EPA 440/1-74/042
Development Document for
Proposed 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
SM'TMBtiK 1974
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DEVELOPMENT DOCUMENT
for
PROPOSED EFFLUENT LIMITATIONS GUIDELINES
and
NEW SOURCE PERFORMANCE STANDARDS
for the
FORMULATED FERTILIZER SEGMENT
of the
FERTILIZER MANUFACTURING
POINT SOURCF CATEGORY
Russell E. Train
Administrator
James L. Aqee
Assistant Administrator for
Water and Hazardous Materials
Allen Cywin
Director, Fffluent Guidelines Division
Elwood E. Martin
Project Officer
September, 1974
Effluent Guidelines Division
Office of Water and Hazardous Materials
U.S. Environmental Protection Agency
Washington, D.C. 2CU6C
- :^eet,"fcG«n 1670
69004
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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.
fertilizer industry has seven distinctly separate
subcategori^s which have different pollutants, effluent treatment
technoloqies, 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
operatina personnel to obtain verifiable information on treatment
technology in corrmercial 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.
111
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CONTENTS
section
I CONCLUSIONS 1
II RECOMMENDATIONS 3
III INTRODUCTION 5
IV INDUSTRY CATEGORIZATION 29
V WASTE CHARACTERIZATION 33
VI SELECTION OF POLLUTANT PARAMETERS 37
VII CONTROL AND TREATMENT TECHNOLOGY 43
VIII COST, ENERGY AND NONWATER 49
QUALITY ASPECTS
IX BEST PRACTICABLE CONTROL TECHNOLOGY 53
CURRENTLY AVAILABLE, GUIDELINES AND
LIMITATIONS
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY 57
ACHIEVABLE, GUIDELINES AND LIMITATIONS
XI NEW SOURCE PERFORMANCE STANDARDS AND 59
PRETREATMENT STANDARDS
XII ACKNOWLEDGEMENTS 61
XIII REFERENCES 63
XIV GLOSSARY 65
V
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FIGURES
Figure Page
-*.. •.. \m•
1 Ammonium Sulfate - Synthetic Plant Locations 14
2 Ammonium Sulfate - By-Product Plant Locations 15
3 Ammonium Sulfate Flow Sheet - Synthetic 17
4 Ammonium Sulfate Flow Sheet - Coke Ovens 19
5 Blend Fertilizer - Plant Locations 21
6 Mixed Fertilizer - Plant Locations 22
7 Mixed Fertilizer Flow Sheet 26
8 Blend Fertilizer Flow Sheet 27
9 Ammonium Sulfate Plant - Effluent Control 45
10 Mixed Fertilizer Process - Effluent Control 46
11 Blend Plants - Airborne Solids Control 48
VI
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TABLES
Tables Page
1 Cost Summary Table 50
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 prac-
tical control technology currently available, best available
technoloay economically achievable, and which will allow n°w
plants to also meet the proposed guidelines without changes in
process design or equipment.
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SECTION II
RECOMMENDATIONS
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
discharae of process waste water pollutants to navigable waters.
^i xed and Blend Fertilizer Production Su beat egory
The proposed effluent limitations 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, 19"77, of effluent limitations for point sources,
other than publicly owned treatment works, which are based on the
application of the best practicable control technolooy currently
available as defined by the Administration pursuant to Section
30Mb) of the Act. Section 301 (b) also requires the achievement
bv 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
proaress 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 3^6 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, operatina
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 cateaory of point sources.
Section 306 of the Act requires the Administrator, within one
vear after a cateaory of sources is included in a list published
pursuant to Section 306 (b) (1) (a) of the Act, to propose regu-
lations establishing Federal Standards of performances for new
sources within such categories. The Administrator published _in
the Federal Register of January 16, 1973 (38 F.R. 162U), 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 included within the list published January 16,
1973.
The effluent limitations guidelines and standards of performance
proposed in this report were developed from operating data,
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samples, and information gathered from some fifteen (15) plants.
The methods and procedures used in the accumulation of that
overall information is described in the following paragraphs.
Summary of Methods Used for Development of the Effluent
Limitations Guidelines and Standards of Performance
The effluent limitations guidelines and standards of performance
proposed herein were develooed in the following manner. The
point source category was first studied for the purpose of
determinincr 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 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
(includina thermal) of all waste waters, including toxic con-
stituents 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 ranqe 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 technoloaies, which are existent or
capable of being designed for each segment. It also included an
identification of, in terms of the amount of constituents
(includina thermal) and the effluent level resulting from the
application of each of the treatment and control 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" 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
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environmental impact (including energy requirements), and oth^r
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. "^he four processes covered in this Phase II portion
of the Formulated Fertilizer report and the correspondina
Standard Industrial Classification (SIC) Codes are defined as:
MIXED_FEPTILIZER, 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. Ey fer-
tilizer terminology it includes three types of plants:
B type - Dry mixing plant that mixes wet or dry,
straiaht 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 speci-
fied as an A type plant.
AMMQNIUM 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
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building block principle. Such classification of data readily
permits the structuring of total water effluent information for
any soecific fertilizer complex regardless of the multiplicity of
processes comprising its make-up.
Bases for_Definitign^gf 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, energy reauirements 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. ^hese 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.
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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:
1) Di.S£i]fl£2.§_Effluent Quantities
Installation with low effluent quantities and/or the ultimate of
"no discharge".
2) Effluent^Contaminant Level
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.
U) 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 coolino 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) hir^Pollution Control
Those olants 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, hiah
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.
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9) Raw_Materials
Installations utilizing different raw materials where effluent
contaminants differ in impurity type or concentration.
10) DiversitY^Qf Processes
On the basis that other criteria are met, then consideration was
aiven to installations having a multiplicity of fertilizer
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.
SampJJ.ng_ Collect ion and Validation^Qf^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 hiqhly experienced operating personnel to the field work.
Three persons were used. The fertilizer plant operating
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.
U) 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 - 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.
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6) Validation of data, via intimate knowledge of plant labora-
tory 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 19^0. 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 1UOO - 1800 kkg/day (100 - 20C
to 1500 - 2000 tons/day); sulfuric acid plant capacity increased
from 270 - H50 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 - non-
mixed 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 re-
action as the binding force; or simply by mechanically blending
together straight fertilizers. The following tabulation lists
the principal straiaht and mixed fertilizers produced in the
United States.
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Straigh^Fertilizers Mi xed_ Fertilizers
Nitrogen Fertilizers
Ammonia
Urea
Ammonium Nitrate
*Ammonium Sulfate
Phosphate Fertilizers
Phosphoric Acid Ammonium Phosphates
Normal Superphosphate *Mixed Fertilizers
Triple Superphosphate *Elend Fertilizers
* Processes included in this study.
This Phase II oortion 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.
Ammoni.um_Sulf ate_rfanujacturina
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.t which with the
exception of 1972, has a history of gradual production decrease.
Production records of recent years are shown below:
Year AjBID2IliiJIB_Sul^ate_Production
Tons per Year
1966 2,859,505
1967 2,82U,255
1968 2,723,267
1969 2,563, 72"
1970 2,U83,985
1971 2,359,800
1972 2,U19,OOC
This unusual situation is attributed to the spectacular
popularity and corresponding production increases of ^diammonium
phosphate (DAP) as a mixed fertilizer material. Ammonium sulfate
"(AS)' and DAP have approximately equal N contents - nominal 21%
and 18% 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
storaae 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.
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There seems to be little question that ammonium sulfate's percen-
tage of total N market will continue to decrease although produc-
tion 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 U6 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 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
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AMMONIUM SULFATE - SYNTHETTf
PLANT LOCATIONS
i. ; ;; i
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AMMONIUM SULFATE - BY PRODUCT
PLANT LOCATIONS
!• TVUUF. 2
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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 tonnacre trend which
started in 1Q65 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 1,2U2,300 738,000
1968 903,700 670,000
1969 758,5CO 638,000
1970 663,900 595,00^
1971 606,700 5UO,COO
1972 578,600 564,000
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.) + H2SOU (liq.) ^ (NHU)2SOU (solid) + HEAT
Ammonia Sulfuric Acid Ammonium Sulfate
This reaction is highly exothermic liberating approximately
67,710 cal/g. mole or U23n 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
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AMMONIUM SULFATE - SYNTHETIC
ATMOSPHERIC PRESSURE CRYSTALLIZATION
Water Vapor
To Atmo s phe r e
/-^
X
Sulfuric Acid -
•^
Ammonia ^
,. fvs.
^ "^
y
•r
i
^ \
Air of 1 iL
**«.
j
Fan Pump
^-^
j
S
'
T
7
Crystallizer
i
r
/
ir
Pum
\
\
. r
n
i Q-1
p Pump
^i
E
Dry Product
^ for Reprocessing
^
Crystal Wash-Water
161-215 i /kkg
42-56
j"s]
"H
r
-^— I
n- — -^ — £>• /
Centrifuge! 1 M r\ i
g a I/ton
Dryer
— .^ 7 To Product
____^l Storage
n o
Process Water
7 W ^ 7
lW— fc
/•*-\ *J
>issolution Pump Mother ////
Tank Liquor
Tank
Leaks , spills
and wash water
from pump
1 seals and
T ////' equipment
washing, etc.
250-585 1/kkg
Li 60-140 gal/ton
Waste Sump
Figure 3
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coolina/evaporation and slurry solids necessary for optimum
crystal size formation. Precipitated crystals are separated from
the mother liauor normally by centrifugation. Following
centrif ucrat ion the crystals are washed, neutralized, and dried to
product specifications.
AMMONIUM SULFA^E - COKE OVEN BY-PRODUC^
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
15-2°% of this quantity can be recovered as ammonia. Ammonia
formation is normally considered to occur at coking temperatures
of approximately lOOCoC (1832oF) such as utilized in steel
industry coking operations. Under these conditions some 35-U5
pounds of ammonium sulfate can be produced per ton of ste^l.
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 ^).
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 I.ndi.rect 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/crystallizer.
The Semi-Direct process is a logical outcome of both the above
described techniques. ^he 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
18
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AMMONIUM SULPHATE - COKE OVENS
Sulfuric Acid
Crystal Wash-Water
To Atomsphere 161-215 1/kkg
gal/ton
Leaks, spills
and wash
111111 water from
pump seals
and equipment
washing, etc
250-585 1/kkg
60-140 gal/ton
Crude Anmonia Pump
Liquor Storage Lime
Leg
Ammonia
Still
Gaseous Ammonia Cleaning Equipment Connected with AS Plant
but not Directly Part of AS Process
Figure 4
-------
reheated to approximately VOoC. 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. 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
aopreciated by noting the large increase in the number of
particularly Blend Fertilizer plants which came into existence
durina the years 1°64 to 1974.
Estimated Number of Operating U.S.
Year Blend Fertilizer Plants,
1960 441
196U 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 fer-
tilizer processes. In fact the ammonium phosphates are indis-
pensable 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
'"he 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 \ising straight fertilizers meant that the farmer had to either
20
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BLEND FERTILIZER
PLANT LOCATIONS
NOTE: DUE TO THE LARGE NUMBER OF PLANTS
IN MAMY STATES ONLY REPRESENTATIVE
SITES WITH THE JPJMBER OF PLANTS ARE INDICATED,
t'lr.URE 5
-------
MIXED FERTILIZER
K)
NOTE: DUE 10 ' IlL L/.PC4H LIUMBKR OF PLANTS
IN yj-.'-.s ST/-.TRO ONLY REPRESENTATIVE
SITES" ..':ii; THI-. N'JMB.'.F 01 PLANTS ARF! INDICATED
-------
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
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 aradual 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
increasina 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 necessitate 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 annual
tonnage of materials produced by the Mixed and Blend Fertilizer
processes over the last 16 years.
23
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Dry, Mixed Fertilizer Ggodg_Consumption
(Short tons)
15,23C,5C5
1960 1U,868,024
1965 17,229,239
197P 18,176,900
1971 18,399,800
The tonnaqe figures do not fully reflect the status of dry mixed
fertilizer aoods. It should be added that the total amount of
mix^d fertilizers - both dry and liquids - applied on U. S. soil
in 1970 was 20,963,CCO tons. Dry mixed fertilizer therefore
represented aoproximately 87% of this 1970 total. Currently the
total quantity of direct application and mixed fertilizers used
in the TT.R. is approximately 12 million tons per y^ar. Agricul-
turists ^stimate that fertilizer usage needs to be 80 million
tons p°r year *-o realize most efficient crop growth. This
indicates that dry mixed fertilizer consumotion 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.
Th° 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
mixe-3 fertilizer process plants in the period 1959 to 1970 -
(e.g. 2n1 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
suifuric acid, phosphoric acid, nitrogen solutions, diammonium
phosphat0, ammonia, urea, ammonium nitrate, ammonium sulfate,
normal superphosphate, triple superphosphate, potash, sand and a
variety of minor elements. The choice of raw materials is depen-
dent 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-^ formulations, two or more raw materials may
be 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
24
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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 aranules are separated
for use as recycle material in the granulator. Product size
aranulps are cooled and conveyed to storage or shippina (See
Figur^ 7) .
BLENp_FERTILIZER_-_PROCES_S_DESCRIPTION
As previously mentioned the development and subsequent availa-
bility 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 pcwders 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.
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 segreaation 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 needed to produce the N-P-K
formulation desired. Raw material addition is normally by batch
weighina. 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) .
-------
Pond
Contaminated,
Water
Process Water
0-92 L/KKG
0-22 Gal/ton
Triple
Superphosphate
% DAP
Normal —
Superphosphate
NPK
Phosphoric
Acid
MIXED FERTILIZER PROCESS
1
Scrubber
System
Contaminated
^~ Water
3120-3330 L/KKG
750-800 Gal/toi
Dust
Collection
Muriate of
Potash Addition
-EN
Granulator
T
Ammonia
Dryer
To Product
Storage
' Figure 7
-------
to
BLEND FERTILIZER PROCESS
f
Dust Bag
Collector
Fertilizer Materials
Weigh/Belt
To Atmosphere
Fan
To Railroad
Elevator
Elevator
Figure 8
-------
SECTION IV
INDUSTRY CATEGORIZATION
The task of dividing the many fertilizer processes into specific
cateaories 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.
U. 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 reasonina 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.
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
29
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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 together into a
common effluent stream or because of the specific contaminant
treatment required, it necessitates that an individual process
effluent be treated separately regardless 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_Indiyidual_Process Effluents
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 separate. The
reasons for this condition are due to a combination of items
including because 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.
RawmMaterials
^ype 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.
30
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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_Sufccateggry
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.
31
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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. ^ach 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
curity of the rav materials used. These differences do not
change the type of water usage or effluent. The AS process
operation has the followinq types of water usage and wastes.
A. Contaminated Wa^er
B. Closed Loop Cooling Tower Water
C. Crvstal 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. contaminat ed 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 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 conseguently
accumulates sizeable concentrations of many cations and
33
-------
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 UOCO-8350
B• Closed Loop 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 con-
tamination 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. Crygtal 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
i/lSJS3 gal/ton
Ammonium Sulfate 161-215 U2 - 56
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:
34
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Process Quantity
1/kkg gal/ton
Ammonium Sulfate 250-^85 6n-lUC
Typical contaminants and concentrations in a Soills and Leak
stream are listed below:
Contaminant Concentrat2on_-_m3/l
Ammonia 12
COD 23
Ph *-«r'
Fluoride ?.fb
F . Non-Point Source Discharge
The oriain of such discharges are dry product, usually from
conveying equiomen4- , dusting over the plant area and then beinq
solubilized by rain or melting snow. The magnitude of this
contaminant source is a function of dust containment,
housekeeping, snow/rainfall quantities and the 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.
The mixed and blend fertilizer processes represent by far the
largest number of individual plants in the entire fertilizer
industry - an estimated 7UO^ plants. In respect to water usaae
and effluents, however, this subcategory is among the lowest
water usage seqments of U. S. industry. The processes have the
follov;ing listed types of water usage and wastes:
A. Contaminated Water
P. Process Water
C. Spills and Leaks
D. Non-Point Source Discharges
35
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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- Contaminatgd Water
Mixed fertilizer plants do have one process function which
requires a significant guantity 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 hiah
instantaneous water usaqe 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 Usage
1/kkg gal/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 guantity used is highly variable 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.
Process Usage
~~ i/]S]S2 gal/ton
Mixed Fertilizer 0-92 0-22
c• Spillg,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.
36
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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 Sufccategory
Effluent waste water from Ammonium Sulfate production units must
be monitored for the following primary parameters: Ammonia
nitroqen 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 orimary
parameters will effect removal of these secondary parameters.
Another reason is that insufficient data exists to establish
effluent limitations.
Mixed and^Blend Fertilizers Subcategory
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 oraanic 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), 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.
37
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Rationale for Selecting_Identifigd 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 (NO_2) , 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 50° ma/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 1C mg/1 of nitrate nitrogen (N03_-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
(NH.U + ) 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
sewaae 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 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.
38
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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 around 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 25C to U50 mg aiving 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 l.n
mg/1 of fluoride will seldom cause mottled enamel in children,
and for adults, concentrations less than 3 or " mg/1 are not
likely to cause endemic cumulative fluorosis and skeletal
effects. Abundant literature is also available describing the
advantaaes 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 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 orcranic CO2 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 sliaht BOD load to the effluent waste stream.
Phosphorus
Durina 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,
39
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frequently are caused by increasing supplies of phosphorus. Such
phenomena are associa-ted 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
swimmina danaerous. 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 around for flies.
Phosphorus in the elemental form is particularly toxic, and
subject to bioaccumulation in much the same way as mercury.
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.C are corrosive to water works
structures, distribution lines, and household plumbing fixtures
and can thus add such constituents to drinking water as iron,
40
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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 ^or providing safe drinkina water.
Fxtremes of pH or rapid pH changes can exert stress conditions or
kill aquatic life outriaht. Dead fish, associated alqal blooms,
and foul stenches are aesthetic liabilities of any waterway.
Even moderate chanaes from "acceptable" criteria limits of pH are
deleterious to some species. The relative toxicity to aquatic
life ot manv materials is increased by changes in the water pH.
Metalocvanide 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 hiaher pH.
The lacrimal fluid of the human eye has a pH of approximately 7.G
and a deviation of C.I oH unit from the norm may result in eye
irritation for the swimmer. Appreciable irritation will cause
severe oain.
METHODS OF ANALYSIS
rr}-,e jnetho^s of analysis to be used for quantitative determination
are aiven in the FederaJ. Register UC CFH 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
41
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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 v;ell 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 con-t-ami nation 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 investigatina treatment
technoloay.
- 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 technoloay
- To determine the degree of treatment cost reasonability
Based upon these stated criterion 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 its
introduction to the saturator/crystallizer. The gas cleanina
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 eras
cleanina and air pollution control mechanism for the oven gas
prior to its use as coke burner fuel.
43
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P£2ce^§_ 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)
Njixgd Fertilizer _ Process-Ef fluent 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 purcre stream includes dryer, cooler, and/or ammoniator
exhaust gas scrubbers. A minor secondary source is effluent from
leaks, spills and housekeeping.
Process^Description
The mixed fertilizer process requires a certain amount of liquid
to satisfy requirements of mixed fertilizer manufacture. The
auantity 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 re-
tention pond (a representative size is 10' wide x 60' lonq x 10'
deep) equipped with a pump to control the clarified (either by
settlina 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 offqases. 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 (5-2C% 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 ac-
44
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AMMQNIUM_SULjFATE PLANT
EFFLUENT CONTROr.
To Process
Make-Up Water
a
Spills,Leaks and Wash Water
Waste Sump
Figure 9
-------
MIXED FERTILIZER PROCESS
EFFLUENT CONTROL
Flow
Element
Contaminated
Water ^
\
Flow Control
Valve
To Scrubber
Contaminated water from
Scrubber, Leaks, Spills and Wash Water
I t I I I I I I
777/V-
Contaminated
Water to
Ammoniator/Granulato
///////////
Pump
Retention Pond
Figure 1C
-------
cumulated 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 v
seem to be one out of place in a study on liquid plant effluents. 1
It is however thought important to briefly discuss this point due ''•
to the large number of plants involved and the possible con- ;<
sideration 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)
47
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BLEND PLANTS
*>.
00
To Atmosphere
AAAAAAAAAA
Screw-
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
us°d 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,OCO
20,^00 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 - 5C 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 pre-
paration; construction and installation; and such other costs
reguired 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% of annual interest rate.
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.
49
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Operating 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 Wastes
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.
INSTALLATION AND OPERATION OF TECHNOLOGIES
Ammonium Sulfate Piant_Effluent Control
The 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.
51
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Fertilizer Process Effluent Control
The 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.
RT_Pnd_Fertilizer Airborne SQlids_Control
The time required for engineering, procurement and construction
is 9 months.
Installation of this equipment could largely proceed concurrent
with production but will require approximately 2U hours of tie-in
work.
52
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SECTION IX
BFST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
AVAILABLE, GUIDELINES AND LIMITATIONS
The effluent limitations which must be achieved by July 1, 1977
are based on the degree of effluent reduction attainable through
the application of the best practicable control technology
currently available. For the fertilizer manufacturing 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 technigues.
Q. Process changes.
f. Nonwater guality 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 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
53
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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:
Ammonium^Sulfate Plant Effluent Control
This control technology was found to be in current industrial use
at all the plants surveyed - both synthetic and coke oven by-
product units. The technoloay consists of simply collecting the
few process effluent streams (including 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.
Prgposed_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 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.
54
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MIXED AND BLEND FERTILIZER SUBCATEGORY
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 197U. 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
technologv is included in Section VII.
Proposed Effluent Lirnitation_Guideline
This technoloay 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_Liguid Effluent
The technology description as applied to this process is a
misnomer in that this process inherently has no liguid
reguirements. Process raw materials include only dry materials
and only dry type air effluent control equipment is used.
P. £°.E2 se d_ E f jrl u en t_ L i m i t at io n_ Guideline
The limitation guideline is simply that the existent technology
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.
55
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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. T'he 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
reauirements) .
Wa t gr _ Gu i de 1 i n e s
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 uoon 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.
Proposed Best Available Technology Economically Achievable
For the processes included in this Phase II survey, the best
available technoloay economically achievable is synonymous with
the technologies described as best practicable technologies
57
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currently available, ^his is no discharge of process waste water
pollutants to navigable waters.
58
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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 improved 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 pro-
duction 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.
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 water pollutants to
navigable waters.
59
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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 qood engineering design, new plants should be able to
eliminate the problem at the source by minimizing air leaks.
Pretreatment Requirements for New Sources
The tyoe 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 Powergas,
Inc., under contract no. 68-C1-15C8. 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.
Woodward Company, Woodward, Ala.
Valley Nitrogen, Helm, Calif.
61
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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.
62
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SECTION XIII
REFERENCES
A. Inorganic Fertilizer and Phosphate Mining. Industries - Water
Control
B. Industrial Pollution Control Handbook by Herbert F. Lund;
McGraw Hill Publishing Co., New York, Library of Conaress
Catalog Card Number 70-10116U.
C. Gauging and SampJ-lncj industrj.al Wastewater by Joseph G.
Robasky and Donald L. Koraido Calgon Corporation; Chemical
Engineering Magazine, Vol. 80, No. 1, January 8, 1973, Pages
111-120.
D. Environmental Protection Agency Stud^ Report Industrial Waste
Studies 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 Phosp_hate 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 X§^£^22lS ~ JJLL?. Walter W. Brown
Publishing Co., Inc. 75 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 Impact of Water Pollution Control Requirement^ 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.
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, 1^25 "K"
Street Northwest, Washington, D. C. 20006.
63
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L. The Chgmical Industry Facts Book by Manufacturing Chemist
Association, Inc., 5th Edition 1962, 1825 Connecticut Ave. ,
Washington, D. C. , Library of Congress Catalog Card No. 59-
154^7.
M. Water Duality. Criteria National Technical Advisory Committee,
Federal Water Pollution Control Administration, Washington,
D. C. , 1968.
N- Industrial Water Pollution Control W. W. Ekenf elder, 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 Chemicaj. Analysis of Water and Wastes EPA,
National Environmental Research Center, Analytical Quality
Control Laboratory, Cincinnati, Ohio (1971) .
Q- Sb^IDiSS! Process Industries R. Norris Shreve, Professor of
Chemical Engineering, Purdue University, Pages 398-4C4, First
Edition Fifth Impression, 1945.
P. AnUD2Hi!JE! §iLLfate 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. Ferjti_lizer Trendy JL22.1 National Fertilizer Development
Center, Muscle Shoals, Alabama 33660.
T. 1.922 Fertilizer Summary Data Norman L. Hargett, National
Fertilizer Development Center, Tennessee Valley Authority,
Muscle Shoals, Alabama.
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- l!S£±iii^§£ 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- l£2£3£nic Fertilizer Materials and Related Acids, Summary for
1222 Lonnie M. Conner, Chief for Chemicals, Wood Products,
and Non-Metalic Minerals Branch, U.S. Department of Commerce,
Bureau of the Census, Industry Division, Washinaton, D.C.
2^233
64
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SECTION XIV
GLOSSARY
TPY
Short Tons per year
Toxic Constituents
Relating to a poison
AS
Ammonium Sulfate
Virain
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.
65
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TABLE
METRIC TABLE
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS) by TO OBTAIN (METRIC UNITS)
ENGLISH UNIT ABBREVIATION CONVERSION ABBREVIATION METRIC UNIT
acre ac
acre - feet ac ft
British Thermal
Unit BTU
British Thermal
Unit/pound BTU/lb
cubic feet/minute cfm
cubic feet/second cfs
cubic feet cu ft
cubic feet cu ft
cubic inches cu in
degree Fahrenheit °F
feet ft
gallon gal
gallon/minute gpm
horsepower hp
inches in
inches of mercury in Hg
pounds lb
million gallons/day mgd
mile mi
pound/square
inch (gauge) psig
square feet sq ft
square inches sq in
ton (short) ton
yard yd
* Actual conversion, not a multiplier
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg
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 ton (1000 kilograms
meter
6f,
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