelines Division
Elwood E. Martin
Project Officer
January, 1975
Effluent Guidelines Division
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 • Price $1.40
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ABSTRACT
This document presents the findings of an in-depth technical
study (Phase II) conducted by Davy Powergas, Inc., on those
fertilizer processes not included in the original (Phase I)
study under Contract Number 68-01-1508, Mod. #1. The
purpose was to determine industry control practices, water
effluent treatment technologies, and cost data related to
these items as information from which meaningful effluent
guidelines could be developed to implement the Federal Water
Pollution Control Act Amendments of 1972.
The fertilizer industry has seven distinctly separate
subcategories which have different pollutants, effluent
treatment technologies, and water management problems.
These subcategories are Phosphate, Ammonia, Urea, Ammonium
Nitrate, Nitric Acid, Ammonium Sulfate and Mixed and Blend
Fertilizers. In this Phase II study, only ammonium sulfate
manufacture as a synthetic and a coke oven by-product
material and the mixed and blend fertilizer processes are
included. The mixed and blend fertilizers in combination
represent by an overwhelming majority the largest number of
individual process plants in the overall fertilizer
category.
Functions performed in the survey included data gathering,
sample collection and analysis, and visitations with
responsible plant operating personnel to obtain verifiable
information on treatment technology in commercial use and in
development.
For the Phase II fertilizer processes of interest, the
effluent treatment technologies consist entirely of
treatment technologies now in use in the better plants. Use
of these technologies coupled with good water management
make the recommended best practicable control technology
currently available, best available technology economically
achievable, and new source performance standards identical
and capable of no discharge of process waste water
pollutants to navigable waters.
iii
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CONTENTS
Section Page
I CONCLUSIONS 1
II RECOMMENDATIONS 3
III INTRODUCTION 5
IV INDUSTRY CATEGORIZATION 31
V WASTE CHARACTERIZATION 35
VI SELECTION OF POLLUTANT PARAMETERS 41
VII CONTROL AND TREATMENT TECHNOLOGY 47
VIII COST, ENERGY AND NONWATER
QUALITY ASPECTS 53
IX BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE, GUIDELINES AND
LIMITATIONS 57
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE, GUIDELINES AND LIMITATIONS 61
XI NEW SOURCE PERFORMANCE STANDARDS AND
PRETREATMENT STANDARDS 63
XII ACKNOWLEDGEMENTS 65
XIII REFERENCES 67
XIV GLOSSARY 71
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FIGURES
Page
1 Ammonium Sulfate - Synthetic Plant Locations 15
2 Ammonium Sulfate - By-Product Plant Locations 16
3 Ammonium Sulfate Flow Sheet - Synthetic 19
4 Ammonium Sulfate Flow Sheet - Coke Ovens 20
5 Blend Fertilizer - Plant Locations 23
6 Mixed Fertilizer - Plant Locations 24
7 Mixed Fertilizer Flow Sheet 29
8 Blend Fertilizer Flow Sheet 30
9 Ammonium Sulfate Plant - Effluent control 49
10 Mixed Fertilizer Process - Effluent Control 51
11 Blend Plants - Airborne Solids Control 52
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TABLES
Table Page
1 Cost Summary Table 54
2 Metric Units 72
vii
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SECTION I
CONCLUSIONS
The fertilizer industry subcategories established in the
original "Development Document for Effluent Limitations
Guidelines and Standards of Performance" document were also
utilized in this Phase II study namely, phosphate, ammonia,
ammonium nitrate, urea, and nitric acid.
Phase II includes ammonium sulfate produced as both a
synthetic and as a coke oven by-product material and the
mixed fertilizer and blend fertilizer materials.
In both of the subcategories the treatment technologies do
exist and are commercially practiced to meet the proposed
best practical control technology currently available, best
available technology economically achievable, and which will
allow new plants to also meet the proposed guidelines
without changes in process design or equipment.
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SECTION II
RECOMMENDATIONS
Ammonium Sulfate Production Subcategory
The proposed effluent limitation representing the degree of
effluent reduction attainable through application of the
best practicable control technology currently available,
best available technology economically achievable and best
demonstrated control technology in the production of
ammonium sulfate - both synthetic and coke oven by-product -
is no discharge of process waste water pollutants to
navigable waters.
Mixed and Blend Fertilizer Production Subcateggry
The proposed effluent limitation representing the degree of
effluent reduction attainable through application of the
best practicable control technologies currently available,
best available technology economically achievable and best
demonstrated control technology from both the mixed
fertilizer and blend fertilizer process plants is no
discharge of process waste water pollutants to navigable
waters.
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SECTION III
INTRODUCTION
Section 301 (b) of the Act requires the achievement by not
later than July 1, 1977, of effluent limitations for point
sources, other than publicly owned treatment works, which
are based on the application of the best practicable control
technology currently available as defined by the
Administrator pursuant to Section 304(b) of the Act.
Section 301(b) also requires the achievement by not later
than July 1, 1983, of effluent limitations for point
sources, other than publicly owned treatment works. These
are to be based on the application of the best available
technology economically achievable which will result in
reasonable further progress toward the national goal of
eliminating the discharge of all pollutants, as determined
in accordance with regulations issued by the Administrator
pursuant to Section 304(b) of the Act. Section 306 of the
Act requires the achievement by new sources of a Federal
standard of performance providing for the control of the
discharge of pollutants which reflects the greatest degree
of effluent reduction which the Administrator determines to
be achievable through the application of the best available
demonstrated control technology, processes, operating
methods, or other alternatives, including, where
practicable, a standard permitting no discharge of
pollutants.
Section 304 (b) of the Act requires the Administrator to
publish within one year of enactment of the Act, regulations
providing guidelines for effluent limitations setting forth
the degree of effluent reduction attainable through the
application of the best practicable control technology
currently available and the degree of effluent reduction
attainable through the application of the best control
measures and practices achievable including treatment
techniques, process and procedure innovations, operation
methods and other alternatives. The regulations proposed
herein set forth effluent limitations guidelines pursuant to
Section 304 (b) of the Act for the fertilizer manufacturing
category of point sources.
Section 306 of the Act requires the Administrator, within
one year after a category of sources is included in a list
published pursuant to Section 306 (b) (1) (a) of the Act, to
propose regulations establishing Federal Standards of
performances for new sources within such categories. The
Administrator published in the Federal Register of January
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16, 1973 (38 F.R. 1624), a list of 27 source categories.
Publication of the list constituted announcement of the
Administrator's intention of establishing, under Section
306, standards of performance applicable to new sources
within the fertilizer manufacturing category of point
sources, which was included within the list published
January 16, 1973.
The effluent limitations guidelines and standards of perfor-
mance presented in this report were developed from operating
data, samples, and information gathered from some fifteen
(15) plants. The methods and procedures used in the
accumulation of that overall information are described in
the following paragraphs.
Summary, of Methods Used for Development of the gffluent
Limitations Guidelines and Standards of Performance
The effluent limitations guidelines and standards of
performance presented herein were developed in the following
manner. The point source category was first studied for the
purpose of determining whether separate limitations and
standards are appropriate for different segments within the
category. This analysis included a determination of whether
differences in raw material used, product produced,
manufacturing process employed, age, size, waste water
constituents, and other factors require development of
separate limitations and standards for different segments of
the point source category.
The raw waste characteristics for each such segment were
then identified. This included an analysis of (1) the
source of flow and volume of water used in the process
employed and the sources of waste and waste waters in the
plant; and (2) the constituents (including thermal) of all
waste waters, including toxic constituents and other
constituents which result in taste, odor, and color in the
water or aquatic organisms. The constituents of the waste
waters which should be subject to effluent limitations
guidelines and standards of performance were identified.
The range of control and treatment technologies existing
within each segment was identified. This included an
identification of each distinct control and treatment
technology, including both in-plant and end-of-process
technologies, which are existent or capable of being
designed for each segment. It also included an
identification of, in terms of the amount of constituents
(including thermal) and the effluent level resulting from
the application of each of the treatment and control
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technologies. The problems, limitations and reliability of
each was also identified. In addition, the nonwater impact
of these technologies upon other pollution problems,
including air, solid waste, noise and radiation were also
identified. The energy requirements of each control and
treatment technology was identified as well as the cost of
the application of such technologies.
The information, as outlined above, was then evaluated in
order to determine what levels of technology constituted the
"best practicable control technology currently available",
the "best available technology economically achievable" and
the "best available demonstrated control technology,
processes, operating methods, or other alternatives". In
identifying such technologies, various factors were
considered. These included the total cost of application of
technology in relation to the effluent reduction benefits to
be achieved from such application, the age of equipment and
facilities involved, the process employed, the engineering
aspects of the application of various types of control
techniques, process changes, nonwater quality environmental
impact (including energy requirements) , and other factors.
Delineation of Study
The effluent limitation guidelines and standards of
performance proposed in this report were developed from
operating data, samples, and information gathered from
fifteen (15) plants. The methods and procedures used in the
accumulation of that overall data is described in the
following paragraphs.
Identification and categorization of the four (4) processes
covered in this report were made during the preparation of
the Phase I portion of the industry report on Basic
Fertilizer Chemicals. The four processes covered in this
Phase II portion of the Formulated Fertilizer report and the
corresponding Standard Industrial Classification (SIC) Codes
are defined as:
MIXED FERTILIZER, SIC Codes 2874 and 2875
This process is defined as one which mixes (wet or dry)
straight and mixed fertilizer materials through chemical
reaction into complete N-P-K fertilizer goods. By fer-
tilizer terminology it includes three types of plants:
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B type - Dry mixing plant that mixes wet or dry,
straight and mixed fertilizer materials
through chemical reaction, into complete
mix goods.
C type - Does same as B type except that normal
superphosphate is also produced on site.
D type - Does same as B and c types plus the manu-
facture of sulfuric acid.
BLEND PLANT, SIC Code 2875
This process is defined as one which physically mixes
dry straight and mixed granular fertilizer materials
to a given N-P-K formulation. By fertilizer terminology
it is specified as an A type plant.
AMMONIUM SULFATE - Steel mill By-Product, SIC Code 2873
AMMONIUM SULFATE - Synthetic, SIC Code 2873
The objective was to categorize the many processes into the
least number of units that are practical for the end purpose
of water effluent monitoring and structuring of specific
fertilizer complexes for EPA and State enforcement
officials. Categorization inherently included determination
of those point sources which required separate limitations
and standards. The overall concept was to provide
sufficient definition and information on an unitized basis
to allow application of a building block principle. Such
classification of data readily permits the structuring of
total water effluent information for any specific fertilizer
complex regardless of the multiplicity of processes
comprising its make-up.
Bases for Definition of Technology Levels
The validated data and samples obtained from the fifteen
plants were the primary basis for choosing the levels of
technology which were considered to be the "best practicable
control technology currently available", the "best available
technology economically achievable," and the "best available
demonstrated control technology, process operating methods,
or other alternatives". This selection of the separate
technologies, of necessity, required consideration of such
additional factors as evaluation of the engineering and
operational problems associated with the technology, effect
on existing processes, total cost of the technology in
relation to the effluent reduction that would be realized,
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energy requirements and cost, the range of control
variations on contaminant concentration and/or quantity, and
non-water quality environmental impact. Information
regarding the influence of these diverse factors was
obtained from a number of sources. These sources include
government research information, published literature, trade
organization publications, information from qualified
consultants, and cross reference with related technologies
utilized in other industries.
Implementation
The value of a study such as this is entirely dependent upon
the quality of the data from which it is made. Particular
attention was, therefore, directed to selecting criteria for
determining the commercial installations to be visited and
from which to collect information.
The multiplicity of plants, wide geographical distribution
(particularly blend plants), and the wide range of plant
capacities (300 to 876,000 TPY) made the Phase I concept of
selecting only exemplary plants for the study impractical.
The selection of plants was based primarily on consideration
of geographical location. Plants of all different
capacities in the states of Alabama and Illinois were
selected for the study. These two states were considered
representative of the two general geographical areas,
Southeast and West North Central, with the highest process
plant density coupled with good proximity of the two
subcategories to each other.
Contact was then made with plants in the two selected areas
to establish a time for a screening visit. The screening
visit had the objective of informing the plant manager on
the purpose and intent of the study. Information acquired
during the visit was used to determine whether that
particular plant was to be included in the study or whether
there were other plants and/or conditions which better
exemplified industry standards. As in the Phase I study a
variety of situations were encountered. These ranged from
decisions not to include a specific plant, although
exemplary, to learning of another plant which could add a
different dimension or production level to the study. It
was found that a very small percentage of the plants had
records of either water or air effluent streams.
A comparative evaluation was made of the various plants
visited. This evaluation was based upon the criteria used
in the Phase I study. It consisted of the following points:
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1) Discharge Effluent Quan-fcj-bj.es
Installations with low effluent quantities and/or the
ultimate of "no discharge".
2) gffluent^Contaminant Lgvel
Installations with low effluent contaminant concentrations
and quantities.
3) Effluent Treatment Method and Effectiveness
Use of best currently available treatment methods, operating
control, and operational reliability.
H) Water Management Practice
Utilization of good management practices such as main water
re-use, planning for seasonal rainfall variations, in-plant
water segregation and proximity of cooling towers to
operating units where airborne contamination can occur.
5) Land Utilization
Consideration of land area involved in water effluent
control system with the most acceptable being those with the
least area.
6) Air Pollution Control
Those plants with the most comprehensive and effective air
pollution control. In turn liquid effluent from such plants
may represent the most serious water effluent condition.
7) Geographic Location
Those facilities in close proximity to sensitive vegetation,
high population density, land availability, and areas where
local or state standards are most restrictive.
8) Management Operating Philosophy
Plants whose management insists upon effective equipment
maintenance and housekeeping practices.
9) Raw Mategialg
Installations utilizing different raw materials where
effluent contaminants differ in impurity type or concen-
tration.
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10) Diversity of Processes
On the basis that, other criteria are met, then consideration
was given to installations having a multiplicity of ferti-
lizer processes.
Each of the above criterion were assigned a range of
numerical values to allow a comparative evaluation of the
different plants visited in each process category.
Sampling Collection and Validation of Data
The most important item in a study of this nature is to
obtain data representative of a given process under all
conditions of operation and range of production rates.
Steps and procedures used in selecting data, stream
sampling, and sample analysis were all designed to
accomplish this goal to the best possible degree.
An important step toward this objective was the assignment
of only highly experienced operating personnel to the field
work. Three persons were used. The fertilizer plant opera-
ting experience of these three people ranged from a minimum
of 16 years to 24 years. With such operational knowledge it
was possible to expeditiously select data, identify specific
process streams for sampling, and conduct sampling under
readily discernible plant operating conditions. The points
considered and identified in all data collection, sampling,
and validation were:
1) Segregation of process effluent streams so that only an
identifiable single process and/or piece of equipment was
represented.
2) Collection of data and samples at different states of
process conditions such as normal steady state, plant
washout when such a procedure is followed on a routine
basis, upset process condition, operation at above/below
plant design rate, and during shutdown conditions if
effluent flow occurs.
3) Evaluation of the effect if any of seasonal rainfall,
particularly on non-point effluent and ponds.
H) Establishment of the existence of flow measurement
devices and/or other means of quantitatively measuring
effluent flows.
5) Making positive identity of the type, frequency, and
handling of the samples represented by collected data -
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i.e., such items as grab, composite, or continuous type;
shift, daily, or weekly frequency, etc. All samples
collected by the contractor were composite samples.
6) Validation of data, via intimate knowledge of plant
laboratory analytical procedures used for sample analysis,
check samples analyzed by independent laboratories, and/or
DPG sampling under known and defined process conditions with
sample analysis by an accredited commercial laboratory, was
conducted on each plant which had liquid effluents. A total
of 15 plants were visited. Data was collected by DPG from
seven of these plants. Verified data on ammonium sulfate
production was also obtained from another contractor who had
collected data in two large complexes which included
ammonium sulfate manufacturing facilities.
GENERAL DESCRIPTION OF THE INDUSTRY
The U. S. fertilizer industry has undergone such significant
changes in the past thirty years that it has lost its old
stigma of "mud chemistry". The sledge hammer and shovel
days have been replaced by large, modern, fume free, plants
operated from an air conditioned control room.
Eighty percent of the volume of agricultural chemicals used
today are materials that were not available in their present
form at the time of World War II. Fertilizer use today, in
terms of plant nutrients, is four and one quarter times as
great as it was in 1940. On the assumption that this
fertilizer is properly used, it represents one of the major
reasons why farm yields are up and unit costs are lower. It
has been estimated that the use of commercial fertilizer
saves the U. S. public $13 billion a year on food bills or
about $70 a year per person. Large scale centrifugal
compressor ammonia plants, increasing single train plant
capacities from 90 - 180 to 1400 - 1800 kkg/day (100 - 200
to 1500 - 2000 tons/day); sulfuric acid plant capacity
increased from 270 - 450 to 1800 kkg/day (300 - 500 to 2000
tons/day); and development of ammonium phosphate granule
fertilizers illustrate the dramatic technology change.
Fertilizer industry jargon identifies two types of product -
nonmixed and mixed. Straight fertilizers are defined as
those which contain only a single major plant nutrient.
Mixed fertilizers are defined as those which contain two or
more primary plant nutrients. Mixed fertilizers can be
produced by chemically reacting different ingredients and
utilizing the chemical reaction as the binding force; or
simply by mechanically blending together straight
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fertilizers. The following tabulation lists the principal
straight and mixed fertilizers produced in the United
States.
Straight Fertilizers Mixed Fertilizers
Nitrogen Fertilizers
Ammonia
Urea
Ammonium Nitrate
*Ammonium Sulfate
Phosphate Fertilizers
Phosphoric Acid Ammonium Phosphates
Normal Superphosphate *Mixed Fertilizers
Triple Superphosphate *Blend Fertilizers
* Processes included in this study.
This Phase II portion of the Basic Fertilizer Chemicals
study considers only those fertilizer processes not included
in the Phase I study scope - namely Ammonium Sulfate and
Mixed and Blend Fertilizers.
Ammonium Sulfate Manufacturing
Ammonium sulfate is one of the older forms of nitrogen
fertilizer and is still used in significant quantity. It
is, however, the one nitrogen fertilizer material in the U.
S., which with the exception of 1972, has a history of
gradual production decrease. Production records of recent
years are shown below:
Year Ammonium Sulfate Production
Tons per Year
1966 2,859,505
1967 2,824,255
1968 2,723,267
1969 2,563,724
1970 2,483,985
1971 2,359,800
1972 2,419,000
This unusual situation is attributed to the spectacular
popularity and corresponding production increases of
diammonium phosphate (DAP) as a mixed fertilizer material.
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Ammonium sulfate (AS) and DAP have approximately equal N
contents - nominal 21% and 1856 respectively. DAP, however,
has both a chemical and physical advantage over AS. The
chemical advantage is that it also has a nominal 48% P2O5.
This in turn means shipping and storage cost advantages to
the mixed fertilizer manufacturers. The physical advantage
is that DAP is a granular rather than a crystalline material
and, therefore, is more compatible with other straight or
mixed fertilizers for either granulation or dry blending.
There seems to be little question that ammonium sulfate's
percentage of total N market will continue to decrease
although production tons may hold relatively steady and even
possibly increase. This possible increase in tonnage would
be a result of by-product material from rapidly increasing
caprolactum and acrynitrile production rather than from new
AS manufacturing facilities. The rapid increase in
synthetic fibers demand (nylon and acrylic) for which
caprolactum and acrynitrile are production intermediates
means that 1.0 to 5.0 tons of AS will come on the market for
every 1.0 ton of intermediates produced.
Ammonium sulfate is generated from basically three sources -
synthetic, chemical, and coke oven. Synthetic AS is
produced by the direct combination of virgin ammonia and
sulfuric acid. Chemical AS is produced as a by-product of
the above mentioned synthetic fiber intermediates. Coke
oven AS is produced from ammonia reclaimed from the coking
of coal by absorption with sulfuric acid. Only AS as
produced synthetically and from coke oven gas are covered in
this report. Chemical AS is covered in a separate
industrial category. Today there are six synthetic plants
and approximately 46 coke oven units. The greatest
concentration of coke oven plants is in the steel producing
states, particularly Ohio and Pennsylvania. Locations of
synthetic and coke oven AS plants are indicated on Figures 1
and 2.
General
Ammonium sulfate (AS) has been an important nitrogen
fertilizer source for many years. One of the early reasons
for AS's rise to importance as a fertilizer material was due
to the fact that it developed as a by-product from such
basic industries as steel and petroleum manufacturing. That
reason is still the primary basis for AS's importance. In
fact, it now has the same status in the rapidly growing
synthetic fibers industry. AS's role as a by-product from
such large and basic industries insures that it will
continue to be an important source of U.S. nitrogen
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FIGURE 1
AMMONIUM SULFATE - SYNTHETIC
PLANT LOCATIONS
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FIGURE 2
AMMONIUM SULFATE - BY PRODUCT
PLANT LOCATIONS
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fertilizer tonnage. An additional reason for the continuing
importance of AS is the growing awareness of the agronomic
need for sulfur addition to many soils.
Ammonium sulfate is a versatile fertilizer material. It can
be used as a straight fertilizer for direct application, as
a raw material for production of blend fertilizer, and as a
raw material for production of mixed fertilizer. AS is a
crystalline material which exhibits those desirable physical
fertilizer characteristics, such as being freeflowing and
relatively non-caking, when additives are used.
Agronomically AS is suitable for use on most crops. It is
especially compatible and desirable for rice, tobacco, tea,
cocoa and millet.
The emphasis on environmental improvement is another issue
which is expected to affect future AS production. Specific
reference is to the restrictions on sulfur oxides emission.
The air pollution control processes for removal of sulfur
oxides either from commercial products such as natural gas,
petroleum and coal or end-of-process streams such as exhaust
gases from sulfuric acid and power generation plants all
have a sulfur base compound as an end product. Sizeable
quantities of these end products are expected to end up as
fertilizer AS principally because this material can accept
small quantities of impurities without detracting from its
value. The AS future is expected to continue to be a
reversal of the decreasing production tonnage trend which
started in 1965 and concluded in 1972. This greater future
tonnage is, however, expected to be as a by-product material
rather than from an increase in synthetic AS production.
The processes studied in this Phase II report included only
two of the three principal AS production processes namely,
synthetic and coke oven-by-product. Ammonium sulfate
production from these two processes for the period 1966
through 1972 are tabulated below:
PRODUCTION - SHORT TONS
Synthetic By-Product
1966 1,155,100 763,800
1967 1,242,300 738,000
1968 903,700 670,000
1969 758,500 638,000
1970 663,900 595,000
1971 606,700 540,000
1972 578,600 564,000
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AMMONIUM SULFATE (SYNTHETIC) - PROCESS DESCRIPTION
Synthetic ammonium sulfate is produced from virgin ammonia
and sulfuric acid. (See Figure 3). The chemical reaction
is essentially the neutralization of sulfuric acid with
ammonia as indicated by following chemical equation:
2 NH3 (gas or liq.) + H2SO4 Uiq.)-»lNHHL2SO4 (SOlid) + HEAT
Ammonia Sulfuric Acid Ammonium Sulfate
This reaction is highly exothermic liberating approximately
67,710 cal/g. mole or 4230 BTU/lb N. The raw materials are
reacted in neutralizer/crystallizer units designed with
means of controlled heat removal. Heat removal is achieved
by controlled water addition and evaporation under either
vacuum (sub-atmospheric) or atmospheric pressure conditions.
Vacuum process units control evaporation by variation of
absolute pressure while the atmospheric pressure process is
controlled by varying the air volume blown into the reaction
vessel.
The major process problem is control of the AS crystal size.
Process control consists of regulating water evaporation and
slurry circulation rates to give that combination of
cooling/evaporation and slurry solids necessary for optimum
crystal size formation. Precipitated crystals are separated
from the mother liquor normally by centrifugation.
Following centrifugation the crystals are washed,
neutralized, and dried to product specifications.
AMMONIUM SULFATE - COKE OVEN BY-PRODUCT
In the process of carbonizing coal to coke such as in the
steel industry, coal volatiles including ammonia, ammonium
hydroxide and ammonium chloride are liberated. Many of the
bituminous coals used in coke production contain 1-2% N and
approximately 15-20% of this quantity can be recovered as
ammonia. Ammonia formation is normally considered to occur
at coking temperatures of approximately lOOOoC (1832oF) such
as utilized in steel industry coking operations. Under
these conditions some 35-45 pounds of ammonium sulfate can
be produced per ton of steel. This AS production is
accomplished by either of three different ways. These three
ways are known as Direct, Indirect and Semi-Direct
processes, according to the method of contacting the ammonia
and sulfuric acid (See Figure 4) .
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AMMONIUM SULFATE - SYNTHETIC
ATMOSPHERIC PRESSURE CRYSTALLIZATION
Water Vapor
To Atmosphere
Sulphuric Acid ^
Ammonia ^
. Ca
L
^ ^^
Air ^/\
^-^
/^
/
^^_
^ ^
•*
Fan Pump
'—---
^v
j
^^
^
7
Crystallizer
^
y
^ /!
I
£
PUIT
i
i
i
j ^
p Pump
_
<1 (^
E
Dry Product
for Reprocessing
M
Crystal Wash-Water
161-215 i/kkg
42-56 qal/ton
*-
r
.Dryer
\^~~^f7 1 • ,
' [J- / f I Tn pj-rM^i-jo^-
Centrifuge! — J a=& i Storage
Y —
Process Water
w ^7 Leaks, spills
and wash wate
from pump
[K^i b ., 1 seals and
V7^ fc ^~in 1
Jissolution Pump Mother //// ^ "" equipment
Tank Liquor washing, etc.
Tank 250-585 1 /kkg
LI 60-140 gal/to
Waste Sump
FIGURE 3
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AMMONIUM SULPHATE - COKE OVENS
-fel
To Atmosphere
Crystal Wash-Water
161-215 1/kkg
42-56 gal/ton
Crude Ammonia Pump
Liquor Storage Lime
Leaks, spills
and wash
If~,y water from
pump seals
and equipment
washing, etc.
250-585 1/kkg
60-140 gal/ton
Leg
Ammonia
Still
Gaseous Ammonia Cleaning Equipment Connected with AS Plant
but not Directly Part of AS Process
FIGURE 4
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The Direct process treats the mixture of volatile off-gases
by first cooling them to remove the maximum possible
quantity of tar. Following tar removal the gases are passed
through a saturator - either a bubbler or spray type - where
they are washed with sulfuric acid. AS crystals form in the
liquor and are recirculated in the saturator until the
desired crystal size is formed. After the desired AS
crystal size is realized they are separated from the liquor
by centrifugation, washed, dried and conveyed to storage.
The Indirect, process was developed primarily to improve AS
crystal purity by further removal of such contaminates as
tar, pyradine and other organic compounds. In this method
the volatile off-gases are first cooled by recirculated wash
liquor and scrubbing water. These liquors are then combined
and treated with steam in a stripping column to release
relatively high purity "free" ammonia present in the form of
such easily disassociated salts as ammonium carbonate and
ammonium sulfide. The partially stripped liquor is then
treated with lime solution to decompose such "fixed" salts
as ammonium chloride. This treated liquor then passes to a
second stripping column where essentially all the remaining
ammonia is freed from the liquor. The stripped ammonia is
recovered as a crude ammonia solution which is in turn
redistilled or converted directly to AS in a
saturator/crystalii zer.
The Semi-Direct process is a logical outcome of both the
above described techniques. The volatile off-gases are
cooled and washed. This processing removes the majority of
the tar and yields an aqueous condensate containing a high
percentage of the ammonia present in the gas. Ammonia is
then released from this aqueous condensate in a small still.
The evolved ammonia is then re-combined with the main gas
stream and the whole stream reheated to approximately 70oC.
This reheated gas stream is then scrubbed with 5-6% sulfuric
acid and a near-saturation 60-70% ammonium sulfate solution.
Spray-absorbers or saturators utilizing cracker pipes are
both used for this operation. AS crystals are formed and
removed as product similar to the previously described
procedure- This Semi-Direct process yields an essentially
pure AS and high ammonia recovery.
Mixed and Blend Fertilizer Industry
Plants utilizing the two mixed fertilizer processes included
in this Phase II Study - Mixed and Blend Fertilizers - have
had a very rapid growth since 1964. This growth has been
primarily due to the first time availability of granular
high analysis straight and mixed fertilizer materials.
21
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Prior to 1965 the predominant materials available to
manufacturers were powders with a comparatively low nutrient
content. Use of these older materials resulted in high
production costs due to freight handling, materials loss, as
well as production of a final product of poor quality and
physical characteristics.
The introduction of good quality high analysis fertilizer
materials represented one of the most significant
technological developments in N-P-K fertilizer production in
the past decade. The extent of the influence of these
materials is best appreciated by noting the large increase
in the number of particularly Blend Fertilizer plants which
came into existence during the years 1964 to 1974.
Estimated Number of Operating U.S.
Year Blend Fertilizer Plants
1960 441
1964 1536
1966 3152
1968 4140
1970 5158
1974 7000
Granular ammonium phosphates and specifically DAP are
ideally suited both chemically and physically for mixed and
blend fertilizer processes. In fact the ammonium phosphates
are indispensable to the manufacture of those fertilizer
formulations containing greater than 45% total plant
nutrients. The mixed and blend plants are located
throughout the country, but concentrated in the Midwest and
South Atlantic (See Figure 5 and 6).
Mixed and Blend Fertilizer - Process Description
General
The use of mixed fertilizer material has always enjoyed wide
popularity in the U.S. This stems primarily from the
farmers' desire to save costs - both time and labor. The
former practice of using straight fertilizers meant that the
farmer had to either apply them himself or mix them prior to
application. The increasingly popular practice is to turn
the entire phase of land fertilization over to the mixed
fertilizer manufacturer. This includes such services as
obtaining soil samples, performing soil analysis,
calculating the specific fertilizer formulation required for
the soil and crop to be grown, and finally the actual
applying of the fertilizer. The only time and labor
22
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FIGURE 5
BLEND FERTILIZER
GO
PLANT LOCATIONS
NOTE: DUE TO THE LARGE NUMBER OF PLANTS
IN MANY STATES ONLY REPRESENTATIVE
SITES WITH THE NUMBER OF PLANTS ARE INDICATED,
-------
S3
FIGURE 6
MIXED FERTILIZER
NOTE: DUE TO THE LARGE NUMBER OF PLANTS
IN MANY ST/VTES ONLY REPRESENTATIVE
SITES WITH THE NUMBER OF PLANTS ARE 'INDICATED.
-------
expended by the farmer is the telephone call to request the
service, approval of the application, and writing of the
check.
This trend, plus the fact that fertilizer application
quantities barely equal the crop uptake of nitrogen,
phosphorous, and potassium assures continued growth of mixed
fertilizer consumption. All these different factors have
served to make the farmers increasingly cost conscious. In
turn this has pressured fertilizer dealers into performing
the above described services at little or no additional
cost. These cost pressures have made manufacturing cost
reduction a necessity. One of the outcomes has been a
gradual reduction in the number of small manufacturers (300
to 10,000 TPY capacity). These small manufacturers have
been replaced by a distribution system based on a large
(30,000-60,000 TPY) central or "mother" plant serving a
number of small distribution centers located within a 25-50
mile radius.
The point in describing the mixed fertilizer industry to
this degree is to emphasize that a transition is in
progress. Manufacturers are becoming increasingly aware of
the need to maintain stable year round operation for maximum
labor and cost economy. Small tonnage mixed fertilizer
producers are going out of business. These defunct
operations are being replaced by an increasing number of
blend fertilizer manufacturers. The end result is that the
mixed and blend fertilizer manufacturers have a new
appreciation of all phases of plant operational efficiency.
This includes provisions for effluent control - both gas and
liquid.
The designation of Mixed and Blend Fertilizer processes made
in this study necessitates some additional description so
that fertilizer people can correlate them to the accepted
Fertilizer Industry terminology. A Mixed Fertilizer process
in this report refers to the process which mixes (wet or
dry) straight and mixed fertilizer materials through
chemical reactions into complete mix goods. The Fertilizer
Industry designates the type of plants which process
fertilizer according to this definition as being B, C, and D
type plants. A Blend Fertilizer process designation refers
to the process which physically mixes dry straight and mixed
granular fertilizer materials to a given N-P-K formulation.
This process is designated by the Fertilizer Industry as an
A type plant.
The following U. S. consumption of dry mixed fertilizer
goods (exclusive of liquids) gives some appreciation of the
25
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annual tonnage of materials produced by the Mixed and Blend
Fertilizer processes over the last 16 years.
Year Dry Mixed Fertilizer Goods Consumption
(Short tons)
1955 15,230,505
1960 14,868,024
1965 17,229,239
1970 18,176,900
1971 18,399,800
The tonnage figures do not fully reflect the status of dry
mixed fertilizer goods. It should be added that the total
amount of mixed fertilizers - both dry and liquids - applied
on U. S. soil in 1970 was 20,963,000 tons. Dry mixed
fertilizer therefore represented approximately 87% of this
1970 total. Currently the total quantity of direct
application and mixed fertilizers used in the U.S. is
approximately 42 million tons per year. Agriculturists
estimate that fertilizer usage needs to be 80 million tons
per year to realize most efficient crop growth. This
indicates that dry mixed fertilizer consumption could
approach 40 million tons per year in the near future. It is
also observed that approximately 88% of the P2O5 used in the
U.S. is applied as mixed fertilizer.
The total annual mixed fertilizer tonnages do not indicate
the major change in the two production processes involved.
Reference is to the great increase in bulk blends plants and
decrease in mixed fertilizer process plants in the period
1959 to 1970 - (e.g. 201 blend plants in 1959 to 5158 in
1970). This trend of increasing numbers of blend plants is
expected to continue. In turn, this means that in the near
future the majority of all U.S. mixed fertilizer goods will
be produced by the Blend Fertilizer process.
MIXED_FERTILIZER - PROCESS DESCRIPTION
The raw materials used to produce mixed fertilizer goods
include inorganic acids, solutions, double nutrient
fertilizers, and all types of straight fertilizers. Typical
raw materials include sulfuric acid, phosphoric acid,
nitrogen solutions, diammonium phosphate, ammonia, urea,
ammonium nitrate, ammonium sulfate, normal superphosphate,
triple superphosphate, potash, sand and a variety of minor
elements. The choice of raw materials is dependent on the
specific N-P-K formulation to be produced and the cost of
the different posible materials from which it can be made.
In some N-P-K formulations, two or more raw materials may be
26
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selected because of the chemical reaction which will take
place between them. The objective is to create conditions -
such as chemical neutralization, dilution, etc., - which
will produce the optimum temperature and moisture conditions
for good physical product formation.
The Mixed Fertilizer process involves the controlled
addition of both dry and liquid raw materials to a
granulator. The granulator is normally a rotary drum, but
pug mills are also used. Raw materials, plus some recycled
product material, are mixed to form an essentially
homogeneous granular product. It is common to also add
water and/or steam to aid the chemical reactions and granule
formation. Wet granules from the granulator are discharged
into a rotary drier where the excess water is evaporated.
Dried granules from the drier are sized on vibrating
screens. Over and under size granules are separated for use
as recycle material in the granulator. Product size
granules are cooled and conveyed to storage or shipping (See
Figure 7) .
BLEND FERTILIZER - PROCESS DESCRIPTION
As previously mentioned the development and subsequent
availability of good quality granular fertilizer materials
in the mid '60's was the catalyst which "made" the blend
fertilizer process. Prior to this time the dry blending of
fertilizer was a limited success. Raw materials available
were largely powders with little or no particle size
control. Consequently, the product had poor handling
characteristics as well as unavoidable tendency to
segregate. In the majority of cases the relationship of the
N-P-K formulation in different sections of a bag or bulk
shipment applied by the farmer to that which he purchased
was purely coincidental. Both state fertilizer regulatory
officers and customers took dim views of such fertilizers.
The availability and like physical characteristics of good
quality straight and mixed fertilizer materials corrected
the majority of these problems. Process problems such as
handling and loss from dusty materials were practically
eliminated. Product segregation was reduced to a minimum.
The process is simple. Raw materials are a combination of
granular dry straight and mixed fertilizer materials with
essentially identical particle size. While many materials
can be utilized the five most commonly used are ammonium
nitrate, urea, triple superphosphate, diammonium phosphate,
and potash. These raw materials are stored in a multi-
compartmented bin and withdrawn in the precise quantities
27
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needed to produce the N-P—K formulation desired. Raw
material addition is normally by batch weighing. This
combination of batch-weighed and granular raw materials are
then conveyed to a mechanical blender for mixing. These
batch units are usually one of two types: a cement-type
mixer, capable of 20 to 30 tons per hour or an auger-type
with a four or five ton per hour capacity. From the blender
the product is conveyed to storage or shipping (See Figure
8).
28
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MIXED FERTILIZER PROCESS
Contaminatedi
Water
Process Water
0-92 L/KKG
0-22 Gal/ton
Triple
Superphosphate
DAP
Normal —
Superphosphate
NPK
1
Scrubber
System
Contaminated
"Water
3120-3330 L/KKG
750-800 Gal/toi
Muriate of
Potash Addition
Granulator
T
Ammonia
Phosphoric
Acid
Dryer
Sizing
FIGURE 7
To Product
Storage
-------
BLEND FERTILIZER PROCESS
LO
O
I I I II II I
' ' ' I I II I
\
t
(III
1 II 1
1 It 1
/
r
i
^
t
To f
t
Fertilizer Materials
Q
Weigh/Belt
IWVVVXA/
Screw
Fan
To Railroad
Elevator
Elevator
FIGURE 8
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SECTION IV
INDUSTRY CATEGORIZATION
The task of dividing the many fertilizer processes into
specific categories was considered one of the most important
aspects of the Phase I Study. One important objective was
to minimize the number of categories by grouping those
processes which had similar characteristics. The factors
considered in the categorization process included the
following:
1. Natural industry division.
2. "Common denominator" contaminants.
3. Raw materials.
4. Problems with separation of individual process
effluents within a plant complex.
The application of these listed criteria resulted in the
establishment of seven subcategories within the Fertilizer
industry. These, together with their listed component
processes, are:
A) Phosphate Subcategory
1. Phosphate Rock Grinding
2. Wet Process Phosphoric Acid
3. Phosphoric Acid Concentration
U. Phosphoric Acid Clarification
5. Normal Superphosphate
6. Triple Superphosphate
7. Ammonium Phosphates
8. Sulfuric Acid
B) Ammonia Subcategory
C) Urea Subcategory
D) Ammonium Nitrate Subcategory
E) Nitric Acid Subcategory
F)* Ammonium Sulfate Subcategory
G)* Mixed and Blend Fertilizer Subcategory
The processes marked by asterisk (*) are the processes
covered by this Phase II Study.
The reasoning applied to the four categorization factors
listed above in the assignment of the Phase II processes to
their specific Industry classification is contained in the
following paragraphs.
31
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Natural Industry Division
Industry traditionally views ammonium sulfate production and
mixed and blend fertilizer production as distinctly
separate. By-product AS plants are part of an overall steel
complex and synthetic plants are tied closely to a nitrogen
and/or phosphate complex, because of the ammonia and
sulfuric acid needed. Mixed, and blend plants in
particular, usually are separate installations.
"Common Denominator" Contaminants
The various processes in the two identified categories all
have like effluent contaminants which are either mixed to-
gether into a common effluent stream or because of the spe-
cific contaminant treatment required, it necessitates that
an individual process effluent be treated separately regard-
less of the categorization. The commonness of contaminants
and intermixing of effluents also permits establishment of a
limitation for a total complex regardless of the number of
different processes involved. This in turn simplifies
matters for enforcement officials and industry monitoring.
Problems with Separation of Individual Process Effluentg
Within a Complex
A somewhat surprising fact brought to light in the study was
the lack of information available on a specific process
within a complex. Industrial complexes are generally not
physically designed to keep individual process streams sepa-
rate. The reasons for this condition are due to a
combination of items, such as there previously was no reason
to do so, simplification of underground sewer systems, and
the practice of using effluent from one process as a liquid
in another process. The realization of this general
situation was a reason in establishing the stated industrial
categorization.
Raw Materials
Type of raw material used was the foremost reason for
establishing the stated industry categorization. Mixed and
blend plants obtain their raw materials from the basic
fertilizer materials, such as Ammonia, Urea, AS, Potash,
Triple Superphosphate, and Diammonium Phosphate. Coke oven
ammonium sulfate raw materials are either a by-product of
the coking process or, in synthetic ammonium sulfate
production, ammonia and sulfuric acid.
32
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Ammonium Sulfate Subcategory
Ammonium sulfate (AS) was included as a distinct subcategory
at least partially because industry historically regards it
as a nitrogen fertilizer, separate from the mixed
fertilizers. Other considerations such as the lack of an
actual process effluent and the relatively "pure"
characteristic of the plant effluent definitely established
the categorization.
Mixed and Blend Fertilizer Subcategory
The assignment of a Mixed and Blend Fertilizer subcategory
was based primarily on the criteria of raw materials used,
products produced, and natural industry division. The raw
materials are principally products obtained from basic
fertilizer processes. Industry has traditionally regarded
this subcategory as distinct from other fertilizers. Many
plants operate at separate geographical locations, not
coupled with an overall complex as are most other fertilizer
processes.
33
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SECTION V
WASTE CHARACTERIZATION
General
The intent of this section is to describe and identify water
usage and waste water flows in each individual process
included in this Phase II report of the two fertilizer
subcategories - ammonium sulfate and mixed and blend
fertilizer. Each type of water usage and effluent is
discussed separately.
Ammonium Sulfate Manufacturing
While the study included AS production in two different
industrial categories, the basic process procedures, water
usage, and effluents are essentially identical. The only
differences between the two procedures involve the source,
concentration, and purity of the raw materials used. These
differences do not change the type of water usage or
effluent. The AS process operation has the following types
of water usage and wastes.
A. Contaminated Water
B. Closed Loop Cooling Tower Water
C. Crystal Wash Water
D. Process Condensate
E. Spills and Leaks
F. Non-Point Source Discharges
Each of the above listed types of water usage and wastes are
identified below as to flow and contaminant content under
their respective headings:
A. Contaminated Water
As previously described in the process descriptions
there are several variations in the way the
saturator/crystallizers are operated and controlled.
One variation is to operate the saturator/crystallizers
under vacuum conditions. This involves the use of a
barometric condenser which requires significant water
35
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quantities which may or may not make direct contact with
the saturator/crystallizer offgases.
In those condensers in which direct water - gas contact
occurs it is common practice to utilize contaminated
water from the overall complex recirculated water
system. This recirculated water is an accumulation of
waters from all the different process units at the
complex site and consequently accumulates sizeable
concentrations of many cations and anions. Each pass
through equipment does add to the water contaminate
level although it is normally impractical to
quantitatively analyze for that increase on an
individual pass. This results from inability to obtain
precise water measurement and human variables in
laboratory techniques. This contaminated water is the
major process stream. This stream is reused by
collection in the sump and returning it to the
crystallizer,.
Process Usage
1/kkg gal/ton
Ammonium Sulfate 16680-3U800 4000-8350
B. Closed Loog Cooling Tower Water
Closed loop cooling tower water may be used to condense
the vapor from the evaporative type crystallizers. In
these cases indirect contact condensers are utilized and
no contamination of cooling waters occurs. Water usage
figures are in the same range as those listed for
contaminated water. There were no cases found where a
cooling tower existed specifically for an AS unit and,
therefore, no cooling tower blowdown is reported.
C. Crystal Wash Water
Following the centrifugation of the AS crystals from the
mother liquor it is necessary to wash the crystals to
remove retained liquor. This wash water is a non-
contaminated water which is in turn added to the mother
liquor tank. The small amount of impurities from the
recycled effluent go into the product, and product AS
can accept these without detracting from its value. The
following figures indicate the usage:
Process Usage
1/kkg gal/ton
Ammonium Sulfate 161-215 U2 - 56
36
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D- Process Condensate
In those units where an indirect contact condenser is
utilized (as described in B above) the water vapor from
the evaporative type crystallizers is condensed. This
condensate is small in quantity and is used to dissolve
under-size AS crystals for return to the process.
E- Spills and Leaks
Spills and leaks are collected as part of normal process
and housekeeping. Sources of this water are pump seal
leaks and plant wash-up. Quantity is minor and it is
reintroduced into the system. The following figures
indicate a representative range for this source:
Process Quantity
i^3£&l gal/ton
Ammonium Sulfate 250-585 60-140
Typical contaminants and concentrations in a Spills and Leak
stream are listed below:
Contaminant Concentration-mg/1
Ammonia 12
BODS 5
COD 23
Ph 6.85
Fluoride 0.60
Total Phosphate 0.77
Nitrite Nitrogen 44
Nitrate Nitrogen 23
Phenol 57 ppb
F. Non-Point Source Dischargg
The origin of such discharges are dry product, usually
from conveying equipment, dusting over the plant area and
then being solubilized by rain or melting snow. The
magnitude of this contaminant source is a function of dust
containment, housekeeping, snow/rainfall quantities and the
37
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design of the general plant drainage facilities. Most of
this material is directed to the sump and returned to the
process. The remainder is runoff, which is not regulated.
Mixed and Blend Fertilizer Industry
The mixed and blend fertilizer processes represent by far
the largest number of individual plants in the entire
fertilizer industry - an estimated 7UOO plants. In respect
to water usage and effluents, however, this subcategory is
among the lowest water usage segments of U. S. industry.
The processes have the following listed types of water usage
and wastes:
A. Contaminated Water
B. Process Water
C. Spills and Leaks
D. Non-Point Source Discharges
Each of the above listed types of water usage and wastes are
identified in the following paragraphs as to flow and
contaminant content under their respective headings.
A. Contaminated Water
Mixed fertilizer plants do have one process function which
requires a significant quantity of water. This is in the
wet scrubbing of drier and/or ammoniator exhaust gases. In
order to minimize fresh water usage and to maintain an
overall negative process water balance, a closed loop
recirculation system of contaminated water is used to
provide the relatively high instantaneous water usage
requirements. Normally the contaminated water recirculation
system used in connection with a fertilizer process is small
and services only that particular unit. The following
figures indicate the usage range.
Process Usacje
1/kkg Sal/ton
Mixed Fertilizer 3120-3330 750-800
B. Process Water
Process water is defined as the fresh water addition to the
contaminated water recirculation system required to maintain
the water inventory. The quantity used is highly variable
38
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due to the liquid requirements of the different fertilizer
grade formulations; collection of spills and leaks; the
periodic addition of water from housekeeping chores; and
rainfall addition to the pond. The following figures
indicate the usage range.
gal /ton
Mixed Fertilizer 0-92 0-22
c • Spi 11s and Leaks
Spills and leaks are collected as part of normal process and
housekeeping. Sources of this water are pump and plant
wash-up. The quantity is minor and it is added to the
contaminated recirculation water system.
D. Non-Point Source Discharge
The origin of this discharge is dry product, usually from
conveying equipment, dusting over the plant area and then
being solubilized by rain or melting snow. This type
discharge is the only liquid effluent.
39
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SECTION VI
SELECTION OF POLLUTANT PARAMETERS
General
The selection of pollutant parameters was a necessary early
step of the study. Collection of meaningful data and
sampling was dependent on knowing what fertilizer process
contaminants are important so far as degradation of natural
water resources are concerned.
The general criteria considered and reviewed in the
selection of pollutant parameters included:
- quality of the plant intake water
- products manufactured
- raw materials used
- environmental harmfulness of the compounds or elements
included in process effluent streams
Ammonium Sulfate ^Sutcategory
Effluent waste water from Ammonium Sulfate production units
must be monitored for the following primary parameters:
Ammonia nitrogen and pH.
Secondary parameters which should be monitored but do not
warrant establishment of guidelines at this time are:
Chemical oxygen demand (COD) , total dissolved solids (TDS) ,
suspended solids, and temperature. The chief reason for not,
establishing standards for the secondary parameters is that
treatment of the primary parameters will effect removal of
these secondary parameters. Another reason is that
insufficient data exists to establish effluent limitations.
Mixed^and Blend FertilizersTSubcategory
Effluent waste water from the Phase II processes - Mixed and
Blend Fertilizer - must be monitored for the following
primary parameters: Ammonia nitrogen, pH, phosphorus,
fluorides, nitrate and organic nitrogen.
Secondary parameters which should be monitored but do not
warrant establishment of guidelines at this time are:
Chemical oxygen demand (COD), total dissolved solids (TDS),
41
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and suspended solids. The setting of standards for these
secondary parameters is not warranted because treatment
technology for the primary parameters (when required) effect
removal.
Rationale^ for_Selecting Identified Parameters
Ammonia and Nitrate Nitrogen
Ammonia is a common product of the decomposition of organic
matter. Dead and decaying animals and plants along with
human and animal body wastes account for much of the ammonia
entering the aquatic ecosystem. Ammonia exists in its non-
ionized form only at higher pH levels and is the most toxic
in this state. The lower the pH, the more ionized ammonia
is formed and its toxicity decreases. Ammonia, in the
presence of dissolved oxygen, is converted to nitrate (NO3)
by nitrifying bacteria. Nitrite (NOJ) , which is an
intermediate product between ammonia and nitrate, sometimes
occurs in quantity when depressed oxygen conditions permit.
Ammonia can exist in several other chemical combinations
including ammonium chloride and other salts.
Nitrates are considered to be among the poisonous
ingredients of mineralized waters, with potassium nitrate
being more poisonous than sodium nitrate. Excess nitrates
cause irritation of the mucous linings of the
gastrointestinal tract and the bladder; the symptoms are
diarrhea and diuresis, and drinking one liter of water
containing 500 mg/1 of nitrate can cause such symptoms.
Infant methemoglobinemia, a disease characterized by certain
specific blood changes and cyanosis, may be caused by high
nitrate concentrations in the water used for preparing
feeding formulae. While it is still impossible to state
precise concentration limits, it has been widely recommended
that water containing more than 10 mg/1 of nitrate nitrogen
(NO3_-N) should not be used for infants. Nitrates are also
harmful in fermentation processes and can cause disagreeable
tastes in beer. In most natural water the pH range is such
that ammonium ions (NH4+) predominate. In alkaline waters,
however, high concentrations of un-ionized ammonia in
undissociated ammonium hydroxide increase the toxicity of
ammonia solutions. In streams polluted with sewage, up to
one half of the nitrogen in the sewage may be in the form of
free ammonia, and sewage may carry up to 35 mg/1 of total
nitrogen. It has been shown that at a level of 1.0 mg/1 un-
ionized ammonia, the ability of hemoglobin to combine with
42
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oxygen is impaired and fish may suffocate. Evidence
indicates that ammonia exerts a considerable toxic effect on
all aquatic life within a range of less than 1.0 mg/1 to 25
mg/1, depending on the pH and dissolved oxygen level
present.
Ammonia can add to the problem of eutrophication by
supplying nitrogen through its breakdown products. Some
lakes in warmer climates, and others that are aging quickly
are sometimes limited by the nitrogen available. Any
increase will speed up the plant growth and decay process.
Fluorides
As the most reactive non-metal, fluorine is never found free
in nature but as a constituent of fluorite or fluorspar,
calcium fluoride, in sedimentary rocks and also of cryolite,
sodium aluminum fluoride, in igneous rocks. Owing to their
origin only in certain types of rocks and only in a few
regions, fluorides in high concentrations are not a common
constituent of natural surface waters, but they may occur in
detrimental concentrations in ground waters.
Fluorides are used as insecticides, for disinfecting brewery
apparatus, as a flux in the manufacture of steel, for
preserving wood and mucilages, for the manufacture of glass
and enamels, in chemical industries, for water treatment,
and for other uses.
Fluorides in sufficient quantity are toxic to humans, with
doses of 250 to 450 mg giving severe symptoms or causing
death.
There are numerous articles describing the effects of
fluoride-bearing waters on dental enamel of children; these
studies lead to the generalization that water containing
less than 0.9 to 1.0 mg/1 of fluoride will seldom cause
mottled enamel in children, and for adults, concentrations
less than 3 or 4 mg/1 are not likely to cause endemic
cumulative fluorosis and skeletal effects. Abundant
literature is also available describing the advantages of
maintaining 0.8 to 1.5 mg/1 of fluoride ion in drinking
water to aid in the reduction of dental decay, especially
among children.
Chronic fluoride poisoning of livestock has been observed in
areas where water contained 10 to 15 mg/1 fluoride.
Concentrations of 30 - 50 mg/1 of fluoride in the total
ration of dairy cows is considered the upper safe limit.
Fluoride from waters apparently does not accumulate in soft
43
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tissue to a significant degree and it is transferred to a
very small extent into the milk and to a somewhat greater
degree into eggs. Data for fresh water indicate that
fluorides are toxic to fish at concentrations higher than
1.5 mg/1.
Organic Nitrogen
Organic nitrogen contaminants in the waste waters consist
mainly of urea and lesser amounts of organic C02 scrubbing
solutions. Such compounds can supply nutrient nitrogen for
increased plant and algae growth in receiving waters.
The organic scrubbing solution - monethanolamine (MEA) - can
add a slight BOD load to the effluent waste stream.
During the past 30 years, a formidable case has developed
for the belief that increasing standing crops of aquatic
plant growths, which often interfere with water uses and are
nuisances to man, frequently are caused by increasing
supplies of phosphorus. Such phenomena are associated with
a condition of accelerated eutrophication or aging of
waters. It is generally recognized that phosphorus is not
the sole cause of eutrophication, but there is evidence to
substantiate that it is frequently the key element in all of
the elements required by fresh water plants and is generally
present in the least amount relative to need. Therefore, an
increase in phosphorus allows use of other, already present,
nutrients for plant growths. Phosphorus is usually
described, for this reasons, as a "limiting factor."
When a plant population is stimulated in production and
attains a nuisance status, a large number of associated
liabilities are immediately apparent. Dense populations of
pond weeds make swimming dangerous. Boating and water
skiing and sometimes fishing may be eliminated because of
the mass of vegetation that serves as an physical impediment
to such activities. Plant populations have been associated
with stunted fish populations and with poor fishing. Plant
nuisances emit vile stenches, impart tastes and odors to
water supplies, reduce the efficiency of industrial and
municipal water treatment, impair aesthetic beauty, reduce
or restrict resort trade, lower waterfront property values,
cause skin rashes to man during water contact, and serve as
a desired substrate and breeding ground for flies.
Phosphorus in the elemental form is particularly toxic, and
subject to bioaccumulation in much the same way as mercury.
44
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Colloidal elemental phosphorus will poison marine fish
(causing skin tissue breakdown and discoloration). Also,
phosphorus is capable of being concentrated and will
accumulate in organs and soft tissues. Experiments have
shown that marine fish will concentrate phosphorus from
water containing as little as 1 ug/1.
p_H, Acidity and Alkalinity
Acidity and alkalinity are reciprocal terms. Acidity is
produced by substances that yield hydrogen ions upon
hydrolysis and alkalinity is produced by substances that
yield hydroxyl ions. The terms "total acidity" and "total
alkalinity" are often used to express the buffering capacity
of a solution. Acidity in natural waters is caused by
carbon dioxide, mineral acids, weakly dissociated acids, and
the salts of strong acids and weak bases. Alkalinity is
caused by strong bases and the salts of strong alkalies and
weak acids.
The term pH is a logarithmic expression of the concentration
of hydrogen ions. At a pH of 7, the hydrogen and hydroxyl
ion concentrations are essentially equal and the water is
neutral. Lower pH values indicate acidity while higher
values indicate alkalinity. The relationship between pH and
acidity or alkalinity is not necessarily linear or direct.
Waters with a pH below 6.0 are corrosive to water works
structures, distribution lines, and household plumbing
fixtures and can thus add such constituents to drinking
water as iron, copper, zinc, cadmium and lead. The hydrogen
ion concentration can affect the "taste" of the water. At a
low pH water tastes "sour". The bactericidal effect of
chlorine is weakened as the pH increases, and it is
advantageous to keep the pH close to 7. This is very
significant for providing safe drinking water.
Extremes of pH or rapid pH changes can exert stress
conditions or kill aquatic life outright. Dead fish,
associated algal blooms, and foul stenches are aesthetic
liabilities of any waterway. Even moderate changes from
"acceptable" criteria limits of pH are deleterious to some
species. The relative toxicity to aquatic life of many
materials is increased by changes in the water pH.
Metalocyanide complexes can increase a thousand-fold in
toxicity with a drop of 1.5 pH units. The availability of
many nutrient substances varies with the alkalinity and
acidity. Ammonia is more lethal with a higher pH.
45
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The lacrimal fluid of the human eye has a pH of
approximately 7.0 and a deviation of 0.1 pH unit from the
norm may result in eye irritation for the swimmer.
Appreciable irritation will cause severe pain.
METHQDg OF ANALYSIS
The methods of analysis to be used for quantitative
determination are given in the Federal Register 40 CFP 130
for the following parameters pertinent to this study:
Alkalinity (and acidity)
ammonia nitrogen
fluoride
hardness
nitrogen, total kjeldahl
oxygen demand, chemical
phosphorus
solids, total
suspended nofilterable solids, total
temperature
46
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SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
The factors and contaminants in fertilizer process effluent
streams have for the most part been quite well identified
and known for many years. As a consequence considerable
effort has been expended to correct or minimize the majority
of those which are particularly detrimental to natural water
receiving bodies. Much of this work has been directed at
correcting the source of the contamination or an in-process
improvement rather than an end-of-pipe type of treatment. A
large part of the motivation for such improvement has been
economics - that is, improved operating efficiency and
costs. Such improvements are just plain good business and
justify capital expenditure required to achieve them.
With an appreciation of the above mentioned facts, the
following criteria were established as bases for
investigating treatment technology.
- To determine the extent of existing waste water
control and treatment technology
- To determine the availability of applicable waste
water control and treatment technology regardless
of whether it be intra-industry transfer technology
- To determine the degree of treatment cost reason-
ability
Based upon these stated criteria, the effort was made to
factually investigate overall treatment technologies dealing
with each of the primary factors and contaminants listed in
Section VI. The results of that investigation are covered
separately for ammonium sulfate and mixed and blend
fertilizers.
Ammonium Sulfate Plant - Effluent Control
Two of the three commercial processes used to produce
Ammonium Sulfate were included in this Phase II study -
synthetic and coke by-product processes. Basic process unit
operations and functions are identical in both processes.
The differences are essentially the ammonia raw material
source.
In the coke oven by-product process appreciable equipment is
involved in removing contaminants from the oven gas prior to
47
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its introduction to the saturator/crystallizer. The gas
cleaning equipment and the liquid flows to and from the
equipment are outside the AS process battery limits and were
not included in the study. Essentially the AS process is an
additional gas cleaning and air pollution control mechanism
for the oven gas prior to its use as coke burner fuel.
Process Description
The highly exothermic ammonia - sulfuric acid neutralization
reaction permits judicious recycle of the minor process
effluents back into the process. These minor streams
include crystal wash, spills and leaks, and
saturator/ammoniator indirect contact gas condensate (where
existent) .
The effluent control consists of a means to collect these
streams and/or their controlled addition to the process
equipment. A common means of accomplishing this is by means
of a trench and sump system complete with pump for
rehandling of the collected effluents. The collected
effluents can then be continuously or batch fed into the
process equipment (See Figure 9).
Mixed Fertilizer Process-Effluent Control
This is the only Phase II phosphate process with liquid
effluent. Each mixed fertilizer plant is very cognizant of
water usage and exercises close control on it. Process
equipment with an effluent purge stream includes dryer,
cooler, and/or ammoniator exhaust gas scrubbers. A minor
secondary source is effluent from leaks, spills and
housekeeping.
Process_Descrip_tion
The mixed fertilizer process requires a certain amount of
liquid to satisfy requirements of mixed fertilizer
manufacture. The quantity of liquid required varies widely
and is dependent on the raw materials and specific
fertilizer formulation. At least a portion of that liquid
can be supplied from the wet scrubber contaminated water
recirculation system.
The effluent control process consists simply of a closed
loop contaminated water system. This system includes a
small retention pond (a representative size is 10• wide x
60' long x 10* deep) equipped with a pump to control the
48
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FIGURE 9
AMMONIUM SULFATE PLANT
EFFLUENT CONTROL
To Process
VO
Make-Up Water
Spills,Leaks and Wash Water
Waste Sump
-------
clarified (either by settling or mechanical means) scrubber
water addition to the ammoniator/granulator (See Figure 10).
The function of the wet scrubber is to remove noxious gases
and particulate material from ammoniator offgases in
addition to the dryer and cooler offgases. Because of the
sizeable difference in temperature between these exhausts,
separate scrubbers are sometimes utilized. The particulate
material collected in the scrubber liquor if not solubilized
must at least partially be removed from the circulated
scrubber liquor before the liquor is added to the process.
Removal of the insoluble material can be accomplished
mechanically by such equipment as hydrocyclones or can be
allowed to gravity settle from the liquor in the small
retention pond. In the case of hydrocyclone equipment, the
reasonably well concentrated solids (5-20% solids) can also
be returned to the ammoniator/granulator as a slurrry. In
the case of use of the retention pond as a settling area,
the solids accumulated on the pond bottom are periodically
(approximately once per year) "mucked out". The removed
solids are then transported to a customer's field for
distribution as a low grade fertilizer.
Blend Fertilizer^Process Airborne Solids Control
The technology involved with the blend fertilizer process
may seem to be one out of place in a study on liquid plant
effluents. It is however thought important to briefly
discuss this point due to the large number of plants
involved and the possible consideration of air pollution
control authorities to allow wet scrubbing as at least an
alternate for removal of airborne solids. Use of wet
scrubbing equipment in this process would create more
problems than it could possibly solve. It is considered
important that only dry type collectors be used for removal
of airborne solids from blend fertilizer process plants (See
Figure 11).
50
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MIXED FERTILIZER PROCESS
EFFLUENT CONTROL
Flow
Element
Contaminated
Water _
To Scrubber
Contaminated water from
Scrubber, Leaks, Spills and Wash Water
/// I I I I I I I I I
1 V
Flow Control
Valve
Contaminated
£. Water to
Ammoniator/Granulato;
/ Pump
Retention Pond
FIGURE 10
-------
BLEND PLANTS
AIRBORNE SOLIDS
CONTROL
I I
11
Bag Collecter
U
AAAAAAAAAA
Screw
To Atmosphere
Fan
Blender
Product to Storage
- - - Major Equipment & Stream Flows
FIGURE 11
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SECTION VIII
COST, ENERGY AND NON-WATER QUALITY ASPECT
General
The costs - capital and operating - have been estimated for
each of the three in-process treatment technologies
described in Section VII. These costs are given as August
1971 dollar values and have been based on a specific plant
capacity. The capacity used was from a moderate size
production unit and is specified on the cost summary table
(See Table 1). An explanation of the various cost elements
included in the table is given under the respective headings
of the chart items.
There is a point in regard to the Mixed Fertilizer Process
Plants which may require some consideration with respect to
guidelines. There are a number of relatively small
production units (8,000 - 20,000 TPY) throughout the United
States. Currently, operating costs have reduced
profitability of these units to a point where they are
gradually going out of business. The trend is for the
establishment of a moderate size plant (30,000 - 60,000 TPY)
in a central location to supply a number of small blend or
distribution centers within a 25 - 50 mile radius. The
point is that when air pollution standards are established
it will force an additional number of these small process
units to either install wet scrubbers or go out of business
at an earlier time than possibly would have been expected.
Based on the wet scrubber capital and operating costs it is
considered unlikely that such costs can be absorbed by
process units of less than 30,000 TPY capacity. As
mentioned previously, this condition will be basically
caused by local, state and/or national air pollution
standards and not by water effluent standards.
Investments
This is the capital cost associated with engineering; site
preparation; construction and installation; and such other
costs required to place the equipment in operation. It does
not include production loss or profits that may be realized
from tying the facilities into the existing plant.
Interest
This cost is based on the assumption that the capital
expenditure was borrowed at a 7.5% annual interest rate.
53
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Depreciation
The nature and service life expected of this type equipment
were the basis for the selection of an assumed ten-year
straight line method depreciation cost.
Operatirig^and Maintenance Costs
The various items included in these costs are operating
supplies, replacement parts, insurance, taxes, operating
labor and maintenance labor.
This item is the power costs to operate the mechanical
equipment. Electrical energy is assumed at the cost of 10
mils per KWH.
Solid waste control must be considered. Best practicable
control technology and best available control technology as
they are known today, require disposal of the pollutants
removed from waste waters in this industry in the form of
solid wastes and liquid concentrates. In most cases, these
are non-hazardous substances requiring only minimal
custodial care. However, some constituents may be hazardous
and may require special consideration. In order to ensure
long term protection of the environment from these hazardous
or harmful constituents, special consideration of disposal
sites must be made. All landfill sites where such hazardous
wastes are disposed should be selected so as to prevent
horizontal and vertical migration of these contaminants to
ground or surface waters. In cases where geologic
conditions may not reasonably ensure this, adequate legal
and mechanical precautions (e.g. impervious liners) should
be taken to ensure long term protection to the environment
from hazardous materials. Where appropriate, the location
of solid hazardous materials disposal sites should be
permanently recorded in the appropriate office of legal
jurisdiction.
Sludges from mixed fertilizer retention ponds could contain
hazardous materials such as fluorides. This creates a
disposal problem. Proper waste disposal procedures for such
materials should be undertaken.
Total Annual Costs
An accumulation of the various cost items described above.
55
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INSTALLATION AND OPERATION OF TECHNOLOGIES
Ammonium Sulfate Plant EffluentnControl
The estimated time required for engineering, procurement and
construction is 3 months.
Installation of this control system would be possible
without interruption of plant operation in the event that it
is an addition to an existing plant.
Mixed Fertilizer_Process Effluent Control
The estimated time required for engineering, procurement and
construction is 12 months.
Installation of this equipment could proceed concurrently
with plant operation except for some 8 hours of tie-in work.
Blend Fertilizer Airborne Solids Control
The estimated time required for engineering, procurement and
construction is 9 months.
Installation of this equipment could largely proceed
concurrent with production but will require approximately 24
hours of tie-in work.
56
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SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
AVAILABLE, GUIDELINES AND LIMITATIONS
Introduction
The effluent limitations which must be achieved by July 1,
1977 are based on the degree of effluent reduction attain-
able through the application of the best practicable control
technology currently available. For the fertilizer manu-
facturing industry, this level of technology is based on the
best existing performance by exemplary plants of various
sizes, ages and chemical processes within each of the
industry's categories.
Best practicable control technology currently available in
the Ammonium Sulfate and Mixed and Blend Fertilizer process
plants involves only control technology within the
processes. The control techniques included are
manufacturing process control, use of recycle water systems,
recovery and reuse of waste water, and use of dry collectors
for airborne solids.
Other factors included in the considerations were:
a. The total cost of application of technology in relation
to the effluent reduction benefits to be achieved from such
application.
b. The size and age of equipment and facilities involved.
c. The process employed.
d. The engineering aspects of the application of various
types of control techniques.
e. Process changes.
f. Nonwater quality environmental impact (including energy
requirements) .
General Water, Guidelines
Process water is defined as any water directly contacting
the reactants, intermediates, waste products, or end-
products of a manufacturing process including contact
cooling water. Not included in the guidelines are
noncontact cooling water or ancillary waste streams
57
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resulting from steam and water supply. No limitations are
established for either pollutant concentration or process
waste water flow.
Based upon the information contained in Sections III through
VIII of this report, the following determinations were made
on the degree of effluent reduction attainable with the
application of the best practicable control technology
currently available to the fertilizer manufacturing
industry.
AMMONIUM SULFATE SUBCATEGORY
General Description
The survey (described in detail under Section III) of
ammonium sulfate plants was the composite of two separate
industry studies. Synthetic AS plants and one coke oven by-
product plant were covered in the first study. A second
study included data obtained from four by-product plants.
The objective of both surveys was to determine the
qualitative and quantitative levels of contaminants being
discharged as well as the in-process technology used to
control plant process effluents.
Best Practicable Control Technology Currently Available
includes:
Ammgnium_gulfate Plant Effluent Control
This control technology was found to be in current indus-
trial use at all the plants surveyed - both synthetic and
coke oven by-product units. The technology consists of
simply collecting the few process effluent streams (inclu-
ding leaks, spills and housekeeping) followed by controlled
addition of the effluents back into the main process
streams. A more detailed discussion of this technology is
included in Section VII.
Proposed Effluent Limitations Guidelines
This technology coupled with judicious use of water in the
process plant has demonstrated that the degree of effluent
reduction obtainable is no discharge of process waste water
pollutants to navigable waters.
The criteria used for selection of the treatment technology
was information obtained at each of the plants - both
synthetic and coke oven by-product process - covered in the
survey. This criteria was obtained by sampling in-process
58
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streams for raw waste load data; inspection and review of
plant operations; collection of validated historical
effluent data; and direct discussions with responsible plant
operational personnel for positive definition of control and
operational techniques practiced. Additional information
was gathered from technical literature and direct contact
with experts.
The proposed limitation of no discharge of process waste
water pollutants is commercially practiced at all the
synthetic AS plants surveyed and, with the additional
feature of either a specific AS plant recirculation or
overall plant recirculation system, also practiced at all
coke oven by-product AS plants.
MIXED AND BLEND FERTILIZER SUECATEGORY
The survey (described in detail under Section III) of
progressive plants with wide capacity variations in the
selected geographical areas was conducted to determine what
level of contaminants was in the effluents from these plants
and what were the treatment methods in use to maintain these
levels. The following technology is considered to be the
best practicable and currently available which is needed to
meet the 1977 requirements.
Best Practicable Control Technology Currently Available
includes:
Mixed Fertilizer Process Effluent Control
This control technology was found in current industrial use
at four of the five plants surveyed. The single plant not
currently using the technology was in the process of
installing it with completion scheduled for early 1974. The
technology consists of a contaminated water recirculation
system with provisions for collecting spills, leaks, and
wash water together with instrumentation to permit
controlled addition of contaminated water to the process. A
more detailed discussion of this technology is included in
Section VII.
Proposed Effluent Limitation Guideline
This technology coupled with judicious use of water in the
process plant has demonstrated that the degree of effluent
reduction obtainable is no discharge of process waste water
pollutants to navigable waters.
Blend Fertilizer Process Liquid Effluent
59
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The technology description as applied to this process is a
misnomer in that this process inherently has no liquid
requirements. Process raw materials include only dry
materials and only dry type air effluent control equipment
is used.
Proposed Effluent Limitation Guideline
The limitation guideline is simply that the existent tech-
nology be maintained on the principle of applying only dry
type air effluent control equipment in blend fertilizer
plants.
Rationale for Best Practicable Control Technology Currently
Available
The proposed limitation of no discharge of process waste
water pollutants is commercially practiced at all blend
fertilizer process plants surveyed in this study.
60
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SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE,
GUIDELINES AND LIMITATIONS
Introduction
The effluent limitations which must be achieved by July 1,
1983, are based on the degree of effluent reduction
attainable through application of the best available
technology economically achievable. This level of
technology was based on the very best control and treatment
technology employed by a specific point source within the
industrial category. Best available technology economically
achievable places equal emphasis upon in-process controls
and control or treatment techniques employed at the end of a
production process.
The following factors were taken into consideration in
determining best available technology economically
achievable:
a. The age of equipment and facilities involved;
b. The process employed;
c. The engineering aspects of the application of
various types of control techniques;
d. Process changes;
e. Cost of achieving the effluent reduction resulting
from application of best available technology
economically achievable;
f. Non-water quality environmental impact (including
energy requirements).
Process Waste Water Guidelines
Process waste water is defined as any water which, during
the manufacturing process, comes into direct contact with
raw materials, intermediates, products, or by-products.
Based upon the information contained in Sections III through
IX of this report, the following determinations were made on
the degree of effluent reduction attainable with the
application of the best available control technology
economically achievable in the various subcategories of the
fertilizer manufacturing industry.
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Proposed Best Available Technology Economically Achievable
For the processes included in this Phase II survey, the best
available technology economically achievable is synonymous
with the technologies described as best practicable
technologies currently available. This is no discharge of
process waste water pollutants to navigable waters.
62
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SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
AND PRETREATMENT RECOMMENDATIONS
Introduction
This level of technology is to be achieved by new sources.
The term "new source" is defined in the Act to mean "any
source, the construction of which is commenced after
publication of proposed regulations prescribing a standard
of performance." New source performance standards are to be
evaluated by adding to the consideration underlying the
identification of best practicable control technology
currently available a determination of what higher levels of
pollution control are available through the use of improved
production processes and/or treatment techniques. Thus, in
addition to considering the best in-plant and end-of-process
control technology, new source performance standards are to
be based upon an analysis of how the level of effluent may
be reduced by changing the production process itself.
Alternative processes, operating methods or other
alternatives are to be considered. However, the end result
of the analysis identifies effluent standards which would
reflect levels of control achievable through the use of im-
proved production processes (as well as control technology),
rather than prescribing a particular type of process or
technology which must be employed. A further determination
which was to be made for new source performance standards is
whether a standard, permitting no discharge of pollutants is
practicable.
The following factors were to be considered with respect to
production processes which were analyzed in assessing new
source performance standards:
a. The type of process employed and process changes.
b. Operating methods.
c. Batch as opposed to continuous operations.
d. Use of alternative raw materials and mixes of raw
materials.
e. Use of dry rather than wet processes (including
substitution of recoverable solvents for water).
f. Recovery of pollutants as by-products.
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Proposed New Source Performance Standard
For the processes included in this Phase II survey, the
proposed new source performance standard is synonymous with
the best practical and best available technologies currently
available. This is no discharge of process waste vater
pollutants to navigable waters.
Rationale and Assumptions in the Development of New Source
Performance Standards
One major problem in trying to treat waste water
contaminants is that of dealing with large quantities of
water with very dilute contaminant concentrations. Most
existing plant complexes have very limited facilities for
keeping different waste waters separated and, therefore, any
treatment system installed has to handle large amounts of
effluent waste water. The construction of a new process
plant allows the design of a contaminated water
separation/collection system to allow more efficient, less
costly treatment of contaminants. More improved use of
plant water including recycling should also aid in treating
waste effluents.
Of particular importance is the placement of cooling towers
in relation to the ammonia, air emissions sources. Downwind
absorption of ammonia by recycled cooling water can
significantly contribute to the raw waste load. New plants
have the freedom of plant arrangement that existing plants
do not. Furthermore, through good engineering design, new
plants should be able to eliminate the problem at the source
by minimizing air leaks.
Pretreatment Requirements for New Sources
The type of waste water effluent that is discharged from an
ammonium sulfate or mixed and blend plant contains
compounds, such as ammonia nitrogen and nitrate nitrogen,
that would pass through a typical activated sludge or
trickling filter waste water plant and, therefore, this
waste water at its normal concentration levels would not be
amenable to treatment by conventional biological treatment
processes. No discharge of process waste water pollutants
from new sources to publicly owned treatment works is
recommended for these subcategories. For the remaining
subcategories, pretreatment and treatment provided by the
publicly owned treatment works must sum to equal the
effluent limitations for discharge to navigable waters for
new sources if a discharge to publicly owned treatment works
is to be allowed.
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SECTION XII
ACKNOWLEDGEMENTS
This report was prepared by the Environmental Protection
Agency on the basis of a comprehensive study performed by
Davy Powergasf Inc., under contract no. 68-01-1508. Mr.
Robert W. Heinz, Project Manager, assisted by Mr. Charles T.
Harding, Mr. Gerald T. Fields, Mr. N. V. Fry, Mr. George
Telatnik and Mr. Jack Frost, prepared the original
(contractor's) report.
This study was conducted under the supervision and guidance
of Elwood E. Martin, Project Officer for the fertilizer
manufacturing industry assisted by Mr. Bruno E. Maier.
Overall guidance and excellent assistance was provided by
the author's associates in the Effluent Guidelines Division,
particularly Messrs. Allen Cywin, Director, Ernst P. Hall,
Deputy Director, and Walter J. Hunt, Branch Chief.
The cooperation of manufacturers who offered their plants
for survey and contributed pertinent data is gratefully
appreciated. The operations and the plants visited were the
property of the following companies:
Borden Chemical Company, Plant City, Fla.
Ellington Equity, Ellington, Illinois
Fertilizer Institute, Washington, D.C.
Gold Kist Chemical Co., Hanceville, Ala.
IMCC Rainbow Div., Atlanta, Ga.
Mississippi Chemical Corp., Dothan, Ala.
N U S - Rice, Pittsburgh, Pa.
Occidental Chemical Co., Houston, Tex.
Olin Corporation, Stamford, Conn.
Perkinson Fertilizer, Decatur, 111.
J. R. Simplot Co., Pocatello, Idaho
Thornton Laboratory, Tampa, Fla.
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Woodward Company, Woodward, Ala.
Valley Nitrogen, Helm, Calif.
Acknowledgement and appreciation is also given to Ms. Kay
Starr, Ms. Nancy Zrubek, Ms. Alice Thompson, Ms. Linda Rose,
and Ms. Brenda Holmone of the Effluent Guidelines Division
secretarial staff and to the secretarial staff of Davy
Powergas, Inc., for their efforts in the typing of drafts,
necessary revisions, and the final preparation of this and
the contractor's draft document.
Thanks are also given to the members of the EPA working
group/steering committee for their advice and assistance.
They are:
Mr. Walter J. Hunt, Effluent Guidelines Division,
Chairman
Mr. Elwood E. Martin, Effluent Guidelines Division
Mr. Harry Trask, Office of Solid Waste Management
Division
Dr. Edmond Lomasney, Region VI
Mr. Paul DesRosiers, Office of Research and Monitoring
Dr. Murray Strier, Office of Permit Programs
Dr. Robert R. Swank, Jr., Office of Research and
Development, NERC - Corvallis, Athens, Georgia
Dr. Chester Rhines, Effluent Guidelines Division
Mr. G. W. Frick, Office of General Counsel
Mr. James Kamihachi, Office of Planning and Evaluation
66
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SECTION XIII
REFERENCES
A. Inorganic Fertiliser and Phosphate Mining Industries -
Water Pollution and Control
B. Industrial Pollution Control Handbgok by Herbert F.
Lund; McGraw Hill Publishing Co., New York, Library of
Congress Catalog Card Number 70-101164.
C. Gauging and Sampling Industrial Wastewater by Joseph G.
Robasky and Donald L. Koraido Calgon Corporation;
Chemical Engineering Magazine, Vol. 80, No. 1, January
8r 1973, Pages 111-120.
D- Environmental Protection Agency Study Report Industrial
W^St6. Studiejs Program Group 6 Fertilizers prepared by
Wellman-Powergas, Inc.; Lakeland, Florida, 33803, for
Environmental Protection Agency, July, 1971, Contract
No. 68-01-0029.
E. The Phosphate Industry in the United States by E. C.
Houston Tennessee Valley Authority, Office of
Agricultural and Chemical Development, Division of
Chemical Development, Muscle Shoals, Alabama, July,
1966.
F. Commercial Fertilizer Yearbook - 19_7_0 Walter W. Brown
Publishing Co., Inc. 7§ "Third Street, N.W. Atlanta,
Georgia, 30308.
G. Characteristics of the World Fertilizer Industry
Phosphatic Fertilizers by Travis Hignett, Director of
Chemical Development, Tennessee Valley Authority, Muscle
Shoals, Alabama, December, 1967, TVA Report No. S-U22-
H- World Fertilizer Forecast 1965-1980 by Wellman-Lord,
Inc. Lakeland, Florida, Copyright 1967, Paramount Press,
Inc., Jacksonville, Florida.
I. Economic Irnpact of W^ter Pollution Control Reguirements
on the Fertilizer Manufacturing Industry by Development
Planning and Research Associates, Inc., P.O. Box 727,
Manhattan, Kansas, 66502. Interim Report to
Environmental Protection Agency, Contract No. 68-01-
0766, November, 1972.
67
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J- World Nitrogen Plants 1968-1973 Chemical Products Series
Report - May 1969, Stanford Research Institute; Menlo
Park, California, 94025.
K. Phosphatic Fertilizers - Properties_and Processes by
David W. Bixby, Delbert L. Rucker, Samuel L. Tisdale,
Technical Bulletin No. 8, October 1966, The Sulphur
Institute, 1725 "K" Street Northwest, Washington, D. C.
20006.
L. The Chemical Industry Facts Book by Manufacturing
Chemist Association, Inc., 5th Edition 1962, 1825
Connecticut Ave.r Washington, D. C., Library of Congress
Catalog Card No. 59-15407.
M- Water Quality Criteria National Technical Advisory
Committee, Federal Water Pollution Control
Administration, Washington, D. C., 1968.
N- Industrial Water Pollution Control W. W. Ekenfelder,
McGraw-Hill Publishing Co., New York, Published 1966,
Library of Congress Catalog Card No. 66 - 17913.
O. Standard Methods for the Examination of Water and Waste
Water 13th Edition, American Public Health Association
(1971).
p- Methods for Chemical Analysis of Water and Wastes EPA,
National Environmental Research Center, Analytical
Quality Control Laboratory, Cincinnati, Ohio (1971).
Q. Chemical Process Industries R. Norris Shreve, Professor
of Chemical Engineering, Purdue University, Pages 398-
404, First Edition Fifth Impression, 1945.
R. Ammonium Sulfate Manufacture J. F. Holt and P. J.
Farley, United States Steel Corporation, Fairless Hills,
Penn. Reprint 12A, Presented at the Symposium on
Nitrogen Fertilizer Manufacturing Sixty-Third National
Meeting, St. Louis, Mo. February 18-21, 1968. American
Institute of Chemical Engineers.
S. Fertilizer Trends J97_1 National Fertilizer Development
Center, Muscle Shoals, Alabama 33660.
T. 1972 Fertilizer Summary Data Norman L. Hargett, National
Fertilizer Development Center, Tennessee Valley
Authority, Muscle Shoals, Alabama.
68
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u- Nitrogen Fertilizer Chemical Processes Christopher J.
Pratt, Robert Noyes, Noyes Development Corp., 16-18
Railroad Ave., Pearl River, N. Y., U.S.A. 1965 Library
of Congress Card Number 64-24901.
V. Fertilizer Nitrogen Vincent Sauchelli. American
Chemical Society Monograph Series, Reinhold Publishing
Corp., N. Y. 1964, pages 128-135 Library of Congress
Catalog Card Number 64-20956.
w- Inorganic Fertilizer Materials and Related Acids ,
Summary for J_9_22 Lonnie M. Conner, Chief for Chemicals,
Wood Products, and Non-Metalic Minerals Branch, U.S.
Department of Commerce, Bureau of the Census, Industry
Division, Washington, D.C. 20233.
X. Water Quality Criteria 1972, National Academy of
Sciences and National Academy of Engineering for the
Environmental Protection Agency, Washington, D.C. 1972
(U.S. Government Printing Office Stock No. 5501-00520).
69
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SECTION XIV
GLOSSARY
TPY
Short Tons per year
Toxic Constituents
Relating to a poison
AS
Ammonium Sulfate
Virgin
Manufactured from essentially pure raw materials
Mother
Central unit furnishing several other satellite units with
material
Contaminated Waste Water
Effluent waste water that has been contaminated due to
contact with process water (could be cooling tower, boiler
blowdown or pond water)
Cooling Water Blowdown
Small quantity of cooling water discharged from a recycling
cooling water system to remove concentrated contaminants
from the tower
Process Water
Any water which, during the manufacturing process, comes
into direct contact with any raw material, intermediate,
product, by-product, or gas or liquid that has accumulated
such constituents
«
Ton
All uses of the term "ton" imply short ton equal to 2,000
Ib.
71
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TABLE 2
METRIC UNITS
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS) by TO OBTAIN (METRIC UNITS)
ENGLISH UNIT ABBREVIATION CONVERSION ABBREVIATION METRIC UNIT
acre ac 0.405 ha
acre - feet ac ft 1233.5 cu m
British Thermal
Unit BTU 0.252 kg cal
British Thermal BTU/lb 0.555 kg cal/kg
Unit/pound
cubic feet/minute cfm 0.028 cu m/min
cubic feet/second cfs 1.7 cu m/min
cubic feet cu ft 0.028 cu m
cubic feet cu ft 28.32 1
cubic inches cu in 16.39 cu cm
degree Fahrenheit oF 0.555(oF-32)*oC
feet ft 0.3048 m
gallon gal 3.785 1
gallon/minute gpm 0.0631 I/sec
horsepower hp 0.7457 kw ,
inches in 2.54 cm
inches of mercury in Hg 0.03342 atm
pounds Ib 0.454 kg
million gallons/day mgd 3,785 cu m/day
mile mi 1.609 km
pound/square inch psig (0.06805 psig +1)*atm
(gauge)
square feet sq ft 0.0929 sq m
square inches sq in 6.452 sq cm
tons (short) ton 0.907 kkg
yard yd 0.9144 m
hectares
cubic meters
kilogram-calories
kilogram calories/
kilogram
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer
atmospheres
(absolute)
square meters
square centimeters
metric tons
(1000 kilograms)
meters
* Actual conversion, not a multiplier
U.S. GOVERNMENT PRINTING OFFICE: 1975- 582—420:224
72
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POSTAGE AND FEES PAID
U.S. ENVIRONMENTAL PROTECTION AGENCY (A-107) ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460 EPA-335
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