EPA 340/1-77-009
MAY 1977
Stationary Source Enforcement Series
INSPECTION MANUAL FOR ENFORCEMENT OF
NEW SOURCE PERFORMANCE STANDARDS
PHOSPHATE FERTILIZER
PLANTS
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Enforcement
Office of General Enforcement
Washington, D.C. 20460
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INSPECTION MANUAL FOR ENFORCEMENT OF
NEW SOURCE PERFORMANCE STANDARDS
PHOSPHATE FERTILIZER PLANTS
By
Contract No. 68-01-3173
Prepared For
U.S. Environmental Protection Agency
Division of Stationary Source Enforcement
Washington, D.C.
March 1977
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This report was furnished to the U.S. Environmental Protection Agency
by TRC - The Research Corporation of New England, Wethersfield, Connecticut,
in fulfillment of Contract No. 68-01-3173. The contents of this report
are reproduced herein as received from the contractor. The opinions, find-
ings, and conclusions expressed are those of the author and not necessarily
those of the U.S. Environmental Protection Agency.
The Enforcement Technical Guideline series of reports is issued by the
Office of Enforcement. Environmental Protection Agency, to assist the
Regional Offices in activities related to enforcement of implementation
plans, new source emission standards, and hazardous emission standards
to be developed under the Clean Air Act. Copies of Enforcement Technical
Guideline reports are available - as supplies permit - from Air Pollution
Technical Information Center, Environmental Protection Agency, Research
Triangle Park, North Carolina 27711, or may be obtained for a nominal cost,
from the National Technical Information Service, 5285 Port Royal Road,
Springfield, Virginia 22161.
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ACKNOWLEDGEMENTS
Mark Antell was the EPA Project Officer for this program. Robert
Kenson, Ph.D., was TRC's Project Director, while Vladimir Boscak, Ph.D.,
was Project Manager. Principal authors were Nicola Formica and Samuel
Cha.
We appreciate the cooperation of the following phosphate fertilizer
companies: CF Industries; Inc., W. R. Grace & Company; Texasgulf, Inc.;
IMC Chemicals Corporation; and Gardinier, Inc.
We also appreciate the advice of Hillsborough County (Florida)
Environmental Protection Commission personnel.
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TABLE OF CONTENTS
SECTION PAGE
1 INTRODUCTION 1
2 PHOSPHATE FERTILIZER INDUSTRY 3
3 SUMMARY OF NEW SOURCE PERFORMANCE
STANDARDS (NSPS) AND REGULATIONS 6
3.1 Federal Emission Standards 7
3.1.1 Monitoring and Reporting 8
3.1.2 Performance Testing 8
3.1.3 Applicability of Standards 9
3.2 State Regulations 10
4 EMISSION CONTROL EQUIPMENT 12
4.1 Spray Towers 15
4.2 Venturi Scrubbers 17
4.3 Spray-Crossflow Packed Scrubbers .... 17
4.4 Impingement Scrubbers 24
4.5 Maintenance of Control Equipment .... 24
5 PHOSPHATE FERTILIZER MANUFACTURING PROCESSES . 28
5.1 Wet Process Phosphoric Acid (WPPA) Plants . 28
5.1.1 Process Description 28
5.1.2 Emission Sources 30
5.1.3 Control Equipment and Inspection
Procedures 33
5.2 Superphosphoric Acid (SPA) Plants .... 34
5.2.1 Process Description 34
5.2.2 Emission Sources 38
5.2.3 Control Equipment and Inspection
Procedures 40
5.3 Diammonium Phosphate (DAP) Plants .... 41
5.3.1 Process Description 41
5.3.2 Emission Sources 44
5.3.3 Control Equipment and Inspection
Procedures 47
5.4 Run-of-Pile Triple Superphosphate (ROP-TSP)
Plants 48
5.4.1 Process Description 48
5.4.2 Emission Sources 48
5.4.3 Control Equipment and Inspection
Procedures 50
5.5 Granular Triple Superphosphate (GTSP)
Plants 51
5.5.1 Process Description 51
5.5.2 Emission Sources 53
5.5.3 Control Equipment and Inpsection
Procedures 55
iii
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TABLE OF CONTENTS (Cont.)
SECTION PAGE
6 FACILITY RECORD KEEPING AND REPORTING
REQUIREMENTS 57
6.1 Record Keeping 57
6.2 Reporting Procedures 57
7 INSPECTIONS 58
7.1 Inspection Preparation 58
7.2 Performance Test 59
7.2.1 Pre-Test Procedures 59
7.2.2 Performance Test Monitoring 60
7.3 Post-Performance Test Inspections 60
7.3.1 Pre-Inspection Procedures 60
7.3.2 Inspection Procedures 65
7.4 Post-Inspection Procedures 65
8 GYPSUM PONDS 74
REFERENCES CITED 76
GENERAL REFERENCES 77
iv
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LIST OF TABLES
TABLE PAGE
3-1 Summary of Fluoride and Other Emission Standards
Related to Phosphate Fertilizer Plants in
Selected States ............ 11
5-1 Fluoride Emission Factors ......... 32
7-1 NSPS Inspection Checklist for Phosphate Fertilizer
Plants During Performance Tests ....... 61
7-2 NSPS Inspection Checklist for Phosphate Fertilizer
Plants After Performance Tests ....... 66
LIST OF FIGURES
FIGURE PAGE
2-1 Organization of the Phosphate Fertilizer
Industrial Processes 4
4-1 Fluoride Scrubbing System 13
4-2 Fluoride Control System on GTSP Plant : . . . . 14
4-3 Relationship Between Gas Temperature and
Scrubber Removal Efficiency 16
4-4 Cyclonic Spray Tower Scrubber 18
4-5 Cyclonic Spray Tower on ROP-TSP Plant 19
4-6a Gas Activated Venturi Scrubber with Cyclonic
Mist Eliminator 20
4-6b Water Actuated Venturi 20
4-7 Water-Induced Venturi on SPA Plant 21
4-8 Venturi Scrubber on DAP Process Facility .... 22
4-9 Spray Cross-Flow Packed Bed Scrubber 23
4-10 Cross-Flow Packed Scrubber on WPPA Plan .... 25
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LIST OF FIGURES (Cont.)
FIGURE PAGE
4-11 Self-Induced Spray Type Scrubber 26
5-1 Wet-Process Phosphoric Acid Production 29
5-2 Submerged Combustion Process for Producing
Superphosphoric Acid 35
5-3 Vacuum Concentration Process for Producing
Superphosphoric Acid 36
5-4 Falling Film Process 37
5-5 Forced-Circulation Evaporation Process 37
5-6 Submerged Combustion Superphosphoric Acid
Production 39
5-7 Diammonium Phosphate Production 42
5-8 Dorr-Oliver Process 45
5-9 T.V.A. Process 46
5-10 Run-of-Pile Triple Superphosphate Production
and Storage 49
5-11 T.V.A. One-Step Process for Granular Triple
Superphosphate 52
5-12 Dorr-Oliver Slurry Granulation Process for
Triple Superphosphate 54
5-13 Control Panel for GTSP Plant 56
VI
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SECTION 1
INTRODUCTION
In accordance with Section 111 of the Clean Air Act (42 USC 1857,
et seq.), the Administrator of the U.S. Environmental Protection Agency
(EPA) promulgated emission standards with an effective date of August 4,
1975 for the phosphate fertilizer industry. These new Source Performance
Standards (NSPS) limit fluoride emissions from the following phosphate
fertilizer processes:
1. Wet Process Phosphoric Acid Plants
2. Super Phosphoric Acid Plants
3. Diammonium Phosphate Plants
4. Triple Superphosphate Plants
5. Granular Triple Superphosphate Storage Facilities
EPA has issued a final guideline document for control of fluoride
emissions from existing phosphate fertilizer plants.
Applicable laws permit EPA to delegate implementation and enforce-
ment authority to the states or local regulatory agencies. Such enforce-
ment requires inspection of facilities that must comply with NSPS. The
purpose of this inspection is:
1. To determine that the facilities with their control
equipment comply with the regulations.
2. To ensure that facilities are operated and maintained
in a manner consistent with good air pollution con-
trol practices.
Phosphate fertilizer plants generally consist of a number of pro-
cesses, some of which are quite complex, that require air pollution con-
trol equipment. In order to make a successful inspection within a
reasonable time, it is essential that inspectors are well prepared for
inspection visits.
This manual will provide the air pollution inspector with necessary
background information to determine at any time whether or not a plant's
operating parameters are consistent with operation during performance
tests which have indicated compliance of emission sources.
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This manual will also assist the inspector in preparing for his
inspection visit to phosphate fertilizer plants by providing:
1. Descriptions of the five fertilizer processes covered
by NSPS;
2. Discussions of the emission control equipment used by
the phosphate fertilizer industry; and
3. Procedures for inspecting the emission control equip-
ment both during and after performance testing.
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SECTION 2
PHOSPHATE FERTILIZER INDUSTRY
The phosphate fertilizer industry, a segment of the agricultural
chemical industry, produces and markets commodities bearing the basic
nutrients—nitrogen, phosphorous, and potash—for crop production. The
industry is totally dependent on phosphate rock deposits, which provide
all fertilizer phosphorous.
The principal raw material in the deposits is fluorapatite,
in which the phosphorous is poorly available as a nutrient
to most growing plants. As normal superphosphate, however, the phosphor-
ous can be used by plants for growth. Although this product was first
made in 1850, it was not until about 1950 that the potential of the phos-
phate fertilizer manufacturing industry was recognized. Fertilizer
products that were of little importance in 1950 were major nutrient sup-
pliers by 1965.
The production of phosphate has been on the increase since 1960,
exceeding 5 x 106 tons P205 in 1971. In that same year, over 1 x 106
tons of triple superphosphate and 2 x 106 tons of ammonium phosphates
were produced.
Phosphate fertilizer production begins with the mining of phosphate
rock, proceeds with the chemical production of phosphoric acid and its
subsequent processing to diammonium phosphate, superphosphoric acid or
triple superphosphate, and terminates with fertilizer formulation and
blending.
The structure of the phosphate industry is very complex as shown
in Figure 2-1. This schematic illustrates the interrelationship of the
various products manufactured by the industry. Many plants consist of
more than one phosphate fertilizer production process and include non-
phosphate operations such as ammonia and sulfuric acid production.
The basic chemical producers of phosphate fertilizers are generally
not identifiable as single product firms, for most fertilizer production
is conducted as a subsidiary activity in well-diversified corporations
such as chemical manufacturers or petrochemical companies. Some com-
panies are farm cooperatives while others derive the main portion of
their revenue from totally unrelated activities. Generally, the basic
chemical producers own the source of their raw materials, the phosphate
rock mines.
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HN03
NH3
Nitric
Phosphate
Phosphate Ore
Phosphoric Acid
NH3
NH3
NH3
Ammonium
Phosphate
Liquid Mixed
Fertilizer
Triple Super-
phosphate
Solid Mixed
Fertilizer
v
Finished Phosphate Fertilizers
H2SOi,
Normal
Superphosphate
Figure 2-1: Organization of the Phosphate Fertilizer
Industrial Processes
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Because the major phosphate rock mining area of the United States
is in Florida, much of the U.S. phosphate industry is located in this
state. One major product, triple superphosphate, is shipped to the
Midwest and other areas for bulk blending or for the production of homo-
genous fertilizers by ammoniation of superphosphate. Other important
sources of phosphate rock are located in Tennessee, North Carolina, and
the Rocky Mountain area (Idaho and surrounding states).
Normal superphosphate is usually produced near the consumption
point rather than near the phosphate ore. Most of these plants are in
the Southeast and on the East Coast where the fertilizer industry first
developed in the United States.
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SECTION 3
SUMMARY OF NEW SOURCE PERFORMANCE STANDARDS (NSPS) AND REGULATIONS
Standards of air pollution control performance for five affected
facilities within the phosphate fertilizer industry were proposed on
October 22, 1974 (39 FR 37602). The final version of the standards was
published on August 6, 1975 (40 FR 33152) with an effective date of
August 4, 1975. These standards are promulgated under the authority of
Section 111 (a), (b), and (c) of the Clean Air Act, and apply to NEW
SOURCES for which construction or modification commenced after the publi-
cation of proposed regulations; i.e., October 22, 1974. These standards
are concerned only with fluoride emissions within the affected facilities.
Section lll(d) of the Clean Air Act requires that EPA establish
procedures under which states must develop emission standards for certain
pollutants from existing sources for which NSPS have been promulgated.
To accomplish this, EPA proposed on October 7, 1974 a procedure for con-
trol of "designated pollutants" from "designated facilities" and promul-
gated that procedure on November 17, 1975 (40 FR 53340). Designated
pollutants are pollutants which are not included on the lists published
under Section 108(a) (National Ambient Air Quality Standards) or Section
102 (b)(l)(A) (Hazardous Air Pollutants) of the Clean Air Act, but for
which NSPS have been established under Section lll(b). A designated fa-
cility is an existing facility which emits a designated pollutant and
for which NSPS have been promulgated.
As required by the procedure, EPA first defined designated pollutants,
such as fluoride, as either a welfare-related or a health-related pollu-
tant, and then established a guideline for existing sources which recom-
mends a level of emission control for these sources. This guideline,
which has determined fluoride emissions from phosphate fertilizer plants
to be a welfare-related pollutant, was published in April 1976 and was
announced to the public for comment on May 12, 1976 (41 FR 19585). The
final guideline was published in November 1976 and announced to the public
on March 1, 1977 (42 FR 12021). This has been incorporated in the State's
implementation plan.
This section will describe the NSPS for the phosphate fertilizer
industry, the emission standards recommended by the guideline for existing
sources, and also the state regulations related to fluoride emissions now
existing.
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3.1 Federal Emission Standards
NSPS limit total fluoride emissions to the atmosphere from phosphate
fertilizer plants and permit different emission rates for each of the
five major components of the industry category. These allowed fluoride
emission rates are listed below:
a. Wet Process Phosphoric Acid (WPPA) plants:
No more than 10 grams of total fluoride per metric ton
of P205 input to the process (0.020 Ib/ton).
b. Superphosphoric Acid (SPA) plants:
No more than 5.0 grams of total fluoride per metric ton
of P205 input to the process (0.010 Ib/ton).
c. Diammonium Phosphate (DAP) plants:
No more than 30 grams of total fluoride per metric ton
of P205 input to the process (0.060 Ib/ton).
d. Triple Superphosphate (TSP) plants, including both Granu-
lar Triple Superphosphate GTSP) and Run-Off Pile (ROP)
TSP process and RPO-TSP storage1facilities:
No more than 100 grams of total fluorides per metric ton
of P205 input to the process (0.20 Ib/ton).
e. Granular Triple Superphosphate (GTSP) storage facilities:
No more than 0.25 grams of total fluoride per hour per
metric ton of P205 stored (5.0 x 1Q'1* Ib/hr/ton stored).
Standards for visible emissions for DAP plants, TSP plants and GTSP
storage facilities were proposed, but were later deleted because there
was no direct correlation between fluoride emissions and plume opacity.
The final guideline document recommends that the fluoride emissions
for existing phosphate fertilizer facilities be as follows:
a. 0.01 g/kg P205 for WPPA production (0.02 Ib/ton).
b. 0.005 g/kg P205 for SPA production (0.01 Ib/ton).
c. 0.030 g/kg P205 for DAP production (0.06 Ib/ton).
d. 0.100 g/kg P205 for ROP-TSP production and storage
(0.2 Ib/ton)
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e. 0.100 g/kg P205 for GTSP production (0.2 Ib/ton).
f. 2.5 x lO'4 g/hr-kg P205 for GTSP storage (5.0 x l
Ib/hr/ton).
3.1.1 Monitoring and Reporting
As required by the NSPS, the owner or operator of any WPPA, SPA, DAP
or TSP plant shall install, calibrate, maintain and operate monitoring
devices which can be used to determine
1. the mass flow rate of phosphorous-bearing feed material
to the process, and
2. the total pressure drop across the process scrubbing
system.
These devices shall have an accuracy of ±5 percent over their operating
range.
The owner or operator of these plants also shall maintain a daily
record of equivalent P205 feed by using
1. the mass flow rate of phosphorous-bearing feed material
and
2. the percent P205 content measured by the molybdovanadophos-
phate spectrophotometric method (Method 9 as described in
the llth edition of Official Methods of Analysis of Associa-
tion of Official Agricultural Chemists [AOAC]).
The owner and operator of any GTSP storage facility shall maintain
1. an accuracte account of TSP in storage to permit the
determination of the amount of equivalent P205stored,
and
2. a monitoring device which measures and records the
total pressure drop across the process scrubbing sys-
tem. This monitoring device shall have an accuracy of
±5 percent over its operating range.
3.1.2 Performance Testing
The NSPS require that the owner or operator of a source subject to
the performance standards conduct a test under representative operating
8
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conditions within 60 days after achieving maximum production rate but not
later than 180 days after initial startup, and that he furnish a written
report of the results of the test to the Environment Protection Agency,
Office of General Enforcement (40 CFR 60.8). Furthermore, the owner or
operator of an affected facility should provide the Administrator 10 days
prior notice of the performance test.
Reference methods in Appendix A of Part 60 of Chapter I, Title 40
CFR (36 FR 24876, 41 FR 23060) shall be used to determine compliance with
the standard as follows:
1. Method 13A or 13B for the concentration of total flu-
orides and the associated moisture content,
2. Method 1 for sample and velocity traverses,
3. Method 2 for velocity and volumetric flow rate, and
4. Method 3 for gas analysis.
3.1.3 Applicability of Standards
The NSPS classify and define the affected facilities as the follow-
ing:
1. Wet-Process Phosphoric Acid (WPPA) plant:
Any facility manufacturing phosphoric acid by reacting
phosphate rock and acid. This includes any combination
of reactors, filters, evaporators, and hot wells.
2. Superphosphoric Acid (SPA) plant:
Any facility which concentrates wet-process phosphoric
acid to 66 percent or greater P205 content by weight for
eventual consumption as a fertilizer. This includes any
combination of evaporators, hot wells, acid sumps and
cooling tanks.
3. Granular Diammonium Phosphate (DAP) plant:
Any plant manufacturing granular diammonium phosphate
by reacting phosphoric acid with ammonia. This includes
any combination of reactors, granulators, dryers, coolers,
screens and mills.
4. Triple Superphosphate (TSP) plant:
Any facility manufacturing triple superphosphate by
reacting phosphate rock with phosphoric acid. This
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includes any combination of mixers, curing belts
(dens),reactors, granulator dryers, cookers, screens,
mills and any facilities which store run-of-pile TSP.
5. Granular Triple Superphosphate (GTSP) Storage facili-
ti es:
Any facility curing or storing granular triple super-
phosphate. This includes any combination of storage
or curing piles, conveyors, elevators, screens and
mills.
While phosphate rock mining, rock crushing, sulfuric acid plants and
nitric acid plants are commonly an intergral part of the phosphate fer-
tilizer industry, they are subject to separate NSPS and therefore are
outside the scope of this manual.
3.2 State Regulations
States in which the majority of phosphate fertilizer plants are
located have been applying existing regulations to control fluoride emis-
sions. Selected state regulations are summarized in Table 3-1.
In addition, since each state may have standards for emissions other
than fluorides, the inspector is therefore inspecting not only for fluor-
ide violations but also for violations of other state regulations.
Therefore, the details of state emission standards and testing regula-
tions must be examined before inspection occurs. The major state stan-
dards applicable to phosphate fertilizer plants are those for visible
emissions, particulate emissions, and ambient air fluoride concentrations.
10
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TABLE 3-1
SUMMARY OF FLUORIDE AND OTHER EMISSION STANDARDS
RELATED TO PHOSPHATE FERTILIZER PLANTS
IN SELECTED STATES
Location
California
Florida
Idaho
Iowa
Mississippi
Montana
N. Carolina
Texas
Virginia
Washington
Fluorides
2.5 mg/DSCF
Standards vary with
specific process
-
0.4 Ib/ton P205 input
max. 100 Ib/day
0.4 Ib/ton P205
0.3 Ib/ton PaOs input
-
-
Particulates
-
(i)
-
(i)
(i)
d)
(*) and controlled
as chemical ferti-
lizer manufacturing
plants
max. 0.07 grains/
SCF
'*' and controlled
as chemical ferti-
lizer manufacturing
plants
Visible l^J
"Ringelmann
Coefficient"
-
2
2
-
-
2
-
Ambient
Fluorides
Standard
-
-
-
-
-
1 ppb (24 hr)
3.5 ppb (24 hr)
-
4.5 ppb (1 hr)
3.5 ppb (24 hr)
2.0 ppb (1 wk)
1.0 ppb (1 mo)
NOTES
(x)Rate of emission shall be calculated based on process weights
(2)visible "Ringelmann Coefficient" 2 is equivalent to 40 percent opacity.
11
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SECTION 4
EMISSION CONTROL EQUIPMENT
Fluorine compounds are the only air pollutants regulated by NSPS for
phosphate fertilizer plants. Of the types of air pollution control equip-
ment available, only those involving adsorption or absorption are capable
of removing gaseous fluorine compounds from air. Although solid packed
beds of limestone or alumina have been proposed for the removal of fluor-
ine by adsorption, wet scrubbers have been used almost exclusively for
control of fluoride emissions.
Most often, the fluoride emissions are controlled by complex scrub-
bing systems rather than by a single control device. Such systems usually
consist of cyclones as primary collectors and a combination of venturi-
spray scrubbers as secondary collectors. The emissions from such control
devices are then frequently combined into a tail gas scrubber as a final
stage. Baghouses and electrostatic precipitators are also used as com-
ponents in these systems. Figure 4-1 shows a schematic of a typical
fluoride scrubbing system; Figure 4-2 is a photograph of the scrubbing
system used by one GTSP plant.
Wet scrubbers are air pollution control devices which remove gases
and particulates from the stream through scrubbing by liquid. The col-
lection principle is to first bring aerosols and gas molecules close to
the collecting bodies (liquid droplets) and then to accomplish the actual
collection through a number of short-range physical and chemical mechan-
isms. The physical and chemical phenomena by which contaminants are
removed from the gas stream are called unit mechanisms.
The basic unit mechanism for removal of gases is mass transfer (dif-
fusion), while the driving force for this operation is concentration
gradient. The basic unit mechanisms for removal of particulate are the
physical forces of interception, inertial impaction, Brownian motion, and
particle growth condensation. Wet scrubbing systems exploit both mech-
anisms to remove particulate and gaseous components from contaminated gas
streams.
The knowledge of fluorine compounds present in the gas and scrubbing
liquids is of prime importance since each compound has its own adsorption
rate and may exist in a gaseous stage and/or as particulate or fume.
Consequently, it is very difficult to predict the efficiency of an abate-
ment system.
12
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2nd Stage
Cyclonic Scrubber
Venturi
Figure 4-1: Fluoride Scrubbing System
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Figure 4-2: Fluoride Control System on 6TSP Plant
14
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In general, the extent of the fluorine abatement system required is
determined by the following parameters:
1. Inlet fluorine concentration,
2. Allowable fluorine emissions,
3. Outlet or saturated gas temperature,
4. Composition and temperature of the scrubbing liquid,
5. Scrubber effectiveness and number of transfer units,
6. Fluorine compounds present, and
7. Effectiveness of entrainment separation.
The inlet concentration and allowable outlet fluorine emissions must
first be established to determine the overall scrubbing requirement.
Figure 4-3 shows the relationship between saturated gas temperatures and
the overall removal efficiency of the scrubbing device.1 The gas stream
leaving the scrubber is saturated with water vapor. When the scrubber is
operated at a relatively low saturated temperature (gas temperature close
to the gypsum pond water temperature), the efficiency is high. Since
absorption decreases with temperature increase, efficiency is lower at a
higher saturated temperature. An additional advantage of scrubber opera-
tion at low temperatures is that silica is kept in a gelatinous stage
which is easily washed from the scrubbing device. At higher temperature,
the silica is crystallized on the scrubber and removed with great diffi-
culty.
The scrubber effectiveness, or the number of transfer units, will
determine the overall scrubbing requirements. Figure 4-3 shows the fluo-
rine removal transfer unit formula.
Transfer units are defined by the following formula:
MTU - i« Inlet F
NTU - 1n Outlet F + a
where: a = vapor pressure contribution of fluorine from scrubbing media
Once the overall transfer unit requirements are determined, the number of
scrubbing stages may then be set based upon the ability of each scrubbing
device employed.
The scrubbers which are likely to perform well in phosphate fertilizer
plants include spray towers, venturi scrubbers, cross-flow packed scrubbers,
and impingement scrubbers.
4.1 Spray Towers
Spray towers provide the contact necessary for gas absorption by
dispersing the scrubbing liquid in the gas phase in the form of a fine
15
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10
u.
c/o
£
«/>
z:
x:
a:
UJ
u
o
o
UJ
1.0
0.1
"21
10
INLET CONCENTRATION MGM AS F/ScF
FLUORINE SCRUBBING
WITH
LOW FLUORINE CONTENT LIQUOR
FLUORINE REMOVAL TRANSFER UNIT FORMULA
100
Nt = In
Yl -
- Y,
Nt = Number of
transfer units
Y = Concentration of fluoride in gas
1 - at inlet
2 - at outlet
a - content based upon gas phase equili-
brium with concentration of fluoride
in scrubbing liquor in concentrations
below 5,000 ppm as F this effect is
neglected.
Figure 4-3: Relationship Between Gas Temperature and Scrubber
Removal Efficiency (Reprint with Permission of the
Mcllvaine Company from Mcllvaine Scrubber Manual,
1976, p. 42, 511)
16
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spray. Cyclonic spray towers eliminate excessive entrainment of scrub-
bing liquid by utilizing centrifugal force to remove entrained droplets.
Figure 4-4 is a schematic of a typical spray tower, while Figure 4-5
shows a cyclonic spray tower being used at a run-of-pile triple super-
phosphate plant. A tangential inlet is used to impart the spinning motion
to the gas stream which flows perpendicular to the water sprays. Pressure
drops across the scrubber range from 2-8 inches of water. Although solids
handling capacity is high, absorption capacity is limited to about two
transfer units.
4.2 Venturi Scrubbers
Although venturi scrubbers are primarily particulate collection
devices, they are also successfully applied to gas absorption work and
are widely used throughout the phosphate fertilizer industry.
When treating effluent streams requiring a high degree of fluoride
removal, venturi scrubbers are often used as the initial component in a
multiple scrubber system. Venturi scrubbers can bring about effective
contact and gas absorption when sufficient energy is imparted to the gas
to atomize the scrubbing liquor and produce very small droplets. The
atomization is obtained from velocity differences between the two phases
and gas-liquid contact is obtained from turbulence in the venturi throat.
As shown in Figure 4-6, both gas and water-actuated systems are in
use, and both types require the use of a mist elimination section for
removal of scrubbing liquid. Figure 4-7 shows a photograph of a water-
induced venturi in use on a superphosphoric acid plant effluent stream.
In this system the scrubbing liquid is introduced at a high velocity
through a nozzle located upstream of the venturi throat. The velocity of
this water stream is used to pump the effluent gases through the venturi.
Because there is no fan, the water-actuated venturi is mechanically
simpler, more reliable, and less costly than the gas-actuated type. In
addition, it is relatively insensitive to variations in the gas stream
flow rate. Pressure drops of air across these scrubbers are as high as
8 to 20 inches of water, and efficiencies reaching 96 percent have been
reported. On the other hand, these units do use large volumes of scrub-
bing liquid and have high energy requirements for pumping.
A venturi scrubber being used on a DAP process is shown in Figure
4-8.
4.3 Spray-Crossflow Packed Scrubbers
The spray-crossflow packed bed scrubber has been accepted as the
most satisfactory fluoride control device available for wet process phos-
phoric acid plants. As shown in Figure 4-9, the spray-crossflow packed
bed scrubber consists of two sections, a spray chamber and a packed bed,
17
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Figure 4-4: Cyclonic Spray Tower Scrubber
18
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Figure 4-5: Cyclonic Spray Tower on ROP-TSP Plant
19
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AIR
INLET
WATER
INLET
VENTURI
AIR
OUTLET
CYCLONIC
MIST ELIMINATION
SECTION
WATER
OUTLET
Figure 4-6a:
Gas Activated Venturi Scrubber with
Cyclonic Mist Eliminator
SPRAY
NOZZLE
WATER
INLET
AIR
INLET
SEPARATOR
BOX
AIR
OUTLET
WATER
OUTLET
Figure 4-6b: Water Actuated Venturi
20
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Figure 4-7: Water-Induced Venturi on SPA Plant
21
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Figure 4-8: Venturi Scrubber on DAP Process Facility
22
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PRIMARY GAS INLET
POND WATER
SECONDARY
GAS INLET
Figure 4-9: Spray Cross-Flow Packed Bed Scrubber
-------
separated by a series of irrigated baffles. Both sections are equipped
with gas inlets. Gas streams with high fluoride and particularly high
Si Fit concentrations are treated in the spray chamber before entering
the packing. This reduces the danger of plugging in the bed, reduces
the loading on the packed stage, and provides some solids handling
capacity. The crossflow design operates with the gas stream moving
horizontally through the bed with the scrubbing liquid flowing verti-
cally through the packing. Solids deposited near the front of the bed
are washed off by a cleaning spray. Pressure losses through the scrub-
ber range from 1-8 inches of water, the average being about five inches.
Recycled gypsum pond water is normally used as the scrubbing liquid
in both the spray and packed sections, the ratio of scrubbing liquid to
gas ranging from 0.02 to 0.07 gpm/acfm (.045-.156 Ipm/m3/hr) depending
on the fluoride content of the gas stream.
Provided that the solids loading of the effluent stream has been
reduced enough to prevent plugging, the fluroide removal efficiency of
the spray-crossflow packed bed scrubber is limited only by the amount of
packing used and the scrubbing liquid. Efficiencies as high as 99.9%
have bben reported.2
Figure 4-10 shows a spray-crossflow scrubber in use at a wet pro-
cess phosphoric acid plant.
4.4 Impingement Scrubbers
Impingement scrubbers have also been used with success to treat ef-
fluent streams containing fluorides. One type of impingement scrubber
shown in Figure 4-11 is most effective and is commonly used by the fer-
tilizer industry. This consists of a rectangular chamber with a sloping
bottom designed to contain a shallow bath of scrubbing liquor. Gases
are driven into the bath at high velocity and water-soluble components
are removed by resulting impingement. Water requirements are low (.5-2
gal/103ft3gas) and efficiencies as high as 99% have been reported.3
Typically, the pressure drop across the scrubber is 5-15 inches.
4.5 Maintenance of Control Equipment
The maintenance of scrubber systems should be less than that re-
quired for fabric filters and precipitation systems if equipment is
properly sized and applied. If, however, the scrubber system is im-
properly designed, maintenance costs can be extremely high.
Preventive maintenance is an important part of any maintenance pro-
gram, and regular measurement of scrubber efficiency can be used as a
tool for preventive maintenance. If the equipment initially functions
at designed efficiency, a regular efficiency test of the system can lead
24
-------
Figure 4-10: Cross-Flow Packed Scrubber on WPPA Plant
25
-------
Figure 4-11:
Self-Induced Spray Type Scrubber (Doyle)
(Reprint with Permission of Pergamon Press from
Industrial Gas Cleaning Equipment. 1966)
26
-------
to identification and correction of problems long before they are dis-
covered by maintenance personnel.
Some of the problems that can surface on scrubbers in operation
include reduction of volumetric flow rate, lowered collection perform-
ance, liquid carryover, and scaling. In order to prevent some of these
problems from becoming too serious, regular inspections should be car-
ried out. The best indication of scrubber operation is the pressure drop
across the unit. Under steady operating conditions, the pressure drop
will stay constant within ±0.2 in. W.G. The scrubber pressure drop
should be observed and recorded at least three times a day. Any change
of pressure drop might indicate scrubber malfunctioning. An increase
in pressure drop will indicate plugging or too high air or scrubbing
liquid flow rate. A decrease in pressure drop will indicate a reduc-
tion in air or scrubbing liquid flow rate. Scrubber inspections should
also include checking of the dampers, fan drive belts, spray nozzles,
drains, and scrubber feed water clarification system, and scrubber inlet
ducts should be examined for leaks or blockage by deposited materials.
Any malfunctions should be corrected as soon as possible.
27
-------
SECTION 5
PHOSPHATE FERTILIZER MANUFACTURING PROCESSES
Five phosphate fertilizer manufacturing processes are regulated by
NSPS for the phosphate fertilizer industry. These processes include the
manufacture of wet process phosphoric acid and superphosphoric acid and
their subsequent processing into diammonium phosphate, run-of-pile
triple superphosphate, and granular triple superphosphate. This sec-
tion of the manual summarizes each of the processes and discusses the
sources of fluoride emissions and applicable air pollution control
techniques.
5.1 Wet Process Phosphoric Acid (WPPA) Plants
5.1.1 Process Description
Phosphoric acid, a major intermediate in fertilizer technology,
is used in the production of superphosphate, ammonium phosphate, and
mixed granular fertilizers.
The manufacture of phosphoric acid itself begins with phosphate
rock as raw material. Typical phosphate rock from the United States
used for wet process phosphoric acid production may contain 31-35% P205
and 1.5 to 4.0% combined iron and aluminum oxides. The process used
for the production of phosphoric acid is often described as the dihy-
drate process because the gypsum byproduct that is formed is substanti-
ally all in the dihydrate form.
Several variations of the dihydrate process are currently in
use by the phosphate fertilizer industry. The Dorr-Oliver, St. Gobain,
Prayon, and Chemico processes are among the better known schemes.
Basically, there is little difference among them, most variations being
in reactor design and operating parameters. All process types consist
of three major steps: reaction, filtration, and evaporation. A pro-
cess flow diagram for the production of wet process phosphoric acid is
shown in Figure 5-1.
In the first step, ground rock is slurried with acid. Although
any common mineral acid may be used to digest phosphate rock, sulfuric
acid is normally used on a commercial scale for wet process phosphoric
acid manufacture. The use of a 66° Be acid (93-98% H2SOit) is preferred
to acids of lower strength.
28
-------
ro
EMISSIONS
PHOSPHATE
ROCK
SULFURIC
ACID
REACTOR
FILTER
V
I
I
^
GYPSUM
r~M
SEAL
TANKS
LyK/v
HOTWELL.
SCRUBBER
54% P205
ACID
EVAPORATOR
A M;A a
GYPSUM POND
Figure 5-1: Wet-Process Phosphoric Acid Production
-------
The reaction that occurs in this step is described by the net
chemical equation:
Ca3(P0lt)2 + 3H2SOn + 6H20 -> SECaSO^ - 2H20] + 2H3P04 (5-1)
The tricalcium phosphate in the rock reacts with sulfuric acid and water
to yield phosphoric acid and gypsum. This reaction is carried out in
the digestion system over a period of approximately eight hours. The
reaction itself is completed to a large extent in a matter of minutes,
but more time is needed to allow for the proper formation of gypsum
crystals. Sulfuric acid and finely-ground phosphate rock are continu-
ously added to a slurry consisting of reactants, products, and enough
recycling weak phosphoric acid to maintain fluidity.
Reactions arising from undesirable components in the rock also
occur and are a potential considerable source of air pollution. These
include the formation of fluorosilicic acid and fluorosilicate which
decompose to precipitate in pipelines, filter cloths, and equipment.
Under process heat, moisture, and acid condtions, SiFi+ reacts with
water to deposit silica as a precipitate in the gas ducts.
The reaction between phosphate rock and sulfuric acid is highly
exothermic. Heat is removed from the process by recycling the slurry
through a cooler chilled by water vaporization. The slurry is agitated
and circulated and a stream of phosphoric acid-calcium sulfate slurry
is withdrawn for filtering.
The filtering and washing operations are carried out on a series
of filter surfaces. Belt or rotary type horizontal tilting pan filters
are superior to other types and are widely used in almost all new plants.
After dewatering of the filter cake, the phosphoric acid-rich liquor
entrapped within the solid CaSOit • 2H20 crystal matrix is replaced by
washing with more and more dilute solutions of phosphoric acid until, on
the final wash, recycled make-up water is used for washing. In many
plants, the make-up water is recycled from the barometric condenser.
The acid, which is about 30% P205, is concentrated to about 54%
P205 (industry uses term 54% acid for actual concentrations in 50-58%
range) in the third and final step by use of multiple stage vacuum
evaporators. These evaporators use steam to distill water overhead and
operate under vacuum to maintain low evaporation temperatures. The
acid is passed through a series of clarifiers to remove as many trace
fines as possible and then it is pumped to storage.
5.1.2 Emission Sources
Air pollutants from wet process phosphoric acid manufacture
originate in every step of the process. The digester/reactor is the
major source of emissions, accounting for nearly 90% of the fluorides
30
-------
entering the control system. Additional sources are the filter, the
filtrate feed and seal tanks, the flash cooler seal tank, the evapora-
tor system hotwell, and the acid storage tanks. Of course, fluoride
emissions will vary depending upon the type of rock treated and the
process used. Table 5-1 lists fluoride emission factors for various
uncontrolled sources as shown in Figure 5- 1.1*
One plant producing 85,200 Ib HaPOit (PaOs) per hour has con-
trolled the emissions from these sources to 1.8 IDS of fluoride per day
using a wet scrubber. For this particular plant, this represents over
99% control of fluoride emissions.
As stated previously, the source requiring the most attention
for control of fluoride emissions is the digester/reactor. Both the
reaction vessel itself and the vacuum flash cooler associated with it
contribute to the fluoride emissions, the primary source being the re-
actor tank, where digestion of the phosphate rock releases SiF^ and HF,
as well as some minor constituents.
Reaction heat is removed by cycling part of the reaction slurry
through a vacuum flash cooler. Vapors from the cooler are condensed in
a barometric condenser and sent to a hotwell while non-condensibles are
removed by steam ejection before being vented to the hotwell. Most of
the fluorides evolved in the cooler are absorbed by the cooling water in
the barometric condenser. Use of air cooling will cause fluoride emis-
sions to be higher.
The filter is the second most important source of fluoride emis-
sions, since most of the fluorides are emitted where the feed acid and
wash liquor are introduced to the filter.
The evaporator, which is used to concentrate the product acid
from 30 to 54% PaOs, is the last significant source of fluoride emissi-
ons. Most of the fluorides vaporized during this operation are re-
turned to solution in the system's barometric condensers. The remainder
exits with the non-condensibles and is sent through the hotwell which
becomes the potential emission source for this operation.
Minor sources of fluoride emissions include vents from sumps,
clarifiers, and acid tanks. Collectively, these sources can be signi-
ficant and may be ducted to a scrubber.
Gaseous fluorides may also evolve from the gypsum pond because
of the vapor pressure of the fluoride. The rate of evolution of fluor-
ide will vary with temperature, concentration, absolute pressure, and
exposed area of the liquid surface.
In addition to gaseous fluoride emissions, there is likely to be
some rock dust generated by the mechanical handling of the rock. This
is not likely, however, in a plant using wet rock grinding.
31
-------
TABLE 5-1
FLUORIDE EMISSION FACTORS
Source Emission Factor (Ib F/ton P20s)
Reactor .04 - 2.2
Filter .01 - .06
Miscellaneous up to .26
(filtrate feed &
seal tanks, hot-
wells, etc.)
32
-------
5.1.3 Control Equipment and Inspection Procedures
5.1.3.1 Control Equipment
The spray-crossflow packed bed scrubber has been accepted for
several years as the most satisfactory fluoride control device avail-
able for wet process phosphoric acid plants. Most wet-acid plants
built since 1967 have probably installed this scrubber as part of the
original design. The conversion of SiFi^ to Si02 in the ductwork causes
deposits which lead to plugging of air pollution control equipment.
Proper maintenance is required to keep equipment functioning effici-
ently.
Providing that the solids loading of the effluent stream has
been reduced sufficiently to prevent plugging, the fluoride removal
efficiency of the scrubber is limited only by the amount of packing used
and the nature and quantity of the scrubbing liquid. Most well-con-
trol led plants use a spray-packed bed type scrubber to control the com-
bined emissions from the reactor, the filter, and several miscellaneous
sources. Efficiencies as high as 99.9% have been reported for WPPA
plants.5
5.1.3.2 Inspection Procedures
Process Instrumentation
Process information should be collected when the NSPS tests are
performed. The inspector should obtain the process rate in terms of
the phosphorous-bearing material feed rate and the equivalent P2Qs feed
rate. The phosphorous-bearing material feed rate should be obtained
directly from monitoring instrumentation.
The inspector should check process instrumentation and note the
operating parameters being used at the time of inspection. These in-
clude the rate of addition of phosphate rock and h^SOi* to the reaction
system, reaction temperatures, the absolute pressures and temperatures
in the evaporator system, and the P20s content of the product being
produced during the test. Finally, all tank levels, liquor flow rates,
water temperatures, and power readings should be noted.
Control Device Instrumentation
The inspector should also collect control device data when the
NSPS tests are first performed. This may then be used as a reference
for future inspections.
Scrubbers
The inspector should make sure all control devices are operative
and that the fans are on. He should also note whether fluorine odors
33
-------
or visible emissions are detectable from the control device. He should
read the total pressure drop across the process scrubbing system from a
manometer or from gauges on the scrubber instrument panel, check the
water flow rate into the scrubber, and make note of any observed leaks
or broken seals. Finally, the pH of the scrubbing liquid should be
noted.
5.2 Superphosphoric Acid (SPA) Plants
5.2.1 Process Description
Superphosphoric acid, a mixture of polymeric forms of phosphoric
acid in addition to orthophosphoric acid, is a dehydration product of
54% P205 phosphoric acid and is used in the manufacture of high analysis
fertilizers and liquid fertilizers. Two commercial processes are used
to concentrate the 54% P205 acid to approximately 70% P205 acid: sub-
merged combustion and vacuum evaporation.
In the submerged combustion process, dehydration of the acid is
accomplished by bubbling hot gases through a pool of the 54% acid in a
submerged combustion evaporator. The hot gases, supplied by burning
natural gas in a separate chamber, are diluted with air to maintain a
gas temperature of 1700°F for introduction into the acid evaporator.
As shown in the process schematic in Figure 5-2, clarified 54% P20s acid
is continuously fed to the evaporator from storage, and acid containing
concentrated P20s is withdrawn from the evaporator to product holding
tanks. Circulation of water through stainless steel cooling tubes in
the product tanks cools the product. The process may be controlled by
regulation of the natural gas and air flows to the combustion chamber,
the dilution air to the combustion stream, or the amount of acid fed to
the evaporator. Water vapor, fluorides, and phosphoric acid mist are
driven from the evaporator solution and ducted to control devices.
Vacuum evaporation, the more important commercial method for con-
centration of phosphoric acid to superphosphoric acid, is shown schem-
atically in Figure 5-3. The procedure for concentrating the acid may
vary from plant to plant, the usual source of variation from one process
design to another occurring in the method of heating and concentrating
the acid. Evaporation may be accomplished by a falling film evaporator
or by forced circulation evaporation. Both types of processes require
clarified 54% feed acid, and both use high-vacuum concentrators with
high-pressure steam to concentrate acid to 70% P205. In addition, both
processes introduce feed acid into a large volume of recycling product
acid to maintain a highly concentrated process acid for lower corrosion
rates.
In the falling film process illustrated in Figure 5-4, the mix-
ture of concentrated product and feed acid is pumped to the top of the
evaporator and distributed to the inside wall of the evaporator tubes.
34
-------
FUEL
TEMPERING
AIR
AIR
a
•' ••• fc—->
COMBUSTION
CHAMBER
EVAPORATOR
54ft CLARIFIED
ACID
SEPARATOR
rn
CONTROLS
ACID MIST, S1F.,
HF H
r
i
WAFER
\
B' 7Z% ACID
' Ifv PRODUCT*
WATER STORAGE
oo
—
ACID COOLER
Figure 5-2: Submerged Combustion Process for Producing
Superphosphoric Acid
35
-------
WATER
STEAM
CONCENTRATOR
==1=
FEED ACID
PUMP
TA
TANK
BAROMETRIC
CONDENSER
FEED ACID
STORAGE. AGITATED
PRODUCT
COOLER
'PRODUCT PUMP
PRODUCT SHIPPING
STORAGE PUMP
Figure 5-3: Vacuum Concentration Process for
Producing Superphosphoric Acid
(Reprint with Permission of the
Sulfur Institute from Phosphate
Fertilizers, 1966, p. 21
36
-------
—Emissions
High-pressure . >
sleorn from
pockqge boiler FALLING-FILM
EVAPORATOR
Condensole,^ .
to pocHoqe i
steam boiler ^
:?/el-process
(phosphoric Concentrated
|ocid(54%P;Oi) ocid
FEED TANK EVAPORATOR
RECYCLE
TANK
To ejectors
BAROMETRIC
CONDENSER
HF
Water
coolant
Superphosphoric
ocid
(68-72%P,0,l
Figure 5-4: Falling Film Process
TO AIR WBCTOH
—Emissions
^F4. HF
Rum
cuiiria
Figure 5-5: Forced-Circulation Evaporation Process
-------
The acid film moves down along the inside wall of the tubes where
evaporation occurs. The concentrated acid separates from the water
vapor in a flash chamber at the bottom of the evaporator, product acid
flows to the evaporator recycle tank, and vapors go to the barometric
condenser. The process off-gases to the condenser consist of steam,
SiF^, and HF. After condensation, these materials flow to a hotwell for
cooling and subsequent draining to the gypsum pond. Concentrated acid
is continuously drawn from the evaporator to product cooling tanks be-
fore being pumped to storage.
In the forced-ciruclation evaporation process shown in Figure
5-5, 54% P205 feed acid is mixed with concentrated acid as it is pumped*
into the concentrator system. Evaporation and subsequent separation
from the water vapor take place as the acid leaves the heated tube
bundle and enters the vapor head. The vapor is vented to a barometric
condenser and the acid flows toward the bottom of the vapor head tank.
Part of the acid is removed to the cooling tank and the remainder is
recycled to the tube bundle.
5.2.2 Emission Sources
The source of atmospheric emissions and, to some degree, the
quality of emissions from superphosphoric acid plants vary with the type
of process used.
5.2.2.1 Emissions from Submerged Combustion Process
The major source of fluoride emissions from the submerged com-
bustion process is the evaporator. These emissions consist of SiF^ and
HF in concentrations depending on the fluoride content of the acid feed
and the final concentration of phosphoric acid produced.
Control of the evaporator off-gases is complicated by the pres-
ence of entrained and volatilized phosphoric acid which may be recov-
ered by an entrainment separator and recycled to the process. The acid
vapor and fume which leaves the separator forms an aerosol which is dif-
ficult to control in anything less than a high pressure drop device.
Some soluble fluoride will be contained in this mist, probably propor-
tional in concentration to the fluoride contained in the feed acid.
The acid sump and product holding tank are secondary sources of
fluoride emissions from the submerged combustion process. All process
emissions are shown in Figure 5-6. Uncontrolled emissions from this
process range from 13 to 22 pounds of fluoride per ton of P205 input.6
5.2.2.2 Emissions from Vacuum Evaporation Processes
There are three main sources of fluoride emissions from the
vacuum evaporation process: the barometric condenser hotwell, the
38
-------
TEMPERING AIR
54% P205 ACID
1
p
E-
i
P
tf
PX
\
t
a
I
\
i
f COMBUSTION
CHAMBER
r"
1
* !
NATURAL GAS
AIR
VENTURI
SCRUBBER
SUMP
—p — —— — — — — EMISSIONS
PRODUCT
HOLDING
TANK
TO STORAGE
GYPSUM
POND
Figure 5-6: Submerged Combustion Superphosphoric Acid Production
-------
evaporator recycle tank, and the product cooling tank. These sources
are shown in Figure 5-4 and Figure 5-5. Most of the fluorides evolved
during evaporation are absorbed by the cooling water in the barometric
condensers so that atmospheric emissions from this source are negli-
gible under normal operating conditions. Non-condensibles flow to the
hotwell with the condenser water, making the hotwell the major source
of process emissions.
Minor sources of fluoride emissions include the evaporator re-
cycle tank and the product cooling tank. Total fluoride emissions for
an uncontrolled plant have been estimated at 0.005 pounds per ton P205
input.7
5.2.3 Control Equipment and Inspection Procedures
5.2.3.1 Control Equipment
Of the several types of wet scrubbers available, venturi scrub-
bers have found the widest application in superphosphoric acid plants.
Water-induced venturi scrubbers are most frequently selected to control
superphosphoric acid plant emissions because the gas flow is very low
during normal operation, the gas flow may vary substantially with time,
and the water-induced scrubber does not require a fan.
Generally the exhaust gases from the process evaporator in the
vacuum evaporation technique are treated for the recovery of entrained
acid before being sent to fluoride controls. The phosphoric acid re-
covery system may consist of an initial cyclonic separator followed by
a baffled spray duct and a second separator. Weak phosphoric acid
(30% P20s) serves as the scrubbing medium in the duct. The scrubbing
requirements for superphosphoric acid plants are nominal, and other
types of scrubbers such as crossflow packed units, conventional venturi
scrubbers, mobile packed scrubbers, and spray towers, each with an ap-
propriate fan, are also acceptable for use in controlling fluoride emis-
sions from superphosphoric acid plants. However, these devices are
mechanically more complicated alternatives to the water-induced venturi
in this application.
5.2.3.2 Inspection Procedures
Process Instrumentation
When NSPS tests are performed, process information should be col-
lected. The inspector should obtain the process rate in terms of the
phosphorous-bearing material feed rate and the equivalent P205 feed rate.
The former should be obtainable directly from monitoring instrumentation,
40
-------
while the latter should be determined by AOAC llth Edition, Method 9.
The inspector should check process instrumentation and note the
operating parameters being used at the time of inspection. These in-
clude the rate of clarified phosphoric acid feed to the process, and
the rate of withdrawal of product acid to the product holding tanks.
The P205 content of the acid should also be verified. Controls for
submerged combustion processes also include the natural gas and air
flows to the combustion chamber and the dilution air to the combustion
stream. These parameters should also be recorded by the inspector.
If the vacuum evaporation process is being used, the absolute
pressure and temperature of the evaporator should be noted, as well as
the acid feed and withdrawal rates. The temperature of the barometric
condenser should also be recorded.
Finally, for both processes, all tank levels, liquor flow rates,
water temperatures, and power readings should be recorded.
Control Device Instrumentation
The inspector should also collect control device data when the
NSPS tests are first performed. This information may then be used for
reference for future inspections.
Scrubbers
The inspector should check to see that all control devices are
operative and that the fans are on, except if a water-actuated venturi
is being used. He should also note whether fluorine odors or visible
emissions are detectable from the control device. He should read the
total pressure drop across the process scrubbing system from a mano-
meter or from gauges on the scrubber instrument panel, check the water
flow rate into the scrubber, and make note of any observed leaks or
broken seals. The pH of the scrubbing medium should also be recorded.
5.3 Diammonium Phosphate (DAP) Plants
5.3.1 Process Description
Diammonium phosphate is manufactured from phosphoric acid and
ammonia. The process consists of three basic steps: reaction, granu-
lation, and finishing operations such as drying, cooling, and screening.
These are illustrated in the general process schematic shown in Figure
5-7.
In the first step, anhydrous ammonia is reacted with phosphoric
acid to form a mixture of hot liquid monoammonium phosphate (MAP)/di-
ammonium phosphate as described by the equations:
41
-------
PHOSPHORIC ACID
EMISSIONS
PHOSPHORIC
ACID
AMMONIA
ro
1
p
' 1
RER.
r 1
EACT
1
1
' 1
COR
J
REACTOR
GRANULATOR
PRODUCT TO
STORAGE
Figure 5-7: Diammonium Phosphate Production
-------
2NH3 + H3P04 -> (NH4)2 HsPOit - 81,500 BTU (20,529,850 calories)
(gas) (liquid) (liquid) (AHR @ 60°F) (5-2)
NH3 + H3P04 -> (NHi») H2P04
(gas) (liquid) (liquid)
The ammonia is generally obtained in bulk as a liquid under pressure.
vaporized in a steam-jacketed coil, and bubbled through the liquid in a
pre-neutralization reactor. Fifty-four percent phosphoric acid and 26-
30% phosphoric acid are also added to the reactor to produce the slurry
of MAP and DAP. The reaction is carried out using an ammonia:phospor-
ic acid molar ratio of about 1.3 to 1.45:1 which permits evaporation
to a water content of 18-22% without thickening of the slurry to a non-
flowing state.
The slurry is then pumped to the ammoniator-granulator where it
is distributed over a bed of recycled fines. Additional ammonia and
recycled product are added to the rolling bed of solids to bring the
NH3:Acid molar ratio up to 1.9 to 2.0 to favor the production of DAP.
Solidification of the product has occurred once this ratio has been
reached.
The solid effluent from the granulator drum is then sent to a
rotary drier where excess moisture is driven off by contact with the
flue gases. Flue gas from the drier is vented through a dry cyclone
collector which collects the dust generated in the granulator-drier
and returns it to a recycle belt. The granular solids discharged from
the drier are then elevated to a screening arrangement for particle
segregation.
A primary screen removes material from the flow stream and
drops it onto the fines return conveyor. Oversized material is passed
to a mill where it is ground to relatively small size and returned to
the belt. Material passing the primary screen falls onto a secondary
screen which rejects any fines that may have been carried over and
passes the material of proper size through a cooler into a product
storage drum.
All other solids are recycled back to the granulator drum where
they are trapped until the particles have grown large enough for them
to be classified as finished product.
Side reactions resulting from the production of ammonium phos-
phates produce ammonium fluoride, ammonium sulfate, and ammonium flu-
orosilicate. In addition, some of the fluorine is liberated as SiF^.
Is should be noted that the product weight, rather than its P205 con-
tent, is the usual basis for rating a DAP plant, although the product
is assayed routinely for ?2Q5-
43
-------
There are two commonly used variations of the DAP manufacturing
process: the Dorr-Oliver Process and the TVA (Tennessee Valley Authori-
ty) Process. In the Dorr-Oliver Process, the reaction is completed in
the fluid state by using additional reactors. The slurry overflows to a
turn-shaft paddlemixer containing recycling dry product. The moist
granules formed in the mixer are then dried, cooled, screened, and
stored. Figure 5-8 is a typical Dorr-Oliver Process flowsheet.
In the TVA Process, the slurry and recycling material are fed
into a revolving drum where final ammoniation and granulation take place
simultaneously. The moist granules are then dried, cooled, screened,
and stored as with other processes. A flowsheet of this process is
shown in Figure 5-9.
5.3.2 Emission Sources
The major sources of fluoride emissions from diammonium phos-
phate plants include the reactor, granulator, dryer, cooler, screens,
and mills. These sources are shown in Figure 5-7.
The preneutralization reaction that occurs in the reactor gene-
rates a large quantity of heat which raises the temperature of the reac-
tants and results in the emission of water vapor, ammonia, and SiF^
with the discharge gas stream. In the granulator, the ventilating air
flow purges a substantial amount of ammonia along with some water vapor
and DAP dust. There is very little evolution of fluorine-containing
gases from the granulator because of the high concentration of ammonia
in the vapor- phase.
Reactor-granulator gases are treated for ammonia recovery in a
scrubber using phosphoric acid as a scrubbing medium. The acid reacts
with the ammonia and the resulting product is recycled back to the pro-
cess. Fluorides, which can be stripped from the acid, are usually con-
trolled by a secondary scrubber.
Drier emissions consist of ammonia, fluorides, and particulate.
Gases are sent through a cyclone for product recovery before being trea-
ted for ammonia or fluoride removal.
Emissions from the screens, mills, and cooler consist primarily
of particulate and gaseous fluorides. Very little volatile material is
given off in the cooler because the temperature is reduced and the vapor
pressure of each of the gaseous species is decreased. All gases are
treated for product recovery before entering fluoride control equipment.
Approximately 0.3 pounds of fluorides per ton P205 are emitted by the
reactor and granulator, and about 0.3 pounds of fluoride per ton P205
are evolved from the dryer, cooler, and screens.8 One plant producing
17 tons ammonium phosphate per hour has been successful in reducing its
total fluoride emissions from the DAP process to 16.4 pounds/day using a
44
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Potash
storage
Phosphoric acid
storage (or supply)
Sulfuric acid
storage
Anhydrous
ammonia storage
Screen
To storage
or bogging
Mill
Flowmeter
Reactors
and air
Dryer
Figure 5-8: Dorr-Oliver Process (Reprint with Permission of the
Sulfur Institute from Phosphatic Fertilizers. 1966,
P. 16)
45
-------
PHOSPHORIC ACID (WET PROCESS)
WATER VAPOR
CRUSHER
AMMONIA
WATER
VAPOR
EXHAUST
DRAIN FOR
CLEANOUT
GRANULAR
DIAMMONIUM
PHOSPHATE
PRODUCT
Figure 5-9: T.V.A. Process (Reprint with Permission of the
Sulfur Institute from Phosphatic Fertilizers,
1966, p. 17)
46
-------
cyclonic spray scrubber. There is also a substantial fugitive dust
problem due to the mechanical handling of granular solids. Transfer
and screening of the solid product and recycle solids cause some genera-
tion and dispersion of product dust which contains a small amount of
fluorine as an impurity.
5.3.3. Control Equipment and Inspection Procedures
5.3.3.1 Control Equipment
The three major sources of atmospheric emissions in DAP plants
are treated exclusively by wet scrubbers, largely because of the neces-
sity for removal of both gaseous and particulate emissions and the pres-
ence of relatively high humidity in the gas streams. The combination of
requirements for particulate collection and gas absorption for NH3
recovery and fluorine emission control permits the application of a wide
variety of scrubber types for DAP plant service.
Venturi scrubbers are the key control devices used in DAP plants,
whereas impingement scrubbers have had only limited success in these
plants because of small particle size. Venturi and cyclonic scrubbers
are generally used to recover ammonia from the reactor/granulator and
the dryers. Cyclones and wet scrubbers are also used to remove particu-
late from the cooler stream. Although additional scrubbers for fluoride
removal are common, the are not typically found.
5.3.3.2 Inspection Procedures
Process Instrumentation
Process information should be collected when NSPS tests are per-
formed. The inspector should obtain the process rate in terms of the
phosphorous-bearing material feed rate and the equivalent P205 feed rate.
The lormer should be obtainable directly from monitoring instrumentation,
while the latter should be determined by Method 9 in the llth Edition of
AOAC.
The inspector should check process instrumentation and note the
operating parameters being used at the time of inspection. These in-
clude the ammonia and phosphoric acid feed rates, the reaction and dryer
temperatures, and the product rate to storage.
Finally, all tank levels, flow rates, and power readings should
be recorded.
Control Device Instrumentation
The inspector should also collect control device data when the
47
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NSPS tests are first performed. This information may then be used for
reference for future inspections.
The inspector should check to see that all control devices are
operative and that the fans are on, except if a water-actuated yenturi
is being used. He should also note whether fluorine odors or visible
emissions are detectable from the control device. He should read the
total pressure drop across the process scrubbing system from a manome-
ter or from gauges on the scrubber instrument panel, check the water
flow rate into the scrubber, and make note of any observed leaks or
broken seals. The pH of the scrubbing medium should also be recorded.
5.4 Run-of-Pile Triple Superphosphate (ROP-TSP) Plants
5.4.1 Process Description
The run-of-pile triple superphosphate process is essentially
very simple and requires a minimum amount of process equipment. Meas-
ured quantities of ground rock and 52-54% P205 phosphoric acid are
mixed at ambient temperature to form a viscous slurry. Most plants
in the United States mix the slurry in a TVA cone mixer, which has no
moving parts. Mixing is accomplished by the swirling action of rock
and acid streams introduced simultaneously into the cone. The reactions
that take place during mixing are described by the equations:
Cai0(P01+)6F2 + 42H3PCV + 3H20 -»• 30CaHif(PO(f)2 • H20 + 6HF (5-3)
6HF + Si02 -»• H2SiF6 + 2H20
H2SiF6 -»- 2HF + SiF^
After mixing, the slurry is dropped onto a slowly-moving belt,
or den, where it solidifies, as shown in the process schematic in Figure
5-10. The porous mass is reduced to small chunks by a cutter at the end
of the belt and then conveyed to a storage pile for curing.. The reac-
tion continues in the storage pile and is considered complete after
about 30 days. The product is then considered cured and ready for ship-
ment.
5.4.2 Emission Sources
Emissions of fluorides and particulates occur during the produc-
tion, conveying, and storage of run-of-pile triple superphosphate. The
main sources of fluoride emissions from ROP plants include the mixing
cone, curing belt (den), transfer conveyors, and storage piles, also
shown in Figure 5-10.
48
-------
10
PHOSPHORIC
PHOSPHATE | ACID
T^CONTROLS
1 SiF4, PARTICULATE
—Emissions
Figure 5-10: Run-of-Pile Triple Superphosphate Production and Storage
-------
Fluoride emissions are primarily silicon tetrafluoride, 35-55%
of the total fluoride content of the acid and rock being volatilized as
SiF4. Distribution of emissions among these sources will vary depend-
ing on the reactivity of the rock and the specific operating conditions
employed. Obviously, emissions from the storage pile are greater when
the pile is being rearranged than when it has lain undisturbed for an
extended period of time.9
Fluoride emissions from ROP-TSP production and storage have
been estimated at 31-48 pounds per ton of P^Os-10 Typical controlled
emissions from plants which control production and storage areas can
range from 0.2 to 3.1 pounds of fluoride per ton of PzOs-11'12 One
existing ROP-TSP plant producing 59,000 Ibs/hr has controlled its
fluoride emissions to 1.49 Ibs/hr using 99+% efficient venturi and
cyclonic scrubbers.
5.4.3 Control Equipment and Inspection Procedures
5.4.3.1 Control Equipment
According to NSPS, run-of-pile plants are subject to the stan-
dards of performance for triple superphosphate plants, which include
any combination of mixers, curing belts, reactors, granulators, dryers,
cookers, screens, mills, and facilities which store run-of-pile triple
superphosphate. NSPS regulates only fluoride emissions from these
facilities. The best demonstrated control of fluoride consists of
scrubbing emissions with water.
Venturi scrubbers and cyclonic spray tower scrubbers with a
packed bed section are used as primary and secondary controls respec-
tively. These have been successfully applied to the mixing cone, den,
transfer conveyor, and storage pile in ROP-TSP plants.
5.4.3.2 Inspection Procedures
Process Instrumentation
Process information should be collected when NSPS tests are
performed. The inspector should obtain the process rate in terms of
the phosphorous-bearing material feed rate and the equivalent P205 feed
rate. The former should be obtainable directly from monitoring instru-
mentation, while the latter should be determined by Method 9 in the
llth Edition of AOAC.
The inspector should check process instrumentation and note the
operating parameters being used at the time of inspection. These in-
clude the ground phosphate rock feed rate, the phosphoric acid feed
50
-------
rate, the rate of product feed to storage, the amount of ROP in stor-
age, and the age of ROP in storage.
Control Device Instrumentation
The inspector should also collect control device data when the
NSPS tests are first performed. This information may then be used for
reference for future inspections.
The inspector should check to see that all control.devices are
operative and that the fans are on, except if a water-actuated yenturi
is being used. He should also note whether fluorine odors or visible
emissions are detectable from the control device. He should read the
total pressure drop across the process scrubbing system from a manome-
ter or from gauges on the scrubber instrument panel, check the water
flow rate into the scrubber, and make note of any observed leaks or
broken seals. The pH of the scrubbing medium should also be recorded.
5.5 Granular Triple Superphosphate (GTSP) Plants
5.5.1 Process Description
Triple superphosphate (also called treble, double, or concen-
trated superphosphate) is an impure monocalcium phosphate made by re-
acting phosphoric acid with phosphate rock. Although it may be made
with any phosphoric acid, the major portion of this material is now
made with wet process phosphoric acid. The P205 equivalent of the pro-
duct ranges from 44-52 percent, depending on the purity of the acid and
rock and the efficiency of the manufacturing process.
Three processes are currently in use for the direct production
of granular triple superphosphate. These are the TVA Process, the Dorr-
Oliver Process, and the process which uses cured ROP-TSP-
A process schematic for the TVA, one-step granular process, is
shown in Figure 5-11. In this process, ground phosphate rock and re-
cycled process fines are fed into the acidulation drum along with con-
centrated phosphoric acid and steam, which helps to accelerate the
reaction and ensure an even distribution of moisture in the mix. The
mixture is discharged into the granulator where solidification occurs,
passes through a rotary cooler, and is screened. Over-sized material
is crushed and returned to the process with undersized material. The
process reactions are described by the equations:
Ca10(POif)6F2 + HHaPOit + 10H20 -> lOCaH^PO.,);, • H20 + 2HF (5-4)
6HF + Si02 -»• H2SiF6+ 2H20
H2SiF6 •* 2HF
51
-------
PARTICULATE
PHOSPHATE _____
HOCK —K 1 ->
STEAM
;NC HLATCR
AC'O ,,.
K>
TMETER
L_
PUMP
i nrfrn rn nrjr-
RECYCLED FINES
STEAM
i „ "; ^ 'I \ |—
ACICHH ATION I
GIlANULATOR
SCREENS
S1F4, PARTICULATE
_ >S1I4, PARTICULATE
—Emissions
Figure 5-11: T.V.A. One-Step Process for
Granular Triple Superphosphate
52
-------
In the Dorr-Oliver slurry granulation process shown in Figure
5-12, phosphate rock is mixed with 40% P205 phosphoric acid in a
series of mixing tanks to form a slurry. A thin slurry is continuously
removed and mixed with a large quantity of dried, recycled fines in a
pugmill mixer, where it coats out on the granule surfaces and builds
up the granule size. The granules are dried and screened and mostly
recycled back into the process.
In a somewhat similar process, cured ROP-TSP is used to pro-
duce 6TSP. The ROP-TSP is treated with water and steam in a rotary
drum and then dried and screened.
After manufacture, the product is sent to a storage building
by a conveyor belt which discharges the material into bins or piles
for curing. The GTSP is held approximately 30 days to stabilize the
composition, after which it is considered cured and ready for ship-
ping. Front-end loaders move the GTSP to elevators or hoppers where
it is conveyed to screens for size separation. Over-sized material is
rejected, pulverized, and returned to the screen, while undersized ma-
terial is returned to the GTSP production plant. Material within
specification is shipped as product.
5.5.2 Emission Sources
Sources of atmospheric emissions from granular triple super-
phosphate plants include all major process components. For plants
using the TVA, one-step process, these are the acidulation drum, the
granulator, the cooler, and the screening and crushing operations.
These are indicated in Figure 5-11. The mixing tanks, the pugmill
mixer, the dryer, and the screens are the major sources for the Dorr-
Oliver process, as shown in Figure 5-12. Fluorides are emitted from
the granulator, mixer, dryer, screens, and mills in both gaseous and
particulate form.
The acidulation drum and granulator (TVA Process) and the mix-
ing tanks and pugmill mixer (Dorr-Oliver Process) account for about
38% of the fluoride emissions; the dryer and screens account for 50%,
and the storage facilities account for the remainder. It has been
estimated that an uncontrolled facility would emit 21 pounds of
fluorides per ton of P205 input.13
One plant, which produces 84,100 Ibs triple superphosphate per
hour, has been able to control its fluoride emissions to 17.1 Ibs per
day. Control equipment at this plant consists of a cyclonic spray
scrubber with efficiencies better than 90%.
53
-------
PHOSPHATE ROCK
ROCK
BIN
_O
PHOSPHORIC ACID
r
^~i '
_t J. .• .'
S1F.
TO AIR POLLUTION
C0.1TROL SYSTEM
ft .
SiF4, PAR!
"
r!CULATE
f
" "~ T
S1F/|.
PARTICIPATE
.d
ACIDULATORS
*- --i
OVERSIZE
SCRF.Ei
GRANULATOR
(ROTARY TYPE
ALSO USED)
OVERSIZE
MILL
PRODUCT TO COOLING
A;ID STORAGE
——"" i
^
—Emissions
Figure 5-12: Dorr-Oliver Slurry Granulation Process for Triple Superphosphate
-------
5.5.3 Control Equipment and Inspection Procedures
5.5.3.1 Control Equipment
Fluorides in both gaseous and particulate form are the only sig-
nificant air pollutants emitted by granular triple superphosphate plants.
Process emissions from these plants are generally treated by wet scrub-
bers. The dust generated by solids handling and the fluorine evolved by
curing of the TSP product can be treated separately by use of a fabric
collector and a cyclonic or packed scrubber or simultaneously by a
scrubber which serves both functions.
5.5.3.2 Inspection Procedures
Process Instrumentation
Process information should be collected when NSPS tests are per-
formed. The inspector should obtain the process rate in terms of the
phosphorous-bearing material feed rate and the equivalent PaOs feed
rate. The former should be obtainable directly from the required pro-
cess monitoring instrumentation, such as that shown in Figure 5-13,
while the latter should be determined by the Spectrophotometric Molyb-
dovanadophosphate Method, Method 9 in the llth Edition of AOAC.
The inspector should check process instrumentation and note the
operating parameters being used at the time of inspection. More spe-
cifically, he should be concerned with the phosphate rock and phosphoric
acid feed rate, and the rate of product feed to storage.
Control Device Instrumentation
The inspector should also collect control device data when the
NSPS tests are first performed. This information may then be used for
reference for future inspections.
The inspector should check to see that all control devices are
operative and that the fans are on, except if a water-actuated venturi
is being used. He should also note whether fluorine odors or visible
emissions are detectable from the control device. He should read the
total pressure drop across the process scrubbing system from a manometer
or from gauges on the scrubber instrument panel, check the water flow
rate into the scrubber, and make note of any observed leaks or broken
seals. The pH of the scrubbing medium should also be recorded.
55
-------
Figure 5-13: Control Panel for GTSP Plant
56
-------
SECTION 6
FACILITY RECORDKEEPING AND REPORTING REQUIREMENTS
6.1 Record keep ing
NSPS for all phosphate fertilizer plants require that the equiva-
lent P20S feed be recorded daily. This should be determined by Method 9
in the llth Edition of AOAC and entered in a logbook for compilation.
All analytical data and calibrations should be kept on record. Triple
superphosphate storage facilities must maintain an accurate account of
triple superphosphate in storage to permit the determination of the
amount of equivalent PZ^S stored. Furthermore, they must maintain a
daily record of total equivalent PaOs stored.
Control device monitoring instrumentation must continuously
measure and permanently record the total pressure drop across the scrub-
bing system. These records should be dated and all records and cali-
bration information kept in the event that they are needed to verify
emission levels.
Finally, NSPS require that the mass flow of the phosphorous-
bearing feed material to the process be monitored and calibrated. This
material should be dated and kept on record for possible future use to
verify production and emissions.
6.2 Reporting Procedures
Although the NSPS do not require periodic submittal of data or
data summaries, they do require that any plant owner or operator submit
the results of a performance test performed within 60 days after achiev-
ing the maximum production rate at which the facility will operate, but
not later than 180 days after initial startup. Furthermore, a record of
the occurrence and duration of any startup, shutdown, or malfunction in
the operation of any affected facility shall be kept for a period of two
years.
57
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SECTION 7
INSPECTIONS
Plant inspections enable the inspector to determine the status of
the plant's emissions and air pollution control equipment. The initial
inspection should take place during the performance test while follow-
up inspections may take place on a regular basis thereafter. Inspec-
tions during the performance test will ensure that the tests are conduc-
ted under the proper operating conditions and that the correct test
procedures are used. Comparison of operating parameters observed during
subsequent inspections with those recorded during the performance test
should indicate whether emissions are within limits specified by NSPS.
7.1 Inspection Preparation
In preparation for all inspections, the inspector should famili-
arize himself with the plant processes, the inspection points and the
control equipment. He should review plant files for process and con-
trol equipment details and enforcement history. The schematics of air
pollution control systems should be prepared at this point in order to
simplify field inspection. He should also obtain inspection checklists
and the necessary safety and inspection equipment, including the follow-
ing:
Safety Equipment Inspection Equipment
Hard hat Tape measure
Safety glasses Flashlight
Steel-toed shoes Thermometer
Respirator with cartridge Manometer
(for acids, bases, and NH3) Velometer
Gloves RPM indicator
Coveralls
As part of the inspection preparation, the inspector and plant
personnel should discuss the process and control data that are required
to complete the inspection checklists. If the plant considers any of
this data proprietary information, the inspector should assure the
plant that the information will be treated as confidential and that it
will be stored in a separate confidential file.
Plants may request that information given to an EPA inspector
58
-------
be treated as confidential in accordance with Part 2, Sub-part B of
Chapter 1 of 40 CFR. This request for confidentiality should be made
at the time that the information is exchanged.
7.2 Performance Test
During the performance test, the inspector must observe both the
process and control equipment operation and the emission tests them-
selves. He must be sure that the tests are conducted under the proper
operating conditions and that the proper test procedures are being used.
The performance test will determine whether the emission standards will
be met when the plant is operating under normally-encountered conditions
that produce maximum emissions. Furthermore, values for key process and
control equipment operating parameters can be obtained to form a basis
of comparison for future plant inspections.
7.2.1 Pre-Test Procedures
Prior to the actual performance test, the inspector should ar-
range a meeting with plant personnel to review details of the New Source
Performance Standards and the applicable testing procedures. The in-
spector should be prepared to provide copies of the Performance Standards
at this meeting if they are needed. He should also inform all parties
of the latest revisions to the Standards. At this time, the unit(s) to
be tested should be properly identified and located on a plant or pro-
cess plan.
The inspector, testing crew, plant personnel, and all parties
concerned with the performance test should hold a meeting prior to the
beginning of the tests. The inspector should make clear that he is
there to monitor the tests and that he will do so as unobtrusively as
possible. He should inform all members of the test party that, if he
sees techniques or equipment used not conforming with the test require-
ments specified in the Standards of Performance for New Sources, he will
make note of his observations and advise the person in charge of con-
ducting the test. He should make it clear that he will not interfere
with or pre-empt any contract agreement between the owner and the test
company, but will simply make his observations known and note them.
A number of process operating parameters must be established dur-
ing the performance tests. These includei tne~"mass flow of phosphorous-
bearing feed material to the process, the equivalent P20s feed, and the
control equipment operating parameters. The inspector should inform
the testing crew as to which process parameters should be recorded dur-
ing the tests.
59
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7.2.2 Performance Test Monitoring
Important process and emission control device operating condi-
tions should be recorded during the compliance test to provide a base-
line for comparison with operating conditions observed during later
inspections. Such information may also indicate reasons for excessive
emissions if the source fails to meet NSPS.
The inspector should observe process operation during the emis-
sion tests to ensure the validity of the data for use in assessing plant
performance and compliance. He should also complete the performance
test checklist shown in Table 7-1. Any additional parameters or obser-
vations that are related to emissions should also be recorded.
As required by 60.8 of 40 CFR, the plant operator shall furnish
EPA a written report of the emission tests. These reports should be
carefully checked and the data compared with values on the inspection
checklist.
7.3 Post-Performance Test Inspections
Regular visits to the plant enable the inspector to determine the
condition of the plant's emission controls and their compliance status.
Comparison of operating parameters observed during periodic inspections
with those recorded in the performance test should indicate whether or
not the source is in compliance.
Although the frequency of inspection is often governed by regula-
tory agency policy, a quarterly inspection is recommended unless com-
plaints necessitate more frequent visits. The major emphasis of the
inspection is placed on checking facility records and observing process
and control equipment operation. The inspector should compare records
of operating hours and process rates to those recorded in the perform-
ance test. Control device and process instrumentation give an indica-
tion of fluoride emissions.
7.3.1 Pre-Inspection Procedures
Because the major emphasis of the inspection is placed upon check-
ing facility records and observing process and control equipment opera-
tion, the inspector should familiarize himself with plant processes and
the New Source Performance Standards prior to his visit. He should read
the performance test report and become familiar with the operating
parameters under which the test was conducted. Furthermore, he should
obtain from the plant or appropriate regulatory agency a schematic of
the emission control equipment and should make himself thoroughly fami-
liar with the control system. This is an important step because fluoride
emission control equipment at phosphate fertilizer plants tends to be a
a complex system of control devices.
60
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TABLE 7-1
NSPS INSPECTION CHECKLIST FOR PHOSPHATE FERTILIZER PLANTS
DURING PERFORMANCE TEST
Facility Name
Facility Location
Name of Plant Contact
Source Code Number
Unit Identification (to be tested)
Design Feed* Rate tons/day**
Actual Feed* Rate tons/day**
Initial Start-up Date
Continuous OpeVation Date
Test Date
Type of Plant (See Table 7-2, Page 66).
A. PRE-TEST DATA (OBTAIN FROM TEST FIELD LEADER)
Test Company
Field Leader
Duct Dimensions in. x in; Area ft2
Nearest Upstream Obstruction ft
Nearest Downstream Obstruction ft
Number of Sampling Ports
Number of Sampling Points
Number of Sampling Points Required
from Figure 1-1 in 40 CFR 60
* Feed of phosphorous-bearing materials
** Record on a separate sheet if company confidential information and
retain in confidential file
61
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TABLE 7-1 (continued)
|Batch
hr/day
B. PROCESS
Loading Method
Operating Schedule _
Actual Feed Rate tons/hr
Equivalent P205 Feed Rate tons/hr
Air Pollution Control System Schematic
|[Continuous
days/wk wk/yr
1. Processes controlled by system (drying, conveying, mixing, etc.)
2. Indicate test points on schematic.
C. PROCESS INSTRUMENTATION
Mass-flow Monitoring Device:
Description:
Reading:**
Is calibration within +B% over operation range?
Scrubbing System:
Water Usage Rate:
Pressure Drop:
gal/min
inches
Gas Volumetric Flow Rate:
Stack Temperature: °F
SCFM
Liquid-to-Gas Ratio:
gallons/SCFM
** Record on a separate sheet if company confidential information and
retain in confidential file
62
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TABLE 7-1 (continued)
D. FLUORIDE PERFORMANCE TEST
Test Number
Start Time
Finish Time
Preliminary Traverse Run (Method 1)
Chosen Nozzle Diamater in.
Train Leak Check
Stack Pressure
Stack Temperature
Moisture Determination (Method 4)
Moisture Content ^_,^ %
ml Collected/Gas Volume ml
Dry Gas Meter Reading Before Test
Dry Gas Meter Reading After Test
Volume Sampled
Test Duration minutes
Average of Meter Orifice Pressure Drop
Average Duct Temperature °F
Velocity Head at Sampling Point
Orifice AH
Meter Ratio
Repetition Start Time
Repetition Finish Time
Yes
1 D
D
D
D
D
ft'
ft3 8 '
ft3 9
No
D
D
n
D
D
1 > (time)
(time)
ft3
inches
inches H20
63
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TABLE 7-1 (continued)
E. CLEANUP PROCEDURE
Filter Condition
Probe Status
Glass Connectors
Cleanup Sample Spillage
Sample Bottle Identification
Blank Taken
Dory
Unbroken
Unbroken
^one Qsiight
DYes
Dves
Dwet
PI Broken
| | Broken
DMajor
Inspector
Signature
Date
F. LAB ANALYSIS
64
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7.3.2 Inspection Procedures
It is suggested that the inspector first tour the plant, observe
the processes, and then monitor the instruments during actual operation.
Questionable areas may be further investigated by checking records and
consulting plant operators. The following areas should be checked dur-
ing the inspection:
• Control Equipment
Read pertinent gauges on scrubber and compare with
values obtained during performance test. Check
that all gauges are operating properly. Note pres-
ence or absence of leaks, visible or odorous emissi-
ons. Inspect equipment for corrosion and check
maintenance schedule.
• Process Equipment
Read the device which monitors the mass flow of phos-
phorous-bearing feed materials to the process. Read
operating parameters such as reaction temperatures
and water flow rates, if possible. Read tank levels
and note power readings.
• Review record of hours of operation, daily loading,
and production rate. Review records on control de-
vice.
The Inspection Checklist form shown in Table 7-2 is derived from
the procedures described above. This Checklist should be completed for
each type of plant (ROP, WPPA, etc.) within the phosphate fertilizer
complex under inspection. If more than one scrubbing system is used at
a single plant, Section A should be completed for each system.
7.4 Post-Inspection Procedures
At the completion of the inspection, the inspector should sign and
date all inspection forms, and check to be sure that all necessary infor-
mation has been recorded. He should briefly convey his findings to the
plant official at the site, but he should not discuss specific violations
at this time.
While it is recognized that inspectors will be subject to various
regional inspection follow-up procedures, it is recommended that the
inspector review all the inspection data, make his recommendations for
action, and present the completed report to his supervisor within 48
65
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TABLE 7-2
NSPS INSPECTION CHECKLIST FOR PHOSPHATE FERTILIZER PLANTS
AFTER PERFORMANCE TEST
Facility Name
Facility Location
Name of Plant Contact
Source Code Number
Type of Plant (Check One)
Qwet Process Phosphoric Acid
QSuperphosphoric Acid
QDiammonium Phosphate
Triple Superphosphate (incl. storage &
handling)
Granular Triple Superphosphate (incl. storage & handling)
Design Process Rate
Actual Process Rate
metric ton**
nour
metric ton**
hour
Equivalent
Feed Rate
Equivalent
Feed Rate
metric ton**
hour
metric ton**
hour
Inspection Date
lime
AM
PM
** Record on a separate sheet if company confidential information and
retain in confidential file
66
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TABLE 7-2 (continued)
A. AIR POLLUTION CONTROL EQUIPMENT
1. Scrubbing System Diagram (obtain from Plant or Regulatory
Agency)
Prepare schematic of control equipment similar to Figure 4-1.
Number the equipment and fill in control device parameters in the
next paragraph.
i. Processes controlled by system (drying, conveying, etc.):
b. System control efficiency:
67
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TABLE 7-2 (continued)
2. Control Device Parameters
1.
2.
3.
4.
Scrubbing System
Component
(List each device
shown in schematic
above: Cyclones,
Venturis, etc.)
Gas Flow
Through
Device
Liquid Flow
Through
Device
Scrubbing
Solution
Solution
PH
Pressure
Drop
Across
• Device
L/G Ratio
or
Surface/Gas
Ratio
(Baghouses)
Control
Efficiency
of
Device
00
-------
TABLE 7-2 (continued)
3. Observations Yes* Ho_
a. Visible leaks or craks in system O f~l
b. System plugged
c. Visible corrosion
d. Fluoride odors noticeable
e. Visible emissions
f. Positive pressure in storage building
g. Fans on d CD
h. Regular maintenance schedule (describe):
i. Additional comments
* If "Yes" is checked for Parts a-g, explain below:
69
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TABLE 7-2 (continued)
Time AM
PM
B. PROCESS CONTROL EQUIPMENT
Fill in the requested information for the type(s) of plant(s) under
inspection:
1. Wet Process Phosphoric Acid
a. Feed measuring device
b. H2SOl| addition rate**
c. Reaction temperature
d. Evaporator temperature
e. Evaporator pressure
2a. Superphosphoric Acid - Submerged Combustion Process
a. Acid feed measuring device
b. Product acid withdrawal device
c. Natural gas flow to combustion chamber
d. Air flow to combustion chamber
e. Dilution air to combustion stream
f. Coolant flow rate
2b. Superphosphoric Acid - Vacuum Evaporation Process
a. Acid feed measuring device
b. Product acid withdrawal device
c. Evaporator pressure
d. Evaporator temperature
e. Barometric condenser temperature
f. Coolant flow rate
** Record on a separate sheet if company confidential information and
retain in confidential file
70
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TABLE 7-2 (continued)
3. D1ammonium Phosphate
a. Ammonia feed rate**
b. Phosphoric acid feed rate**
c. Reaction temperature**
d. Dryer temperature
e. Product rate to storage**
4. Run-of-Pile Triple Superphosphate
a. Ground phosphate rock feed rate**
b. Phosphoric acid feed rate**
c. Phosphoric acid concentration
d. Amount of product to storage**
5a. Granular Triple Superphosphate - TVA One-Step Process
a. Phosphate rock feed rate**
b. Phosphoric acid feed rate**
c. Product rate to storage**
5b. Granular Triple Superphosphate - Dorr-Oliver Process
a. Phosphate rock feed rate**
b. Phosphoric acid feed rate**
c. Slurry removal rate**
d. Product removal to storage**
** Record on a separate sheet if company confidential information and
retain in confidential file
71
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TABLE 7-2 (continued)
C. RECORDS
1. AH Plants
a. Mass flow of phosphorous-bearing feed
Calibration records
Calibration within +5% over operation range
Maintenance and monitoring records
b. Equivalent P205 feed
Analytical data
c. Pressure drop across scrubber
Calibration records
Calibration within +5% over operation range
Maintenance records
d. Plant operation
Satisfactory since performance tests
Satisfactory since last inspection
2. GTSP Plants Only
a. Amount of GTSP in storage
b. Equivalent P205 stored
Time
Yes
D
D
D
D
D
D
D
D
D
D
D
_AM
PM
No
D
D
D
D
D
D
D
D
D
Inspector
Signature
Date
72
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hours of his inspection visit. Any decisions for subsequent action
should then be made by both the inspector and the supervisor.
If the facility is obviously in violation of standards, then a
citation should be issued. The inspector should precisely state the
reasons for issuing the citation. The citation can be given only if
the plant does not maintain proper records, does not monitor the rate
of phosphorous-bearing feed to the process, or does not monitor the
pressure drop across the scrubber according to NSPS specifications.
If the affected facility is in compliance with standards and
the plant is found to be operating and maintaining its facilities in
a manner consistent with good air pollution control practice, then no
further action need be taken.
If the facility is not being operated or maintained precisely
in accordance with the New Source Performance Standards, but violations
are not clearly evident, the inspector should conclude the inspection
report with recommendations to improve specific operating or mainten-
ance procedures. These recommendations should aim at consistence with
performance test conditions and at good air pollution control practice.
If these recommendations are not followed, he should request another
performance test be carried out under present plant operating condi-
tions.
Regardless of the findings, the designated plant official should
be notified in writing of the inspection results and any required action
on the company's part should be precisely stated.
73
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SECTION '8
GYPSUM PONDS
NSPS for the phosphate fertilizer industry focuses on atmospheric
total fluoride emissions from five fertilizer manufacturing processes and
storage facilities, except for fluorides from gypsum ponds. The plants
that manufacture wet process phosphoric acid, diammonium phosphate, and
triple superphosphate pass a large amount of fluorides to gypsym ponds.
It has been estimated that up to 85% of the fluorine originally present
in the phosphate rock may find its way to the gypsum pond. The water of
the gypsum pond, which is used as a scrubbing liquid in most processes,
is normally acidic with a pH around 1.5. Fluoride concentrations in the
gypsum ponds around the country have been found to be in the range of
2000 - 12,500 ppm. The fluoride concentration of a given pond does not
continue rising but tends to stabilize. This may be due to precipitation
of complex calcium silicofluorides in the pond water. There would be an
equilibrium involving these complexes, hydrogen ion, and soluble or vola-
tile dissolved fluorides.
Emissions of fluorides from gypsum ponds have been estimated, meas-
ured, and calculated. The emission rate depends on pond temperature,
fluorine content of pond water, and wind speed. The emissions vary from
0.2 to 10 Ibs F/acre/day. Based on studies of wet process phosphoric
acid production, the plants have gypsum ponds of surface areas in the
range of 0.1 - 0.4 acres per daily ton of P20s. Consequently, a large
plant may have a gypsum pond with surface area of 200 acres or more.
This means that a gypsum pond is a major source of fluoride emissions
from a phosphate fertilizer plant.
The most effective way to reduce fluoride emission from'a gypsum
pond would be to reduce the fluoride partial pressure. The most effec-
tive method now known would be to increase the pH through liming. Liming
to a pH of 6.1 can reduce the partial pressure of fluorides 30-fold. The
indicated lime addition rate would be high, so that this control method
might not be economically feasible. The cost could be reduced if a
method can be found to reduce phosphoric acid loss to the gypsum pond.
In the light of a strict control of fluoride emission from phos-
phate fertilizer processes, the fluoride emission from the gypsum pond
becomes a real challenge. Any additional reduction from these plants
should be achieved through a control of gypsum pond emission. Since
described control methods are not economically feasible, a study of al-
ternative control methods would be most welcome. One useful line of
environmental research could be directed at reduction of gypsum pond
74
-------
emission, perhaps by precipitation of fluoride compounds in an organic
complex or by covering of the pond with a hydrophobic liquid cover.
75
-------
REFERENCES CITED
1. Mcllvaine Scrubber Manual (Mcllvaine Company, Northbrook, 111.: 1976),
pp. 42-511.
2. Atmospheric Emissions from Wet Process Phosphoric Acid Manufacture.
National Air Pollution Control Administration, Publication Number AP-57
(Raleigh, N.C.: April 1970).
3. Doyle and Brooks, Industrial Engineering Chemistry. 49_ (12): 57A (1957).
4. Engineering and Cost Effectiveness Study of Fluoride Emission Control,
EPA Contract EHSD 71-14 (Resources Research, Inc., McClean, Va.:
January 1972), pp. 3-152.
5. Reference 1, pp. 25-26.
6. Control Techniques for Fluoride Emissions. Environmental Health Service,
Second Draft (unpublished),(September 1970), pp. 4-71.
7. Air Pollution Control Technology and Costs in Seven Selected Areas.
Phase I, EPA Contract 68-02-0289 (Industrial Gas Cleaning Institute,
Stanford, Conn.: March 1973), p. 86.
8. Reference 3, pp. 3-161.
9. Background Information for Standards of Performance: Phosphate Fertili-
zer Industry. Vol.~T:Proposed Standards, EPA-450/2-74-019a (U.S.
Environmental Protection Agency, October 1974).
10. Draft Guideline Document: Control of Fluorfde Emissions from Existing
Phosphate Fertilizer Plants (U.S. Environmental Protection Agency,
Research Triangle Part, N.C.: April 1976), pp. 5-11.
11. Technical Report: An Investigation of the Best Systems of Emission
Reduction for Six Phosphate Fertilizer Processes (Environmental Protec-
tion Agency, Research Triangle Park, N.C.: April 1974), p. 47.
12. Reference 3, pp. 3-107-
13. Reference 3, pp. 3-167.
76
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GENERAL REFERENCES
1 Bixby, D. W., et al, "Phosphatic Fertilizers--Properties and Processes,"
Technical Bulletin No. 8 (The Sulfur Institute, Washington, D.C.:
October 1966).
2. Sauchelli, Vincent, Chemistry and Technology of Fertilizers (Reinhold
Publishing Corporation, New York, N.Y.: 1960).
3. Slack, N. V., Phosphoric Acid, Vol. 1 (Marcel Dekker, Inc., New York,
N.Y.: 1968).
4. Teller, A. J., "Control of Gaseous Fluoride Emissions," Chemical Engi-
neering Progress, 63_ (3) (March 1967).
5. Development Document for Effluent Limitations Guidelines and New Source
Performance Standards for the Phosphorous Derived Chemicals Segment of
the Phosphate Manufacturing Point Source Category, EPA-440/l-74-006-a
(U.S. Environmental Protection Agency:January 1974).
6. Technical Report: An Investigation of the Best Systems of Emission
Reduction for Six Phosphate Fertilizer Processes. APTIC X100 (U.S.
Environmental Protection Agency:April 1974).
7. Strauss, W., Industrial Gas Cleaning Equipment (Pergamon Press, New York,
N.Y.: 1966).
77
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APPENDIX
1. Standards of Performance for New Stationary Sources
2. Method 13 A,B: Determination of Total Fluoride Emission
-------
33152
RULES AND REGULATIONS
Title 40—Protection of Environment
CHAPTER I—ENVIRONMENTAL
PROTECTION AGENCY
[PBL 392-7]
PART 60—STANDARDS OF PERFORM-
ANCE FOR NEW STATIONARY SOURCES
Five Categories of Sources in the
Phosphate Fertilizer Industry
On October 22, 1974 (39 FB 37602),
under section 111 of the Clean Air Act,
as amended, the Administrator proposed
standards of performance for nve new
affected facilities -within the phosphate
fertilizer Indus try as follows: Wet-
process phosphoric acid plants, super-
phosphoric acid plants, diammonium
phosphate plants, triple superphosphate
plants, and granular triple superphos-
phate storage facilities.
Interested parties participated in the
rulemaking by sending comments to
EPA. The Freedom of Information Cen-
ter, Rm 202 West Tower, 401 M Street,
SW., Washington, D.C. has copies of the
comment letters received and a summary
of the issues and Agency responses avail-
able for public inspection. In addition,
copies of the issue summary and Agency
responses may be obtained upon written
request from the EPA Public Informa-
tion Center (PM-215), 401 M Street, SW.,
Washington, D.C. 20460 (specify "Com-
ment Summary: Phosphate Fertilizer
Industry"); The comments have been
considered and where determined by the
Administrator to be appropriate, revi-
sions have been made to the proposed
standards, and the revised version of the
standards of performance for five source
categories within the phosphate fertilizer
industry are herein promulgated. The
principal revisions to the proposed stand-
ards and the Agency's responses to major
comments are summarized below.
DEFINITIONS
The comment was made that the desig-
nation of affected facilities (§§ 60.200,
60.210, 60.220, 60.230, and 60.240) were
confusing as written in the proposed
regulations. As a result of the proposed
wording, each component of an affected
facility could have been considered a
separate affected facility. Since this was
not the intent, the affected facility desig-
nations have been reworded. In the new
wording, the listing of components of an
affected facility is intended for identifi-
cation of those emission sources to which
the standard for fluorides applies. Any
sources not listed are not covered by the
standard. Additionally, the definition of
a "superphosphoric acid plant" has been
changed to include facilities which con-
centrate wet-process phosphoric acid to
66 percent or greater P=O,. content in-
stead of 60 percent as specified in the
proposed regulations. This was the result
of a comment stating that solvent ex-
tracted acids could be evaporated to
greater than 60 percent PA using con-
ventional evaporators in the wet-process
phosphoric acid plant. The revision clar-
ifies the original intention of preventing
certain wet-process phosphoric acid
plants from being subject to the morf
restrictive standard for superphosphoric
acid plants.
One commentator was concerned that
a loose interpretation of the definition of
the affected facility for diammonium
phosphate plants might result in certain
liquid fertilizer plants becoming subject
to the standards. Therefore, the word
"granular" has been inserted before
"diammonium phosphate plant" in the
appropriate places in subpart V to clarify
the intended meaning.
Under the standards for triple super-
phosphate plants in §60.23Kb), the
term "by weight" has been added to the
definition of "run-of-pile triple super-
phosphate." Apparently it was not clear
as to whether "25 percent of which
(when not caked) will pass through a
16 mesh screen" referred to percent by
weight or by particle count.
OPACITY STANDARDS
Many commentators challenged the
proposed opacity standards on the
grounds that EPA had shown no correla-
tion between fluoride emissions and
plume opacity, and that no data were
presented which showed that a violation
of the proposed opacity standard would
indicate simultaneous violation of the
proposed fluoride standard. For the
opacity standard to be used as an en-
forcement tool to indicate possible vio-
lation of the fluoride standard, such a
correlation must be established. The
Agency has reevaluated the opacity test
data and determined that the correlation
is Insufficient to support a standard.
Therefore, standards for visible emissions
lor diamTionium phosphate plants, triple
superphosphate plants, and granular
triple superphosphate storage facilities
have been deleted. This action, however,
is not meant to set a precedent re-
garding promulgation of visible emission
standards. The situation which necessi-
tates this decision relates only to fluoride
emissions. In the future, the Agency will
continue to set opacity standards for
affected facilities where such standards
are desirable and warranted based on
test data.
In place of the opacity standard, a pro-
vision has been added which requires an
owner or operator to monitor the total
pressure drop across an affected facility's
scrubbing system. This requirement will
provide an affected facility's scrubbing
system. This requirement will provide for
a record of the operating conditions of
the control system, and will serve as an
effective method for monitoring compli-
ance with the fluoride standards.
REFERENCE METHODS 13A AND 13B
Reference Methods 13A and isB,
which prescribed testing and analysis
procedures for fluoride emissions, were
originally proposed along with stand-
ards of performance for the primary
aluminum industry (39 FR 37730). How-
ever, these methods have been included
with the standards of performance for
the phosphate fertilizer industry and the
the fertilizer standards are being prom-
ulgated before the primary aluminum
standards. Comments were received tram
the phosphate fertilizer industry and the
primary aluminum industry as the meth-
ods are applicable to both industries. The
majority of the comments discussed pos-
sible changes to procedures and to equip-
ment specifications. As a result of these
comments some minor changes were
made. Additionally, it has been deter-
mined that acetone causes a positive
interference in the analytical procedures.
Although the bases for the standard are
not affected, the acetone wash has been
deleted in both methods to prevent po-
tential errors. Reference Method 13A has
been revised to restrict the distillation
procedure (Section 7.3.4) to 175°C in-
stead of the proposed 180'C in order to
prevent positive interferences introduced
by sulfuric acid carryover in the distil-
late at the higher temperatures. Some
commentators expressed a desire to re-
place the methods with totally different
methods of analysis. They felt they
should not be restricted to using only
those methods published by the Agency.
However, in response to these comments,
an equivalent or alternative method may
be used after approval by the Adminis-
trator according to the provisions of
§ 60.8(b) of the regulations (as revised
in 39 FR 9308).
FLUORIDE CONTROL
Comments were received which ques-
tioned the need for Federal fluoride
control because fluoride emissions are lo-
calized and ambient fluoride concentra-
tions are very low. As discussed in the
preamble to the proposed regulations,
fluoride was the only pollutant other
than the criteria pollutants, specifically
named as requiring Federal action In
the March 1970 "Report of the Secre-
tary of Health, Education, and Welfare
to the United States (91st) Congress."
The report concluded that "inorganic
fluorides are highly irritant and toxic
gases" which, even in low ambient con-
centrations, have adverse effects on
plants and animals. The United States
Senate Committee on Public Works in
its report on the Clean Air Amendments
of 1970 (Senate Report No. 91-1196, Sep-
tember 17, 1970, page 9) included fluo-
rides on a list of contaminants which
have broad national impact and require
Federal action.
One commentator questioned EPA's
use of section 111 of the Clean Air Act, as
amended, as a means of controlling fluo-
ride air pollution, Again, as was men-
tioned in the preamble to the proposed
regulations, the "Preferred Standards
Path Report for Fluorides" (November
1D72) concluded that the most appro-
priate control strategy is through section
111. A copy of this report is available
for inspection during normal business
hours at the Freedom of Information
Center, Environmental Protection
Agency, 401 M Street, SW., Washington,
D.C.
Another objection was voiced concern-
ing the preamble statement that the
"phosphate fertilizer industry is a major
source of fluoride air pollution." Accord-
ing to the "Engineering and Cost Effec-
tiveness Study of Fluoride Emissions
FrDERAl REGISTER, VOL. 40, MO. 152—WEDNESDAY, AUGUST 6, 1975
-------
RULES AND REGULATIONS
33153
Control" (Contract EHSD 71-14) pub-
lished In January 1972. the phosphate
fertilizer Industry ranks near the top
of the list of fluoride emitters In the
U.S., accounting for nearly 14 percent
of the total soluble fluorides emitted
every year. The Agency contends that
these facts Justify naming the phosphate
fertilizer Industry a major source of
fluorides.
DlAMMONITTM PHOSPHATE STANDARD
One commentator contended that the
fluoride standard for dlammonium phos-
phate plants could not be met under
certain extreme conditions. During pe-
riods of high air flow rates through the
scrubbing system, high ambient temper-
atures, and high fluoride content in
scrubber liquor, the commentator sug-
gested that the standard would not be
met even by sources utilizing best dem-
onstrated control technology. This com-
ment was refuted for two reasons: (1)
The surmised extreme conditions would
not occur and (2) even If the conditions
did occur, the performance of the control
system would be such as to meet the
standard anyway. Thus the fluoride
standard for diammonium phosphate
plants was not revised.
POND WATER STANDARDS
The question of the standards for pond
water was raised in the comments. The
commentator felt that it would have
been more logical if the Agency had post-
poned proposal of the phosphate fer-
tilizer regulations until standards of per-
formance for pond water had also been
decided upon, instead of EPA saying that
such pond water standards might be set
In the future. EPA researched pond
water standards along with the other
fertilizer standards, but due to the com-
plex nature of pond chemistry and a gen-
eral lack of available information, si-
multaneous proposal was not feasible.
Bather than delay new source fluoride
control regulations, possibly for several
years, the Agency decided to proceed
with standards for five categories of
sources within the industry.
ECONOMIC IMPACT
As was indicated by the comments re-
ceived, clarification of some of the
Agency's statements concerning the eco-
nomic Impact of the standards is neces-
sary. First, the statement that "for three
of the five standards there will be no
increase in power consumption over that
which results from State and local stand-
ards" Is misleading as written in the
preamble to the proposed regulations.
The statement should have been qualified
in that this conclusion was based on pro-
jected construction in the industry
through 1980, and was not meant to be
applicable past that time. Second, some
comments suggested that the cost data in
the background document were out of
date. Of course the time between the
gathering of economic data and the pro-
posal of regulations may be as long as a
year or two because of necessary Inter-
mediate steps in the standard setting
process, however, the economic data are
developed with future industry growth
and financial status in mind, and there-
fore, the analysis should be viable at the
time of standard proposal. Third, an ob-
jection was raised to the statement that
"the disparity in cost between triple
superphosphate and dlammonium phos-
phate will only hasten the trend toward
production of diammonium phosphate."
The commentator felt that EPA should
not place Itself in a position of regulating
fertilizer production. In response, the
Agency does not set standards to regu-
late production. The standards are set to
employ the best system of emission re-
duction considering cost. The standards
will basically require use of a packed
scrubber for compliance in each of the
five phosphate fertilizer source catego-
ries. In Uils instance, control costs (al-
though considered reasonable for both
source categories) are higher for triple
superphosphate plants than for dlam-
monium phosphate plants. The reasons
for this are that (1) larger gas volumes
must be scrubbed in triple superphos-
phate facilities and (2) triple suprephos-
phate storage facility emissions must also
be scrubbed. However, the greater costs
can be partially offset In a plant produc-
ing, both granular triple superphosphate
and diammonium phosphate with the
same manufacturing facility and same
control device. Such a facility can op-
timize utilization of the owner's capital
by operating his phosphoric acid plant at
full capacity and producing a product
mix that will maximize profits. The in-
formation gathered by the Agency indi-
cates that all new facilities equipped to
manufacture dlammonium phosphate
will -also produce granular triple super-
phosphate to satisfy demand for direct
application materials and exports.
CONTROL OF TOTAL FLUORIDES
Most of the commentators objected to
EPA's control of "total fluorides" rather
than "gaseous and water soluble flu-
orides." The rationale for deciding to set
standards for total fluorides is presented
on pages 5 and 6 of volume 1 of the back-
ground document. Essentially the ra-
tionale is that some "insoluble" fluoride
compounds will slowly dissolve If allowed
to remain hi the water-impinger section
of the sample train. Since EPA did not
closely control the time between capture
and nitration of the fluoride samples, the
change was made to Insure a more ac-
curate data base. Additional comments on
this subject revealed concern that the
switch to total fluorides would bring
phosphate rock operations under the
standards. EPA did not intend such op-
erations to be controlled by these regula-
tions, and did not include them in the
definitions of affected facilities; however,
standards for these operations are cur-
rently under development within the
Agency.
MONITORING REQUIREMENTS
Several comments were received with
regard to the sections requiring a flow
measuring device which has an accuracy
of ± 5 percent over Its operating range.
The commentators felt that this accu-
racy could not be met and that the
capital and operating costs outweighed
anticipated utility. First of all, "weigh-
belts" are common devices in the phos-
phate fertilizer Industry as raw material
feeds are routinely measured. EPA
felt there would be no economic Impact
resulting from this requirement because
plants would have normally Installed
weighing devices anyway. Second, con-
tacts with the Industry led EPA to be-
lieve that the ± 5 percent accuracy re-
quirement would be easily met, and a
search of pertinent literature showed
that weighing devices with ± 1 percent
accuracy are commercially available.
PERFORMANCE TEST PROCEDURES
Finally some comments specifically
addressed § 60.245 (now § 60.244) of the
proposed granular triple superphosphate
storage facility standards. The first two
remarks contended that it is Impossible
to tell when the storage building Is filled
to at least 10 percent of the building
capacity without requiring an expensive
engineering survey, and that it was also
Impossible to tell how much triple super-
phosphate in the building is fresh and
how much is over 10 days old. EPA's ex-
perience has been that plants typically
make surveys to determine the amount
of triple superphosphate stored, and
typically keep good records of the move-
ment of triple superphosphate Into and
out of storage so that it is possible to
make a good estimate of the age and
amount of product. In light of data
gathered during testing, the Agency
disagrees with the above contentions and
feels the requirements are reasonable. A
third comment stated that I 60.244 (pro-
posed f 60.245) was too restrictive, could
not be met with partially filled storage
facilities, and that the 10 percent re-
quirement was not valid or practical. In
response, the requirement of S 60.244(d) •
(1) is that "at least 10 percent of the
building capacity" contain granular
triple superphosphate. This means that,
for a performance test, an owner or op-
erator could have more than .10 percent
of the building filled. In fact it Is to his
advantage to have more than 10 percent
because of the likelihood of decreased
emissions (in units of the standard) as
calculated by the equation in ! 60.244 (g).
The data obtained by the Agency
show that the standard can be met with
partially filled buildings. One commenta-
tor did not agree with the requirement in
§ 60.244(e) [proposed § 60.245(e) ] to
have at least five days maximum produc-
tion of fresh granular triple superphos-
phate in the storage building before a
performance test. The commentator
felt this section was unreasonable
because It dictated production schedules
for triple superphosphate. However,
this section applies only when the re-
quirements of i 60.244 (d) (2) [proposed
5 60.245(d) (2) ] are not met. In ad-
dition this requirement is not unreason-
able regarding production schedules
because performance tests are not re-
quired at regular intervals. A perform-
ance' test is conducted after a facility
begins operation; additional perform-
ance tests are conducted only when the
facility is suspected of violation of the
standard of performance.
FEDERAL REGISTER, VOL. 40, NO. 152—WEDNESDAY, AUGUST 6, 1975
-------
33151
RULES AND REGULATIONS
Effective date. In accordance with sec-
tion 111 of the Act, these regulations pre-
scribing standards of performance for
the selected stationary sources are effec-
tive on August 4, 1975, and apply to
sources at which construction or modifi-
cation commenced after October 22,1974.
RUSSELL E. TRAIN,
Administrator.
JULY 25, 1975.
Part 60 of Chapter I, Title 40 of the
Code of Federal Regulations Is amend-
ed as follows:
1. The table of sections Is amended by
adding Subparts T, U, V, W, and X and
revising Appendix A to read as follows:
Subpart T—Standards of Performance for the
Phosphate Fertilizer Industry: Wet Process
Phosphoric Acid Plants
60.200 Applicability and designation of
affected facility.
60.201 Definitions.
60.202 Standard for fluorides.
60.203 Monitoring of operations.
60.204. Test methods and procedures.
Subpart U—Standards of Performance for the
Phosphate Fertilizer Industry: Superphosphoric
Acid Plants
60.210 Applicability and designation of
affected facility.
60.211 Definitions.
60.212 Standard for fluorides.
60.213 Monitoring of operations.
60.214 Test methods and procedures.
Subpart V—Standards of Performance for the
Phosphate Fertilizer Industry: Dlammonium
Phosphate Plants
60.220 Applicability and designation of
affected facility.
60.221 Definitions.
60.222 standard for fluorides.
60.223 Monitoring of operations.
60.224 Test methods and procedures.
Subpart W—Standards of Performance for the
Phosphate Fertilizer Industry: Triple Super-
phosphate Plants
60.230 Applicability and designation of af-
fected facility.
60.231 Definitions.
60.232 Standard for fluorides.
60.233 Monitoring of operations.
60.234 Test methods and procedures.
Subpart X—Standards of Performance for the
Phosphate Fertilizer Industry: Granular Triple
Superphosphate Storage Facilities
60.240 Applicability and designation of af-
fected facility.
60.241 Definitions.
60.242 Standard for fluorides.
60.243 Monitoring of operations.
60.244 Test methods and procedures.
APPENDIX A—REFERENCE METHODS
Method 1—Sample and velocity traverses for
stationary sources.
Method 2—Determination of stack gas ve-
locity and volumetric flow rate (Type S
pltot tube).
Method 3—Gas analysis for carbon dioxide,
excess air, and dry molecular weight.
Method 4—Determination of moisture in
stack gases.
Method 5—Determination of partlculate
emissions from stationary sources.
Method 6—Determination of sulfur dioxide
emissions from stationary sources.
Method 7—Determination of nitrogen oxldo
emissions from stationary sources.
Method 8—Determination of sulfurlc acid
mist and sulfur dioxide emissions from
stationary sources.
Method 9—Visual determination of the opac-
ity of emissions from stationary sources.
Method 10—Determination of carbon monox-
ide emissions from stationary sources.
Method 11—Determination of hydrogen sul-
ude emissions from stationary sources.
Method 12—Reserved.
Method 13A—Determination of total fluoride
emissions from stationary sources—
SPADNS Zirconium Lake Method.
Method 13B—Determination of total fluoride
emissions from stationary sources—Spe-
cific Ion Electrode Method.
2. Part 60 is amended by adding sub-
parts T, U, V, W, and X as follows:
Subpart T—Standards of Performance for
the Phosphate Fertilizer Industry: Wet-
Process Phosphoric Acid Plants
§ 60.200 Applicability and ilcsignalion
of affected facility.
The affected facility to which the pro-
visions of this subpart apply Is each wet-
process phosphoric acid plant. For the
purpose of this subpart, the affected
facility Includes any combination of: re-
actors, filters, evaporators, and hotwells.
§ 60.201 Definitions.
As used In this subpart, all terms not
defined herein shall have the meaning
given them In the Act and In subpart A
of this part.
(a) "Wet-process phosphoric acid
plant" means any facility manufactur-
ing phosphoric acid by reacting phos-
phate rock and acid.
(b) "Total fluorides" means elemental
fluorine and all fluoride compounds as
measured by reference methods specified
In § 60.204, or equivalent or alternative
methods.
(c) "Equivalent PaO5 feed" means the
quantity of phosphorus, expressed as
phosphorous pentoxide, fed to. the proc-
ess.
§ 60.202 Standard for fluorides.
(a) On and after the date on which
the performance test required to be con-
ducted by § 60.8 is completed, ho owner
or operator subject to the provisions of
this subpart shall cause to be discharged
Into the atmosphere from any affected
facility any gases which contain total
fluorides in excess of 10.0 g/metrlc ton
of equivalent P3Oc feed (0.020 Ib/ton).
§ 60.203 Monitoring of operations.
(a) The owner or operator of any wet-
process phosphoric acid plant subject to
the provisions of this subpart shall in-
stall, calibrate, maintain, and operate a
monitoring device which can be used to
determine the mass flow of phosphorus-
bearing feed material to the process. The
monitoring device shall have an accu-
racy of ±5 percent over its operating
range.
(b) The owner or operator of any wet-
process phosphoric acid plant shall
maintain a daily record of equivalent
PjOB feed by first determining the total
mass rate in metric ton/hr of phosphorus
bearing feed using a monitoring device
for measuring mass flowrate which meets
the requirements of paragraph (a) of
this section and then by proceeding ac-
cording to § 60.204 (d) (2).
(c) The owner or operator of any wet-
process phosphoric acid subject to the
provisions of this part shall Install, cali-
brate, maintain, and operate a monitor-
Ing device which continuously measures
and permanently records the total pres-
sure drop across the process scrubbing
system. The monitoring device shall have
an accuracy of ±5 percent over its op-
erating range.
§ 60.201 Test methods and procedures.
(a) Reference methods In Appendix A
of this part, except as provided In § 60.8
(b), shall be used to determine compli-
ance with the standard prescribed In
§ 60.202 as follows:
(1) Method 13A or 13B for the concen-
tration of total fluorides and the asso-
ciated moisture content,
(2) Method 1 for sample and veloeity
traverses,
(3) Method 2 for velocity and vol-
umetric flow rate, and
(4) Method 3 for gas analysis.
(b) For Method 13A or 13B, the sam-
pling time for each run shall be at least
60 minutes and the minimum sample
volume shall be 0.85 dscm (30 dscf) ex-
cept that shorter sampling times or
smaller volumes, when necessitated by
process variables or other factors, may
be approved by the Administrator.
(c) The air pollution control system
for the affected facility shall be con-
structed so that volumetric flow rates
and total fluoride emissions can be ac-
curately determined by applicable test
methods and procedures.
(d) Equivalent PiOt feed shall be de-
termined as follows:
(1) Determine the total mass rate In
metric ton/hr of phosphorus-bearing
feed during each run using a flow
monitoring device meeting the require-
ments of § 60.203(a).
(2) Calculate the equivalent P=OS feed
by multiplying the percentage PiOs con-
tent, as measured by the spectrophoto-
metric molybdovanadophosphate method
(AOAC Method 9), times the total mass
rate of phosphorus-bearing feed. AOAC
Method 9 Is published In the Official
Methods of Analysis of the Association
of Official Analytical Chemists, llth edi-
tion, 1970, pp. 11-12. Other methods may
be approved by the Administrator.
(e) For each run, emissions expressed
in g/metrlc ton of equivalent P»O5 feed
shall be determined using the following
equation:
,- (C,Q,) JO-J
where:
E=Emtsslons of total fluorides In g/
metric ton of equivalent P,O.
feed.
C.=--Concentration of total fluorides In
mg/dscm as determined by
Method ISA or 13D.
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RULES AND REGULATIONS
33155
Subpart U — Standards of Performance for
the Phosphate Fertilizer Industry: Super-
phosphoric Acid Plants
§60.210 Applicability and
of a/Tcclcd facility.
The affected facility to which the pro-
visions of this suhpart apply Is each
superphosphorlc acid plant. For the pur-
pose of this subpart, the affected facility
includes any combination of: evapora-
tors, liotwells, acid sumps, and cooling
tanks.
§ 60.211 Definitions.
As used in this subpart, all terms not
defined herein shall have the meaning
given them In the Act and In subpart A
of this part.
(a) "Superphosphorlc acid plant"
means any facility which concentrates
wet-process phosphoric acid to 66 per-
cent or greater P»OB content by weight
for eventual consumption as a fertilizer.
(b) "Total fluorides" means elemen-
tal fluorine and all fluoride compounds
as measured by reference methods spe-
cified in § 60.214, or equivalent or alter-
native methods.
(c) "Equivalent PiOe feed" means the
quantity of phosphorus, expressed as
phosphorous pentoxide, fed to the
process.
§ 60.212 Standard for fluorides.
(a) On and after the date on which
the performance test required to be con-
ducted by {60.8 is completed, no owner
or operator subject to the provisions of
this subpart shall cause to be discharged
into the atmosphere from any affected
- facility any gases which contain total
fluorides In excess of 5.0 g/metric ton of
equivalent P,O. feed (0.010 Ib/ton).
§ 60.213 Monitoring of operations.
.(a) The owner or operator of any
superphosphoric acid plant subject to
the provisions of this subpart shall in-
stall, calibrate, maintain, and operate
a flow monitoring device which can be
used to determine the mass flow of
phosphorus -bearing feed material to the
process. The flow monitoring device shall
have an accuracy of ±5 percent over its
operating range.
(b) The owner or operator of any
superphosphoric acid plant shall main-
tain a dally record of equivalent P2OS
feed by first determining the total mass
rate In metric ton/hr of phosphorus-
bearing feed using a. flow monitoring de-
vice meeting the requirements of para--
graph (a) of this section and then by
proceeding according to 8 60. 214 (d) (2).
(c) The owner or operator of any
superphosphoric acid plant subject to the
provisions of this part shall install, cali-
brate, maintain, and operate a monitor-
ing device which continuously measures
and permanently records the total pres •
sure drop across the process scrubbing
system. The monitoring device shall have
nn accuracy of ± 5 percent over its
operating range.
§ 60.214 Test mrllioJs mid procedures.
(a) Reference methods In Appendix
A of this part, except as provided In
|C0.8(b>, shall be used to determine
compliance with the standard prescribed
in £ 60.212 as follows:
(1) Method 13A or 13B for the concen-
tration of total fluorides and the asso-
ciated moisture content.
(2) Method 1 for sample and velocity
traverses,
(3) Method 2 for velocity and volu-
metric flow rate, and
(4) Method 3 for gas analysis. ''
(b) For Method 13A or 13"., the sam-
pling time for each run shall be at least
60 minutes and the minimum sample
volume shall be at least 0.85 dscm (30
dscf ) except that shorter sampling times
or smaller volumes, when necessitated by
process variables or other factors, may
be approved by the Administrator.
(c) The air pollution control system
for the affected facility shall be con-
structed so that -volumetric flow rates and
total fluoride emissions can be accurately
determined by applicable test methods
and- procedures. >
(d) Equivalent P,O, feed shall be deter-
mined as follows:
(1) Determine the total mass rate In
metric ton/hr of phosphorus-bearing
feed during each run using a flow moni-
toring device meeting the requirements
of §60.213 (a).
(2) Calculate the equivalent P2O5 feed
by multiplying the percentage PiOj con-
tent, as measured by the spectrophoto-
metric molybdovanadophosphate method
(AOAC Method 9) , times the total mass
rate of phosphorus-bearing feed. AOAC
Method 9 Is published in the Official
Methods of Analysis of the Association of
Official Analytical Chemists, llth edition,
1970, pp. 11-12. Other methods may be
approved by the Administrator.
(e) For each run, emissions expressed
in g/metric ton of equivalent P»O. feed,
shall be determined using the following
equation :
.) 10"
where:
E= Emissions of total fluorides In g/
metric ton of equivalent P,OS
feed.
C,= Concentration of total fluorides In
mg/dscm as determined by
Method 13A or 13B.
Q, = Volumetric flow' rate of the effluent
gas stream In dscm/hr as deter-
mined by Method 2.
10-'= Conversion factor for mg to g.
Mr^i; Equivalent P,OC feed in metric
ton/hr as determined by [ 60.-
214(d).
Subpart V — Standards of Performance for
the Phosphate Fertilizer Industry: Diam-
inonium Phosphate Plants
§ 60.220 Applicability und dt"aliou
of ttffcclcJ facility.
The affected facility to which the pro-
visions of this subpart apply Is each
granular diammonium phosphate plant.
For the purpose of this subpart, the af-
fected facility includes any combination
of: reactors, eranulators, dryers, coolers,
screens and mills.
§60.221 Di>niiiiioii9.
As used in this subpart, nil terms not
defined herein shall have the meaning
given them in the Act and In subpart A
of this part,
(a) "Granular diammonium phos-
phate plant" means any plant manu-
facturing granular diammonium phos-
phate by reacting phosphoric acid with
ammonia.
(b) "Total fluorides" moans elemental
fluorine and all fluoride compounds as
measured by reference methods speci-
fied in § 60.224, or equivalent or alter-
native methods.
(c) "Equivalent P:O0 feed" means the
quantity of phosphorus, expressed as
phosphorous pentoxide, fed to the proc-
ess.
§ 60.222 Slundurd for fluorides.
(a) On and after the date on which
the performance test required to be con-
ducted by § 60.8 is completed, no owner
or operator subject to the provisions of
this subpart shall cause to be discharged
into the atmosphere from any affected
facility any gases which contain total
fluorides in excess of 30 g/metric ton of
equivalent P:Oi feed (0.060 Ib/ton).
§ 60.223 Monitoring of operations.
(a) The owner or operator of any
granular diammonium phosphate plant
subject to the provisions of this subpart
shall install, calibrate, maintain, and
operate a flow monitoring device which
can be used to determine the mass flow
of phosphorus-bearing feed material to
the process. The flow monitoring device
shall have an accuracy of ±5 percent
over its operating range.
(b) The owner or operator of any
granular diammonium phosphate plant
shall maintain a daily record of equiv-
alent P2Ot feed by first determining the
total mass rate in metric ton/hr of phos-
phorus-bearing feed using a flow moni-
toring device meeting the requirements
of paragraph (a) of this section and then
by proceeding according to § 60.224 (d)
(2).
,(c) The Downer or operator of any
granular diammonium phosphate plant
subject to the provisions of this part shall
install, calibrate, maintain, and operate
a monitoring device which continuously
measures and permanently records the
total pressure drop across the scrubbing
system. The monitoring device shall have
an accuracy of ±5 percent over its op-
erating range.
§ 60.221 Test methods and procedures.
(a) Reference methods in Appendix A
of this part, except as provided for in
.5 60.8 (b), shall be used to determine com-
pliance with the standard prescribed in
§ 60.222 as follows:
(1) Method 13A or 13B for the con-
centration of total fluorides and the as-
sociated moisture content,
(2) Method 1 for sample and velocity
traverses,
(3) Method 2 for velocity and volu-
metric flow rate, and
(4) Method 3 for gas analysis.
(b) For Method 13A or 13B. the
sampling time for each run shall be at
least 60 minutes and the minimum
sample volume shall be at least 0.85 dscm
(30 dscf) except that shorter sampling
FEDERAL REGISTER, VOL. 40, NO. 152—WEDNESDAY, AUGUST 6. 1975
-------
33156
times or smaller volumes when neces-
sitated by process variables or other
factors, may be approved by the Ad-
ministrator.
(c) The air pollution control system
for the affected facility shall be con-
structed so that volumetric flow rates
and total fluoride emissions can be ac-
curately determined by applicable test
methods and procedures.
(d) Equivalent PaOB feed shall .be de-
termined as follows:
(1) Determine the total mass rate irk
metric ton/hr of phosphorus-bearing
feed during each run using a flow moni-
toring device meeting the requirements
of § 60.223 (a).
(2) Calculate the equivalent PS05' feed
by multiplying the percentage P=05 con-
tent, as measured by the spectrophoto-
metric molybdovanadophosphate method
(AOAC Method 9) , times the total mass
rate of phosphorus-bearing feed. AOAC
Method 9 Is published in the Official
Methods of Analysis of the Association
of Official Analytical Chemists, llth edi-
tion, 1970, pp. 11-12. Other methods may
be approved by the Administrator.
(e) For each run, emissions expressed
In g/metrlc ton of equivalent PaOa feed
shall be determined using the following
equation:
(C.Q.) 10-'
where:
£= Emissions of total fluorides In g/
metric ton of equivalent P2OS.
C, = Concentration of total fluorides In
mg/dscm as determined by
Method ISA or 13B.
Q, = Volumetric flow rate of the effluent
gas stream In dscm/hr as deter-
mined by Method 2.
10-'=: Con version factor for mg to g.
flf>zo6=Equlvalent P.O5 feed In metric
ton/hr as determined by 5 60.-
224(d).
Subpart W — Standards of Performance for
the Phosphate Fertilizer Industry: Triple
Superphosphate Pla.nts
§ 60.230 Applicability and designation
of affected facility.
The affected facility to which the pro-
visions of this subpart apply is each
triple superphosphate plant. For the
purpose of this subpart, the affected
facility includes any combination of:
Mixers, curing belts (dens), reactors,
granulators, dryers, cookers, screens,
mills and facilities which store run-of-
pile triple superphosphate.
§ 60.231 Definitions.
As used in this subpart, pll terms not
defined herein shall have the meaning
given them in the Act and in subpart A
of this part.
(a) "Triple superphosphate plant"
means any facility manufacturing triple
superphosphate by reacting phosphate
rock with phosphoric acid. A rule-of-pile
triple superphosphate plant includes
curing and storing.
(b) "Run-of-pile triple superphos-
phate" means any triple superphosphate
that has not been processed in a granu-
lator and Is composed of "articles at
RULES AND REGULATIONS
least 25 percent by weight of which
(when not caked) will pass through a 16
mesh screen.
. (c) "Total fluorides" means ele-
mental fluorine and all fluoride com-
pounds as measured by reference
methods specified in i 60.234. or equiva-
lent or alternative methods.
(d) "Equivalent P,Oa feed" means the
quantity of phosphorus, expressed as
phosphorus pentoxide, fed to the process.
§ 60.232 Standard for fluorides.
(a) On and after the date on which the
performance test required to be con-
ducted by § 60.8 is completed, no owner
or operator subject to the provisions of
this subpart shall cause to be discharged
into the atmosphere from any affected
facility any gases which contain total
fluorides in excess of 100 g/metric.ton of
equivalent PaO. feed (0.20 Ib/ton).
§ 60.233 Monitoring of operations.
(a) The owner or operator of any triple
superphosphate plant subject to the pro-
visions of this subpart shall Install, cali-
brate, maintain, and operate a flow moni-
toring device which can be used to deter-
mine the mass flow of phosphorus-bear-
ing feed material to the process. The flow
monitoring device shall have an accuracy
of. ±5 percent over its operating range.
(b) The owner or operator of any
triple superphosphate plant shall main-
tain a daily record of equivalent P-O5 feed
by first determining the total mass rate
in metric ton/hr of phosphorus-bearing
feed using a flow monitoring device meet-
ing the requirements of paragraph (a)
of this section and then by proceeding
according to § 60.234(d) (2).
(c) The owner or operator of any triple
superphosphate plant subject to the pro-
visions of this part shall install, calibrate,
maintain, and operate a monitoring de-
vice which continuously measures and
permanently records the total pressure
drop across the process scrubbing system.
The monitoring device shall have an ac-
curacy of ±5 percent over its operating.
range.
§ 60.234 Test methods and procedures.
(a) Reference methods in Appendix A
of this part, except as provided for in
§ 60.8(b), shall be used to determine com-
pliance with the standard prescribed in
§ 60.232 as follows:
(1) Method 13A or 13B for the concen-
tration of total fluorides and the asso-
ciated moisture content,
(2) Method 1 for sample and velocity
traverses,
(3) Method 2 for velocity and volu-
metric flow rate, and
(4) Method 3 for gas analysis.
(b) For Method ISA or 13B, the sam-
pling time for each run shall be at least
60 minutes and the minimum sample
volume shall be at least 0.85 dscm (30
dscf) except that shorter sampling times
or smaller volumes, when necessitated by
process variables or other factors, may
be approved by the Administrator.
(c) The air pollution control system
for the affected facility shall be con-
structed so that volumetric flow rates
and total fluoride emissions can be ac-
curately determined by applicable test
methods and procedures.
(d) Equivalent P2Oa feed shall be deter-
mined as follows:
(1) Determine the total mass rate in
metric ton/hr of phosphorus-bearing
feed during each run using a flow moni-
toring device meeting the requirements
of 5 60.233 (a).
(2) Calculate the equivalent P2OD feed
by multiplying the percentage PaO0 con-
tent, as measured by the spectrophoto-
mctric molybdovanadophosphate method
(AOAC Method 9), times the total mass
rate of phosphorus-bearing feed. AOAC
Method 9 is published in the Official
Methods of Analysis of the Association of
Official Analytical Chemists, llth edition,
1970, pp. 11-12. Other methods may be
approved by the Administrator.
(e) For each run, emissions expressed
in g/metric ton of equivalent PaO5 feed
shall be determined using the following
equation :
E_(C.Q.) 10-'
Mptot
where:
E= Emissions of total nuorldea In g/
metric ton of equivalent P,ps
feed.
C, = Concentration of total fluorides In
mg/dscm as determined by
Method 13A or 13B.
Q,= Volumetric flow rate of the effluent
gas stream In dscm/hr as deter-
mined by Method 2.
10-'= Conversion factor for mg to g.
MP,O^ Equivalent P2OS feed In metric
ton/hr as determined by 5 60.-
Subpart X — Standards of Performance for
the Phosphate Fertilizer Industry: Gran-
ular Triple Superphosphate Storage Fa-
cilities
§ 60.240 Applicability and designation
of affected facility.
The affected facility to which the pro-
visions of this subpart apply is each
granular triple superphosphate storage
facility. For the purpose of this subpart,
the affected facility includes any com-
bination of: storage or curing piles, con-
veyors, elevators, screens and mills.
§ 60.241 Definitions.
As used in this subpart, all terms not
denned herein shall have the meaning
given them in the Act and in subpart A
of this part.
(a) "Granular triple superphosphate
storage facility" means any facility cur-
ing or storing granular triple superphos-
phate.
(b) "Total fluorides" means elemental
fluorine and all fluoride compounds as
measured by reference methods specified
in § 60.244, or equivalent or alternative
methods.
(c) "Equivalent P.O-, stored" means
the quantity of phosphorus, expressed as
phosphorus penloxide, being cured or
stored in the affected facility.
(d) "Fresh granular triple superphos-
phate" means granular triple superphos-
phate produced no more than 10 days
prior to the date of the performance test.
FEDERAL REGISTER, VOL 40, NO. 152—WEDNESDAY, AUGUST 6, 1975
-------
RULES AND REGULATIONS
33157
§ 60.242 Standard for fluorides.
(a) On and after the date on which the
performance test required to be con-
ducted by S 60.8 Is completed, no owner
or operator subject to the provisions of
this subpart shall cause to be discharged
into the atmosphere from any affected
facility any gases which contain total
fluorides in excess of 0.25 e/hr/melric
ton of equivalent P.O. stored (5.0 x 10-'
Ib/hr/ton of equivalent P,O0 stored).
§ 60.213 Monitoring of operations.
(a) The owner or operator of any
granular triple superphosphate storage
facility subject to the provisions of tills
subpart shall maintain an accurate ac-
count of triple superphosphate in storage
to permit the determination of the
amount of equivalent P«OB stored.
(b) The owner or operator of any
granular triple superphosphate storage
facility shall maintain a daily record of
total equivalent P,OB stored by multiply-
ing the percentage P,O, content, as
determined by § 60.244 (f) (2), times the
total mass of granular triple superphos-
phate stored.
(c) The owner or operator of any
granular triple superphosphate storage
facility subject to the provisions of this
part shall install, calibrate, maintain,
and operate a monitoring device which
continuously measures and permanently
records the total pressure drop across the
process scrubbing sytem. The monitoring
device shall have an accuracy of ±5 per-
cent over its operating range.
§ 60.241 Test methods and procedures.
(a) Reference methods in Appendix A
of this Pf.it, except as provided for in
§G0.8(b), shall be used to determine
compliance with the standard prescribed
in 5 60.242 as follows:
(1) Method ISA or 13B for the con-
centration of total fluorides and the as-
sociated moisture content,
(2) Method 1 for sample and velocity
traverses,
(3) Method 2 for velocity and volu-
metric flow rate, and
(4) Method 3 for gas analysis.
(b) For Method 13A or 13B, the sam-
pling time for each run shall be at least
60 minutes and the minimum sample
volume shall be at least 0.85 dscm (30
dscf) except that shorter sampling times
or smaller volumes, when necessitated
by process variables or other factors, may
be approved by the Administrator.
(c) The air pollution control system
lor the affected facility shall be con-
structed so tfiat volumetric flow rates
and total fluoride emissions can be ac-
curately determined by applicable test
methods and procedures.
(d) Except as provided under para-
graph (e) of this section, all perform-
ance tests on granular triple superphos-
phate storage facilities shall be con-
ducted only when the following quanti-
ties of product are being cured or stored
in the facility:
(1) Total granular triple superphos-
phate—at least 10 percent of the build-
ing capacity.
(2) Fresh granular triple superphos-
phate—at least 20 percent of the amount
of triple superphosphate in the building.
(e) If the provisions set forth in para-
graph (d) (2) of this section exceed pro-
duction capabilities for fresh granular
triple superphosphate, the owner or oper-
ator shall have at least five days maxi-
mum production of fresh granular triple
superphosphate in the building during
a performance test.
(f) Equivalent PSO, stored shall be
determined as follows:
(1) Determine the total mass stored
during each run using an accountability
system meeting the requirements of
§60.243(a).
(2) Calculate the equivalent P3OC
stored by multiplying the percentage
PaOi> content, as measured by the spec-
trophotometric molybdovanadophos-
phate method (AOAC Method 9) , times
the total mass stored. AOAC Method 9
is published in the Affioial Methods of
Analysis of the Association of Official
Analytical Chemists. llth edition, 1970,
pp. 11-12. Other methods may be. ap-
proved by the Administrator.
- (g) • For each run, emissions expressed
in g/hr/metric ton of equivalent P2O«
stored Khali be determined using the fol-
lowing equation :
(C.O.) IP"'
where:
£= Emissions of total fluorides In g/
' hr/metrlc ton of equivalent P,O,
- stored.
C,= Concentration of total fluorides In
mg/dscm as determined by
Method ISA or 13B.
Q,= Volumetric flow rate of the effluent
gas stream, in dscm/hr as deter-
mined by Method 2.
10-'= Conversion factor tor mg to g.
Mp,8,=Equlvalent P,O, feed In metric
tons as measured by 5 60. 244 (d).
3. Part 60 is amended by adding Reference
Methods ISA and 13B to Appendix A as
follows:
METHOD 13 — DETETMINATION OP TOTAL FLUO-
EIDE EMISSIONS FROM STATIONARY SOURCES -
SPADNS ZIRCONIUM LAKE METHOD
1. Principle and. Applicability.
1.1 Principle. Gaseous and partlculate
fluorides are withdrawn Isoklnetlcally from
the source using a sampling train. The fluo-
rides are collected In the Implnger water and
on the filter of the sampling train. The
weight of total fluorides In the train Is de-
termined by the SPADNS Zirconium Lake
colorlmetrlc method.
1.2 Applicability. This method Is applica-
ble for the determination of fluoride emis-
sions from stationary sources only when
specified by the test procedures for deter-
mining compliance with new source per-
formance standards. Fluorocarbons. such as
Freons, are not quantitatively collected or
measured by this procedure.
Z. Range, and Sensitivity.
The SPADNS Zirconium Lake analytical
method covers the range from 0-1.4 «/g/ml
fluoride. Sensitivity has not been determined.
3. Interferences.
During the laboratory analysis, aluminum
lu excess of 300 mg/llter and silicon dioxide
In excess of 300 /
-------
33158
pltot tube shall be at least 1.9 cm (0.75 In.).
The free space shall be set based oil a 1.3 cm
(0.5 In.) ID nozzle, which Is the largest size
nozzle used.
The pltot tube imist also meet the criteria
specified In Method 2 and be calibrated ac-
cording to the procedure lu tho calibration
section of that method.
6.1.4: Differential pressure gauge—In-
clined manometer capable ot measuring ve-
locity head to within 10% of the minimum
measured value. Below a differential pressure
of 1.3 mm (0.05 In.) water gauge, micro-
manometers with sensitivities of 0.013 mm
(0.0005 lu.) should be used. However, micro-
manometers are not easily adaptable to field
conditions and are not easy to use with pul-
sating flow. Thus, other methods or devices
acceptable to the Administrator may be
used when conditions warrant.
5.1.5 Filter holder—Boroslllcate glass with
a glass frit filter support and a silicone rub-
ber gasket. Other materials of construction
may be used with approval from the Ad-
ministrator, e.g., If probe liner la stainless
steel, then filter holder may be stainless steel.
The holder design shall provide a positive
seal against leakage from the outside or
around the filter.
5.1.6 Filter heating system—When mois-
ture condensation is a problem, any heating
system capable of maintaining a temperature
around the filter holder during sampling of
no greater than 120±14°C (248±26°F).
A temperature gauge capable of measuring
temperature to within 3°C (6.4°F) "shall be
Installed so that when the filter heater Is
used, the temperature around the filter
holder can be regulated and monitored dur-
ing sampling. Heating systems other than
the one shown in APTD-0581 may be used.
6.1.7 Implngers—Four implngers con-
nected as shown In Figure 13A-1 with ground
glass (or equivalent), vacuum tight fittings.
The first, third, and fourth Implngers are
of the Greanburg-Snnlth design, modified by
replacing the tip with e. 1% cm ('/i In.)
Inside diameter glass tube extending to 1 %
cm ('/a In.) from the bottom of the flask.
The second Implnger Is of the Greensburg-
Smith design with the standard tip.
5.1.8 Metering system—Vacuum gauge,
leak-free pump, thermometers capable of
measuring temperature to within 3'C
(~6°F), dry gas meter with 2% accuracy at
the required sampling rate, and related
equipment, or equivalent, as required to
maintain an Isoklnetlc sampling rate and
to determine sample volume. When the
metering system is used In conjunction with
a pltot tube, the system shall enable checks
of isokinetlc rates.
6.1.9 Barometer—-Mercury, aneroid, or
other barometers capable of measuring at-
mospheric pressure to within 2.6 mm Hg
(0.1 In. Hg). In many cases, the barometric
reading may be obtained from a nearby
weather bureau station, In which case the
station value shall bo requested and an ad-
justment for elevation differences shall bo
applied at a rate of minus 2.5 mm Hg (0.1
in. Hg) per 30 m (100 ft) elevation increase.
6.2 Sample recovery.
5.2.1 Probe liner and probe nozzle
brushes—Nylon bristles with stainless steel
wire handles. The probe brush shall have
extensions, at least as long as the probe, of
stainless steel, teflon, or similarly inert mate-
rial. Both brushes shall be properly sized and
shaped to brush out the probe liner and
nozzle.
5.2.2 Glass wash bottles—Two.
6.2.3 Sample storage containers—Wide
mouth, high density polyethylene bottles,
1 liter.
5.2.4 Plastic storage containers—Air tight
containers of sufficient volume to store silica
got
RULES AND REGULATIONS
6.2.6 Graduated cylinder—250 ml.
6.2.8 Funnel and rubber policeman—to
aid In transfer of silica gel to container; not
necessary if silica gel Is weighed In the field.
6.3 Analysis.
5.3.1 Distillation apparaUis—Glass distil-
lation apparatus assembled as shown In Fig-
ure 13A-2.
5.3.2 Hot plate—Capable of heating to
600° C.
5.3.3 Electric muffle furnace—Capable of
heating to 600° C.
6.3.4 Crucibles—Nickel, 75 to 100 ml ca-
pacity.
6.3.6 Beaker, 1600 ml.
6.3.8 Volumetric flask—50 ml.
5.3.7 Erlcnmeyer flask or plastic bottle—
600 ml.
5.3.8 Constant temperature bath—Capa-
ble of maintaining a constant temperature of
±1.0° C in the range of room temperature.
6.3.9 Balance—300 g capacity to measure
to ±0.5 g.
6.3.10 Spectrophotometer — Instrument
capable of measuring absorbance at 570 nm
and providing at least a 1 cm light path.
5.3.11 Spectrophotometer cells—1 cm.
6. Reagents
6.1 Sampling.
6.1.1 Filters—Whatman No. 1 filters, or
equivalent, sized to fit filter holder.
6.1.2 Silica gel—Indicating type, 6-16
mesh. II previously used, dry at 176° C
(350° F) for 2 hours. New silica gel may be
used as received.
6.1.3 Water—Distilled.
6.1.4 Crushed Ice.
6.1.6 Stopcock grease—Acetone Insoluble,
heat stable slllcone grease. This Is not neces-
sary if screw-on connectors with teflon
sleeves, or similar, are used.
6.2 Sample recovery.
6.2.1 Water—Distilled from same con-
tainer as 6.1.3.
6.3 Analysis,
6.3.1 Calcium oxide (CaO)—Certified
grade containing 0.005 percent fluoride or
less.
6.3.2 Phenolphthaleln Indicator—0.1 per-
cent in 1:1 ethanol-water mixture.
6.3.3 Silver sulfato (Ag^SO,)—ACS re-
agent grade, or equivalent.
6.3.4 Sodium hydroxide (NaOH)—Pellets,
ACS reagent grade, or equivalent.
6.3.5 Sulfurlc acid (HaSO4)—Concen-
trated, ACS reagent grade, or equivalent.
G.3.6 Filters—Whatman No. 541, or equiv-
alent:
6.3.7 Hydrochloric acid (HC1)—Concen-
trated, ACS reagent grade, or equivalent.
6.3.8 Water—Distilled, from same con-
tainer as 6.1.3.
6.3.9 Sodium fluoride—Standard solution.
Dissolve 0.2210 g of sodium fluoride to 1
liter of distilled water. Dilute'100 ml of this
solution to 1 liter with distilled water. One
mllllllter of tho solution contains 0.01 mg
of fluoride.
6.3.10 SPADNS solution—[4,5dihydroxy-
3-(p-sulfophenylazo)-2,7-naphthaleno - dl-
sulfonlc acid trisodlum salt]. Dissolve 0.960
±.010 g of SPADNS reagent In 600 ml dis-
tilled water. This solution Is stable for at
least one month, if stored In a well-sealed
bottle protected from sunlight.
6.3.11 Reference solution—Add 10 ml of
SPADNS solution (6.3.10) to 100 ml distilled
water and acidify with a solution prepared by
diluting 7 ml of concentrated HC1 to 10 ml
with distilled water. This solution Is used to
set the spcctrophotomcter zero point and
should be prepared dally.
6.3.12 SPADNS Mixed Reagent—Dissolve
0.135 ±0.005 g of zlrconyl chloride octahy-
drate (ZrOClj.SHp), In 25 ml distilled water.
Add 350 ml of concentrated HC1 and dilute to
600 nil with distilled water. Mix equal vol-
umes of this solution and SPADNS solution
to form a single reagent. This reagent is
btnblo for at least two months.
7. Procedure.
NOTE: Tho fusion and distillation steps of
this procedure will not bo required. If It can
bo shown to the satisfaction of the Adminis-
trator that the samples contain only water-
soluble fluorides.
7.1 Sampling. The sampling shall be con-
ducted by competent personnel experienced
with this test procedure.
7.1.1 Pretest preparation. All train com-
ponents shall be maintained and calibrated
according to the procedure described In
APTD-0576, unless otherwise specified herein.
Weigh approximately 200-300 g of silica gel
in air tight containers to tho nearest 0.5 g.
Record the total weight, both silica gel and
container, on the container. More silica gel
may be used but care should be taken during
sampling that It is not entrained and carried
out from the Implnger. As an alternative, the
silica gel may be weighed directly In the Im-
plnger or its sampling holder Just prior to
the train assembly.
7.1.2 Preliminary determinations. Select
the sampling site and the minimum number
of sampling points according to Method 1 or
as specified by the Administrator. Determine
the stack pressure, temperature, and the
range of velocity heads using Method 2 and
moisture content using Approximation Meth-
od 4 or Its alternatives for the purpose of
making isokinetic sampling rate calculations.
Estimates may be used. However, final results
will bo based on actual measurements made
during the test.
Select a nozzle size based on the range of
velocity heads such that It Is not necessary
to change the nozzle size in order to main-
tain Isoklnetlc sampling rates. During the
run, do not change the nozzle size. Ensure
that the differential pressure gauge Is capable
of measuring the minimum velocity head
value to within 10%, or as specified by tho
Administrator.
Select a suitable probe liner and probe
length such that all traverse points can be
sampled. Consider sampling from opposite
sides for large stacks to reduce the length of
probes.
Select a total sampling time greater than
or equal to the minimum total sampling time
specified In the test procedures for the spe-
cific industry such that the sampling time
per point Is not less than 2 mln. of select
some greater time Interval as specified by the
Administrator, and such that the sample
volume that will bo taken will exceed the re-
quired minimum total gas sample volume
specified in the test procedures for the spe-
cific industry. -The latter Is based on an ap-
proximate average sampling rate. Note also
that the minimum total sample volume la
corrected to standard conditions.
It Is recommended that a half-Integral or
integral number of minutes bo sampled ait
each point In order to avoid timekeeping
errors.
In some circumstances, e.g. batch cycles, It
may be necessary lo sample for shorter times
at the traverse points and to obtain smaller
gas sample volumes. In these cases, the Ad-
ministrator's approval must first be obtained.
7.1.3 Preparation of collection train. Dur-
ing preparation and assembly of the sam-
pling train, keep all openings where contami-
nation can occur covered until Just prior to
assembly or until sampling Is about to begin.
Ploco 100 ml of water In each of the first
two Impingers. leave the third Implnger
empty, and place approximately 200-300 g
or more, if necessary, of prewelghed silica
gel in the fourth Implnger. Record the weight
of the silica gel and container on the data
sheet. Place tho empty container In a clean
place for later use In tho sample recovery.
Placo r. filter In the filter holder. Be sure
that the filter is properly centered and tho
FEDERAL REGISTER, VOL. 40, NO. 152—WEDNESDAY, AUGUST 6, 1975
-------
RULES AND REGULATIONS
33159
gnsket properly phoced so as to not allow the
sample gas stream to circumvent the flltor.
Check niter for tears after assembly la com-
pleted.
When glass liners are used, Install selected
nozzle using a Vlton A O-rlng; the Vlton A
O-rlng Is Installed as a seal where the nozzle
Is connected to a glass liner. See AFTD-0576
for details. When metal liners are used, In-
stall the nozzle as above or by a leak free
direct mechanical connection. Mnrk the
probe with heat resistant tape or by some
other method to denote the proper dlstanco
Into the stack or duct for each sampling
point.
Unless otherwise specified by the Admin-
istrator, attach a temperature probe to the
metal sheath of the sampling probe so that
the sensor extends beyond the probe Up and
does not touch any metal. Its position should
be about 1.9 to 2.61 cm (0.75 to 1 In.) from
the pltot tube and probe nozzle to avoid
interference with the gas flow.
Assemble the train as shown In Figure
13A-1 with the niter between the third and
fourth Implngers. Alternatively, the filter
may be placed between the probe and the
first Implnger. A filter heating system may
be used to prevent moisture condensation,
but the temperature around the filter holder
Shall not exceed 120±14°C (248±25'F).
((Note: Whatman No. I filter decomposes at
150'C (300-F)).J Record filter location on
the data sheet.
Place crushed Ice around the implngers.
7.11 Leak check procedure—After the
sampling train has been assembled, turn on
and set (If applicable) the probe and filter
heating system (s) to reach a temperature
sufficient to avoid condensation In the probe.
Allow time for the temperature to stabilize.
Leak check the train at the .sampling site by
plugging the nozzle and pulling a 380 mm Hg
(IB In. Hg) vacuum. A leakage rate In ex-
cess of 4% of the average sampling rate or
0.00057 mVmln. (0.02 cf m), whichever is less,
Is unacceptable.
The following leak check instructions for
the sampling train described in APTD-0576
and APTD-0581 may be helpful. Start the
pump with by-pass valve fully open and
coarse adjust valve completely closed. Par-
tially open the coarse adjust valve and slowly
close the by-pass valve until 380 mm Hg (IS
in. Hg) vacuum is reached. Do not reverse
direction of by-pass valve. This will cause
water to back up Into the filter holder. If
880 mm Hg (15 In. Hg) is exceeded, either
teak check at this higher vacuum or end the
leak check as described below and start over.
When the leak check is completed, first
•lowly remove the plug from the inlet to the
probe or filter holder and Immediately turn
off the vacuum pump. This prevents the
water in the Implngers from being forced
backward Into the filter holder (If placed
before the Implngers) and silica gel from
being entrained backward into the third
Implnger.
Leak checks shall be conducted as described
whenever the train Is disengaged, e.g. for
silica gel or filter changes during the test,
prior to each test run, and at the completion
of each test mn. If leaks are found to be In
excess of the acceptable rate, the test will bo
considered Invalid. To reduce lost time due
to leakage occurrences. It is recommended
that leak checks be conducted between port
changes.
7.1.6 Partlculnte train operation—During
the sampling run, an Isoklnctlc sampling rate
within 10%, or as specified by the Adminis-
trator, of true Isoklnotlc shall be maintained.
For each run, record the data required on
the tru.-r.iple data sheet shown hi Figure 13A-
3. Bo sure to record the initial dry gns meter
reading. Record the dry gas meter readings at
tho beginning and end of each sampling time
Increment, when changes In flow rates are
made, and when sampling IB halted. Take
other data point readings at least once n/t
each sample point during each time Incre-
ment and additional readings when signifi-
cant changes (20% variation in velocity head
readings) necessitate additional adjustments
In fiow rate. Be sure to level and zero the
manometer.
Clean the portholes prior to the test run to
minimize chance of sampling deposited
material. To begin sampling, remove the
nozzle cap, verify (if applicable) that the
probe heater Is working and filter heater Is
up to temperature, and that the pltot tube
nnd probp are properly positioned. Position
the nozzle at the first traverse point with the
tip pointing directly Into the gas stream. Im-
mediately start tho pump and adjust the
flow to isoklnetlo conditions. Nomographs are
available for sampling trains using type S
pltot tubes with 0.85±0.02 coefficients (Cn),
and when sampling in air or a stack gas with
equivalent density (molecular weight, Mj,
equal to 29±4), which aid in the rapid ad-
justment of the Isoklnetlc sampling rate
wlthqiit excessive computations. APTi>0576
details the procedure for using these nomo-
graphs. If C, and MJ are outside the above
stated ranges, do not use the nomograph
unless approplrate steps are taken to com-
pensate for the deviations.
When the stack Is under significant nega-
tive pressure (height of Impingcr stem), take
care to close the coarse adjust valve before
Inserting the probe into the stock to avoid
water backing Into the filter holder. If neces-
sary, the pump may be turned on with the
coarse adjust valve closed.
When the probe is In position, block off
the openings around the probe and porthole
to prevent unrepresentative dilution of the
gas stream.
Traverse the stack cross section, as required
by Method 1 or as specified by the Adminis-
trator, being careful not to bump the probe
nozzle into the stack walls when sampling
near the walls or when removing or inserting
the probe through the portholes to minimize
chance of extracting deposited material.
During the test run, make periodic adjust-
ments to keep the probe and (If applicable)
filter temperatures at their proper values. Add
more Ice and, If necessary, salt to the Ice
bath, to maintain a temperature of less than
20°C (68*F) at the Implnger/slllca gel outlet,
to avoid excessive moisture losses. Also, pe-
riodically check the level and zero of the
manometer.
If the pressure drop across the filter be-
comes high enough to make isoklnetlc sam-
pling difficult to maintain, the filter may be
replaced in the midst of a sample run. It is
recommended that another complete filter
assembly be used rather than attempting to
change the filter Itself. After the new filter or
filter assembly Is Installed conduct a leak
check. The final emission results shall be
based on the summation of all filter catches.
A single train shall bo used for the entire
sample run, except for filter and silica gel
changes. However, If approved by the Admin-
istrator, two or more trains may be used for
a single test run when there are two or more
ducts or sampling ports. The final emission
results shall be bused on the total of all
sampling train catches.
• At tho end of the sample run, turn off the
pump, remove the probe and nozzle from
the stack, and record the final Afy gas meter
reading. Perform a leak check.1 Calculate
percent Isoklnctlc (BCO calculation section)
to determine whether another test run
should be made. If there Is difficulty In main-
taining liioklnctlc rates due to source con-
-------
• 33160
RULES AND REGULATIONS
Place the crucible In a cold muffle furnace
«nd gradually (to prevent smoking) Increase
tho temperature to 600°C, and maintain un-
til the contents arc reduced to an ash. Re-
move tho crucible from the furnace and allow
It to cool.
7.3.1.3 Add approximately 4 g of crushed
NaOH to the crucible and mix. Return tho
crucible to the muffle furnace, and fuse the
sample for 10 minutes at 600°C.
Remove the sample from the furnace and
cool to ambient temperature. Using several
rinsings of worm distilled water transfer tho
contents of the crucible to the beaker con-
taining the filtrate from container No. 1
(7.3.1). To assure complete sample removal,
rinse finally with two 20 ml portions of 25
percent (v/v) sulfurlc acid and carefully add
to the beaker. Mix well and transfer a one-
liter volumetric flask. Dilute to volume with
distilled water and mix thoroughly. Allow
any undlssolved solids to settle.
7.3.2 Container No. 2. Weigh the spent
ell lea gel and report to the nearest 0.5 g.
7.3.3 Adjustment of acid/water ratio In
distillation flask—(Utilize a protective shield
when carrying out this procedure.) Place 400
ml of distilled water In the distilling flask
and add 200 ml of concentrated H.,SO4. Cau-
tion: Observe standard precautions when
mixing the H,SO< by slowly adding the acid
to the flask with constant swirling. Add some
soft glass beads and several small pieces of
broken glass tubing and assemble the ap-
paratus as shown In Figure 13A-2. Heat the
flask until It reaches a temperature of 175°C
to adjust the acid/water ratio for subsequent
distillations. Discard the distillate.
7.3.4 Distillation—Cool the contents of
the distillation flask to below 80°C. Pipette
on aliquot of sample containing less than 0.6
mg P directly Into the distilling flask and add
distilled water to make a total volume of 220
ml added to the distilling flask. [For an es-
timate of what size aliquot does not exceed
0.6 mg P. select an aliquot of the solution
and treat as described In Section 7.3.6. This
will give an approximation of the fluoride
content, but only an1 approximation since
Interfering ions have not been removed by
the distillation step.]
Place a 250 ml volumetric flask at the con-
denser exit. Now begin distillation and grad-
ually Increase the heat and collect all the
distillation up to 175°C. Caution: Heating"
the solution above 175 °C will cause sulfuric
acid to distill over.
The acid in the distilling flask can be used
until there Is carryover of interferences or
poor fluoride recovery. An occasional check of
fluoride recovery with standard solutions Is
advised. The acid should bo changed when-
ever there Is less than 90 percent recovery
or blank values are higher than 0.1 Mg/ml.
Note: If the sample contains chloride, add
5 mg Ag.SO, to the flask for every mg of
chloride. "Gradually Increase the heat and
collect at the distillate up to I75°C. Do not
exceed 175°C.
7.3.5 Determination of Concentration—
Bring the distillate In the 250 ml volumetric
flask to the mark with distilled water and
mix thoroughly. Pipette a suitable aliquot
from the distillate (containing 10 Mg to 40
jtg fluoride) and dllxite to 50 ml with dis-
tilled water. Add 10 ml of SPADNS Mixed Rea-
gent (sec Section 0.3.12) and mix thoroughly.
After mixing, place the sample In tv con-
stant temperature bath containing the stand-
ard solution for thirty minutes before read-
Ing the absorbance with the spectropho-
tometer.
Set the spectrophotometer to zero absorb-
anco at 670 nm with reference solution
(6.3.11), and check tho spectrophotometer
calibration with.the standard solution. De-
termine the absorbance of tho samples and
determine tho concentration from the cali-
bration curve. If the concentration does not
full within the range of the calibration curve,
repeat tho procedure using a different size
aliquot.
8. Calibration.
Maintain a laboratory log of all calibrations.
8.1 Sampling Train.
8.1.1 Probo nozzle—Using a micrometer,
measure the Inside diameter of the nozzle
to the nearest 0.025 mm (0.001 In.). Mnko
3 separate measurements using different
diameters each time and obtain the average
of the measurements. The dlderenco between
the high and low numbers shall not exceed
0.1 mm (0.004In.).
When nozzles become nicked, dented, or
corroded, they shall be reshaped, sharpened,
and recalibrated before use.
Each nozzle shall be permanently and
uniquely Identified.
8.1.2 Pltot tube—The pltot tube shall be
calibrated according to the procedure out-
lined In Method 2.
8.1.3 Dry gas meter and orifice meter.
Both meters shall be calibrated according to
the procedure outlined In APTD-0576. When
diaphragm pumps with by^pass valves are
used, check for proper metering system de-
sign by calibrating the dry gas meter at an
additional flow rate of 0.0057 mVmln. (0.2
cfm) with the by-pass valve fully opened
and then with it fully closed. If there Is more
than ±2 percent difference In flow rates
when compared to the fully closed position
of the by-pass valve, the system is not de-
signed properly and must be corrected.
8.1.4 Probe heater calibration—The probe
heating system shall be calibrated according
to the procedure contained in APTD-0576.
Probes constructed according to APTD-0581
need not be calibrated If the calibration
curves In APTD-0576 are used.
8.1.5 Temperature gauges—Calibrate dial
and liquid filled bulb thermometers against
mercury-ln-glass thermometers. Thermo-
couples need not be calibrated. For other
devices, check with the Administrator.
8.2 Analytical Apparatus. Spectrophotom-
eter. Prepare the blank standard by adding
10 ml of SPADN3 mixed reagent to 60 my of
distilled water. Accurately prepare a series
of standards from the standard fluoride solu-
tion (sea Section 6.3.9) by diluting 2, 4, 8,
8. 10, 12, and 14 ml volumes to 100 ml with
distilled water. Pipette 60 ml from each solu-
tion and transfer to a 100 ml beaker. Then
add 10 ml of SPADNS mixed reagent to each.
These standards will contain 0, 10, 20, 30,
40, 60, 60, and 70 /ig of fluoride (0—1.4 /ig/ml)
respectively.
After mixing, place the reference standards
and reference solution in a constant tem-
perature bath for thirty minutes before read-
Ing the absorbance with the spectrophotom-
eter. All samples should be adjusted to this
same temperature before analyzing. Since
a 3"C temperature difference between samples
and standards will produce an error of ap-
proximately 0.005 mg F/llter, care must be
taken to see that samples and standards are
at nearly Identical temperatures when ab-
Borbances are recorded.
With the spectrophotometer at 670 nm,
use the reference solution (see section 6.3.11)
to set the absorbance to zero.
Determine tho absorbance of the stand-
ards. Prepare a calibration curve by plotting
lig F/60 ml versus absorbnnce on linear graph
.paper. A standard curve should be prepared
Initially and thereafter whenever the
SPADNS mixed reagent is newly made. Also,
a calibration standard should bo run with
each set of samples and If It differs frt'iii tho
calibration curve by ±2 percent, « new
standard curve should be prepared.
9. Calculations.
Carry out calculations, retaining at least
one extra decimal figure beyond that of the
Required data. Round off figures after final
calculation.
9.1 Nomenclature.
^
-------
RULES AMD REGULATIONS 331 fit
rp , A//-]
„ r.lt\ ' tmr+TS3 \ Kv p».r+AH/13.0
.<„*» V. -y- [/-/T^—J-A *. jr
ccjualion 13A-1
where:
Jf=0.3855 'K/mm US far-metric units.
=17.00 'It/In. Kg for English units.
9.4 Volume of water vapor.
, = V,c £- —,—= KV,, equation 13A-2
where:
K=0.00131 mVml for metric units.
=0.0*72 ftVml for English units.
9.5 Moisture content.
V
*J WM — Yr | I/
\ M(ll«H- I l» (•(,!)
cqualiou 13A-3
If the liquid droplets are present In the
gas stream assume the stream to be saturated
and use a psychrometrlc chart to obtain an
approximation of the moisture percentage.
9.6 Concentration.
9.G.1 Calculate the amount of fluoride in
the sample according to Equation 13A-4.
equation 13A-4
where:
0.0.2 Concentration of fluoride In stack
gas. Determine the Concentration of fluoride
In the stack gas according to Equation 13A-5.
.= ~-
I m(«(iO
equation 13A-5
where :
X = 35.31 ttVm".
9.7 Isokliietlc variation.
9.7.1 Calculations from raw data.
100 T. [KVlc+(Va/Tm) (PW + A///13.G)] „„„„,-•,,» R
: ±^—'.— '_ equation loA-o
where:
K=6.00340 mm Hg-mVml-"K for metric
units.
=0.00267 la. Hg-ftVml-"B for English
units.
9.7.2 Calculations from Intermediate val-
ues.
.v.1,1* p.,,, IPO
~~
T V
~^-rrr^TT~\ equation 13A-7-
whcre: Fluoride Determination In Stack Emission
K=4.323 for metric units. Samples," Analytical Chemistry 40: 1272-
=0.0944 for English units. 1273(1973).
9.8 Acceptable results. The following Martin, Robert M.. "Construction Details
range sets tlic limit on acceptable Isoklnctlc of Isoklnetlc Source Sampling Equipment,"
campling results: Environmental Protection Agency, Air Pollu-
If 00 percent n^ u-nth.. w j tr , T <-. i i bv American Public Health Association,
MacLeod. Kathryn E.( and Howard L. Crist. A^ncrlcnll Watt.r Works AssoclaUoll Bnd'
•Comparison of the SPADNS--Zirconium Water Pollution Control Federation, 13tll
Lake and Spccinc Ion Electrode Methods of Edition (1971).
FEDERAL REGISTER, VOL. 40, NO. 152—WEDNESDAY, AUGUST 6, 1975
-------
33162
RULES AND REGULATIONS
1.9? 3 cm
(0.7S lin.)
.
1.3cm (0.vViii.P
HTOTTUBE
TEMPERATURE
StNSOR
PROBE
RF!
OPTIONAL I
i FILTERHoinun i
STACKWALL j_ IOMTIOH |
PROBE j^jX "'riLTERIIOLOER
<, p .-:T.———-=-=•—^.-T^TI ^ ..^ t v f x 'p^l
filVEr.SC-TYPE
FITOTTUBE
\ /^" J
ORIFICE MANOMETER
•-AIRTIGHT
PUMC
Fiijuro 13A 1. Fkiorifji-s.ini|j!ing trjin.
CC.MWEUTiNGTUBE
t"2'110
THERMOMETER TIP MUST EXTEUD BELOW
TKELIQUIU LEVEL
WiTHf 10/30
{24/40
JZ4/40
HEATING
MANTLE
250 ml
VOLUMETRIC
FLASK
-igurc 13A-2. Fluoride Distillation Apparatus
FEDERAL REGISTER, VOL. 40, NO. 152—WEDNESDAY, AUGUST 6, 1975
-------
RULES AND REGULATIONS
KMT.
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mum
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r.gi.rc 13A-3. Field daw.
METHOD 13B DETERMINATION OP TOTAL FLUO-
RIDE EMISSIONS FROM STATION AH Y bOURCES
SPECIFIC ION ELECTRODE METHOD.
1. Principle and Applicability.
1.1 Principle. Gaseous and paniculate flu-
orides are withdrawn Isoklnetically from the
source using a sampling train. The fluorides
are collected in the impingcr water and on
the filter of the sampling train. The weight
or total fluorides in the train is determined
by the specific-Ion electrode method.
1.2 Applicability. This method is ap-
plicable lor the determination of fluoride
emissions from stationary sources only when
specified by the test procedures for deter-
mining compliance with new source per-
formance standards. Fluorocarbons such as
Frcons, are not quantitatively collected or
measured by this procedure.
2. Range and Sensitivity.
The fluoride specific Ion electrode analyti-
cal method covers the range of 0.02-2,000 /ig
F/nil; however, measurements of less than
0.1 /ig F/ml require extra care. Sensitivity has
not been determined.
3. Interference}.
During the laboratory analysis, aluminum
In excess of 300 mg/liter and silicon dioxide
In excess of 300 /iQ/liter will prevent complete
recovery of fluoride.
4. Precision, Accuracy and Stability.
The accuracy of fluoride electrode measure-
ments has been reported by various re-
searchers to be In the range of 1-5 percent In
a concentration range of 0.04 to 80 mg/1. A
change in the temperature of the sample will
change the electrode response; a change of
1'C will produce a 1.5 percent relative error
In the measurement. Lack of stability In the
electrometer ilscd to measure EMF can intro-
duce error. An error of 1 millivolt In the EMF
measurement produces a relative error of 4
percent regardless of the absolute concen-
tration being measured.
5. Apparatus.
5.1 Sample train. Sec Figure 13A-1
(Method 13A); It Is similar to the Method 5
train except for the intcrchangcablllty of
the position of the filler. Commercial models
of this train are available. However, If one
desires to build his own, complete construc-
tion details lire described In APTD-OD81; for
changes from tho APTD- 0531 document and
for allowable modifications to Figure 13A-1,
see the following subsections.
The operating and maintenance procedures
for the sampling train are described In
APTD-0570. Since correct xtsage is Impor-
tant In obtaining valid results, all users
should read the APTD-0576 document and
adopt the operating and maintenance pro-
cedures outlined In It, unless otherwise spec-
ified herein.
5.1.1 Probe nozzle-—Stainless steel (316)
with sharp, tapered leading edge. The angle
of taper shall be 530° and the taper shall be
on the outside to preserve a constant inter-
nal diameter. The probe nozzle shall be of
the button-hook or elbow design, unless
otherwise specified by the Administrator.
The wall thickness of the nozzle shall be
less than or equal to that of 20 gauge tub-
ing, I.e., 0.165 cm (0.065 in.) and the distance
from the tip of the nozzle to the first bend
or point of disturbance shall be at least two
times the outside nozzle diameter. The noz-
zle shall be constructed from seamless stain-
less steel tubing. Other configurations and
construction material may be used with ap-
proval from the Administrator.
A range of sizes suitable for Isoklnetlc
sampling should be available, e.g., 0.32 crn
(>i in.) up to 1.27 cm (Vi in.) (or larger If
higher volume sampling trains are used)
inside diameter (ID) nozzles in increments
of 0.10 cm (Via in.). Each nozzle shall be
calibrated according to the procedures out-
lined in the calibration section.
5.1.2 Probe liner—Borosilicate pl.iss or
stainless steel (310). When the filter Is lo-
cated Immediately after the probe, a probe
heating system may be \iscci to prevent filter
plugging resulting from moisture conden-
sation. The temperature In tho probe shall
not exceed 120±14°C (248-.!:25'F).
5.1.3 Pilot tube—Type S, or other device
approved by the Administrator, attached to
probe to allow constant monitoring of tho
stack gas velocity. The fnce openings of tho
pitot tube and the probe noirule shall be ad-
jacent and parallel to each other, not neces-
sarily on the snme plane, during sampling.
The free space between the no?zle nnd pilot
tube .shall bo at least 1.9 cm (0.75 in.). Tho
free space shall bo set based on a 1.3 cm
(0.5 in.) ID nozzle, which Is the largest size-
nozzle used.
The pilot tube must also meet the criteria
specified in Method 2 and be calibrated ac-
cording to the procedure in the calibration
section of that method.
6.1.4 Differential pressure gauge—In-
clined manometer capable of measuring
velocity head to within 10 percent of the
minimum measured value. Below a differen-
tial pressure of 1.3 mm (0.05 In.) water
gauge, mlcromsinometcrs with sensitivities
of 0.013 mm (0.0005 In.) should be used.
However, mlcromanomcters arc not easily
adaptable to field conditions and are not
easy to use with pulsating flow. Thus, other
methods or devices acceptable to the Ad-
ministrator may be used when conditions
warrant.
6.1.5 Filler holder—Borosilicate gla^s
with a glass frit niter support and a slllcone
rubber gasket. Other materials of construc-
tion may be used with approval from the
Administrator, e.g. if probe liner Is stain-
less steel, then filter holder may be stainless
steel. The holder design shall provide a posi-
tive seal against leakage from the outside
or around the filter.
5.1.6 Filter heating syslem—When mois-
ture condensation is a problem, any heatin;;
system capable of maintaining a temperature
around the filter holder during sampling of
no greater than 120±U'C (248±25°F). A
temperature gauge capable of measuring tem-
perature to within 3°C (5.4'F) shall be In-
stalled so that when the filter heater is used,
the temperature around the filter holder can
be regulated and monitored during sampling.
Heating systems other than the one shown
In APTD-0581 may be used.
5.1.7 Implngers—Four implngers con-
nected as shown In Figure 13A-1 with ground
glass (or equivalent), vacuum tight fittings.
The first, third, and fourth Implngers are ol
the Greenburg-Smith design, modified by re-
placing the tip with a 1% cm (% In.) Jnside
diameter glass tube extending to 1% cm ('/2
In.) from the bottom of the flask. The second
Impinger is of the Greenburg-Smlth design
with the standard tip.
5.1.9 Melering system—Vacuum gauge.
leak-free pump, thermometers capable of
measuring temperature to within 3'C
(~5°F), dry gas meter with 2 percent ac-
curacy at the required sampling rate, and
related equipment, or equivalent, as required
to maintain an Isokinetlc sampling rate and
to determine sample volume. When the
metering system is used In conjunction with
a pitot tube, the system shall enable checks
of Isokinetic rates.
5.1.0 Barometer—Mercury, aneroid, or
other barometers capable of measuring at-
mospheric pressure to within 2.5 mm Hg (0.1
in Hg). In many cases, the barometric read-
ing may be obtained from a nearby weather
bureau station, in which case the station
value shall be requested and an adjustment
for elevation differences shall be applied at a
rate of minus 2.5 mm H^ (0.1 In. Hg) per 30
m (100 ft) elevation Increase.
5.2 Sample recovery.
5.2.1 Probe liner and probe nozzle
brushes—Nylon bristles with stainless steel
wire handles. The probe brush shall have
extensions, at least as long as the probe, of
stainless steel, teflon, or similarly inert mate-
rial. Both brushes shall bo properly sized untl
shaped to brush out the probe liner and noz-
zle.
fi.2.2 Glass wash bottles—Two.
5.2.3 Sample storage containers—Wldo
mouth, high density polyethylene bottles, 1
liter.
6.2.4 Plastic storage containers—Air tight
containers of sufficient volume to store silicii
gel.
5 2.6 Graduated cylinder—250 ml.
6.3.0 Funnel and rubber policeman—To
aid in transfer of silica gel to container; not
necessary if silica gel Is weighed In the Held.
FEDERAL REGISTER, VOL. 40, NO. 152—WEDNESDAY, AUGUST 6, 1975
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-33164
RULES AND REGULATIONS
5.3 Analysis.
5.3.1 Distillation apparatus—Glass distil-
lation apparatus assembled as shown In FJg-
uro 13A-2 (Method 13A).
6.3.2 Hot plate—Capable of heating to
600°C.
6.3.3 Electric muffle furnace—Capable of
heating to 600 °C.
6.3.4 Crucibles—Nickel, 75 to 100 ml
capacity. _ .
6.3.5 Beaker—1500 ml.
6.3.6 Volumetric flask—50 ml.
6.3.7 Erlenmeyer flask or plastic bottle—
600 ml.
6.3.8 Constant temperature bath—Cap-
able of maintaining a constant temperature
of ±1.0°C In the range of room temperature.
5.3.9 Trip balance—300 g capacity to
measure to ±0.5 g.
5.3.10 Fluoride Ion activity sensing elec-
trode.
5.3.11 Reference electrode—Single Junc-
tion; sleeve type. (A combination-type elec-
trode having the references electrode and
the fluoride-ion sensing electrode built Into
one unit may also be used).
5.3.12 Electrometer—A pH meter with
millivolt scale capable of ±0.1 mv resolu-
tion, or a specific Ion meter made specifically
for specific Ion use.
6.3.13 Magnetic stirrer and TFE fluoro-
carbon coated stripping bars.
6. Reagents.
6.1 Sampling.
6.1.1 Filters—Whatman No. 1 filters, or
equivalent, sized to fit filter holder.
6.1.2 Silica get—Indicating type, 6-16
mesh. If previously used, dry at 175°C
(350°F) for 2 hours. New silica gel may bo
tised as received.
6.1.3 Water—Distilled.
6.1.4 Crushed Ice.
0.1.5 Stopcock grease—Acetone Insoluble,
heat stable silicone grease. This Is not neces-
sary If screw-on connectors with teflon
sleeves, or similar, are used.
6.2 Sample recovery.
6.2.1 Water—Distilled from same con-
tainer as 6.1.3.
6.3 Analysis.
6.3.1 Calcium oxide (CaO)—Certified
grade containing 0.005 percent fluoride or
less.
6.3.2 Phenolphtlialeln Indicator—0.1 per-
cent in 1:1 ethanol water mixture.
6.3.3 Sodium hydroxide (NaOH)—Pel-
lets, ACS reagent grade or equivalent.
6.3.4 SuUuric acid (H..SO,)—Concen-
trated, ACS reagent grade or "equivalent.
6.3.' Filters—Whatman No. 641, or
equivalent.
6.3.6 Water—Distilled, from same con-
tainer as 6.1.3.
6.3.7 Total Ionic Strength Adjustment
Buffer (TISAB)—Place approximately 600
ml of distilled water in a 1-liter beaker. Add
57 ml glacial acetic acid, 50 g sodium chlo-
ride, and 4 g CDTA (Cyclohexylcne dlnltrilo
tetrnacetic acid). Stir to dissolve. Place the
beaker In a water bath to cool it. Slowly
add 6 M NaOH to the solution, measuring
the pH continuously with a calibrated pH/
reference electrode pair, until the pH Is 5.3.
Cool to room temperature. Pour Into a 1-liter
flask and dilute to volume with distilled
water. Commercially prepared TISAB buffer
may be substituted for the above.
0.3.8 Fluoride Standard Solution—0.1 M
fluoride reference solution. Add 4.20 grams of
reagent grade sodium fluoride (NaF) to a 1-
Hter volumetric flask and add enough dis-
tilled water to dissolve. Dilute to volume
with distilled water.
7. Procedure.
NOTE: The fusion and distillation steps of
this procedure will not be required, If It can
bo shown to the satisfaction of the Admin-
istrator that the samples contain only water-
soluble fluorides.
7.1 Sampling. The sampling shall be con-
ducted by competent personnel experienced
with this test procedure.
7.1.1 Pretest preparation. All train com-
ponents shall bo maintained and calibrated
according to the procedure described In
APTD-0576, unless otherwise specified
herein.
Weigh approximately 200-300 g of silica gel
In air tight containers to the nearest 0.5 g.
Record the total weight, both silica gel and
container, on the container. More silica gel
may be used but care should be taken during
sampling that it Is not entrained and carried
out from the impingcr. As an alternative, the
silica gel may be weighed directly In the 1m-
plnger or its sampling holder Just prior to
the train assembly.
7.1.2 Preliminary determinations. Select
the sampling site and the minimum number
of sampling points according to Method 1 or
as specified by the Administrator. Determine
the stack pressure, temperature, and the
range of velocity heads using Method 2 and
moisture content using Approximation
Method 4 or Its alternatives for the purpose
of making Isokinetic sampling rate calcula-
tions. Estimates may be used. However, final
results will be based on actual measure-
ments made during the test.
Select a nozzle size based on the range of
velocity heads such that it is not necessary
to change the nozzle size In order to maintain
isoklnetlc sampling rates. During the run, do
not change the nozzle size. Ensure that the
differential pressure gauge Is capable of
measuring the minimum velocity head value
to within 10 percent, or as specified by the
Administrator.
Select a suitable probe liner and probe
length such that all traverse points can be
sampled. Consider sampling from opposite
sides for large stacks to reduce the length of
probes.
Select a total sampling time greater than
or equal to the minimum total sampling
time specified in the test procedures for the
specific Industry such that the sampling time
per point Is not less than 2 min. or select
some greater time Interval as specified by
the Administrator, and such that the sample
volume that will be taken will exceed the re-
quired minimum total gas sample volume
specified in the test procedures for the spe-
cific industry. The latter Is based on an ap-
proximate average sampling rate. Note also
that the minimum total sample volume Is
conected to standard conditions.
It Is recommended that a half-Integral or
Integral number of minutes be sampled at
each point In order to avoid timekeeping
errors.
In some circumstances, e.g. batch cycles, It
may be necessary to sample for shorter times
at the traverse points and to obtain smaller
fj'as sample volumes. In these cases, the Ad-
ministrator's approval must first be obtained.
7.13 Preparation of collection train. Dur-
ing preparation and assembly of the sampling
train, keep all openings where contamination
can occur covered until Just prior to assembly
or until sampling is about to begin.
Place 100 ml of water in each of the first
two impingers. leave the third linpinger
empty, and place approximately 200-300 g or
more, if necessary, of prcwelghed silica gel In
the fourth Implnger. Record the weight of
the silica gel and container on the datasheet.
Place the empty container In a clean place
for later use In the sample recovery.
Place a filter In the filter holder. Be sure
that the filter Is properly centered and the
gasket properly placed so as to not allow the
cample gas stream to circumvent the filter.
Check filter for tears after assembly is com-
pleted. ,
When glass liners are used, Install selected
nox//,)o using a Vlton A O-rlng; the Vlton A
O-rlng Is Installed as a peal where the nozzle
Is connected to a glass liner. See APTD-0576
for details. When metal liners are used, In-
stall the nozzle as above or by a leak frco
direct mechanical connection. Mark the probe
with heat resistant tape or by some other
method to denote the proper distance Into
the stack or duct for each sampling point.
Unless otherwise specified by the Admin-
istrator, attach a temperature probe to the
metal sheath of the sampling probe so that
the sensor extends beyond the probe tip and
does not touch any metal. Its position should
be about 1.9 to 2.51 cm (0.75 to 1 in.) from
the pltot tube and probe nozzle to avoid In-
terference with the gas flow.
Assemble the train as shown In Figure
13A-1 (Method 13A) with the filter between
the third and fourth Impingers. Alterna-
tively, the filter may be placed between the-
probe and first Implnger. A filter heating sys-
tem may be used to prevent moisture con-
densation, but the temperature around the
filter holder shall not exceed 1200±14°C
(248±25°F). [(Note: Whatman No. 1 filter
decomposes at 150°C (300°F)).J Record
filter location on the data sheet.
Place crushed Ice around the Impingers.
7.1.4 Leak check procedure—After the
sampling train has been assembled, turn on
and set (If applicable) the probe and..fllter
heating system(s) to reach a temperature
sufficient to avoid condensation In the probe.
Allow time for the temperature to stabilize.
Leak check the train at the sampling site by
plugging the nozzle and pulling a 380 mm
Hg (15 In. Hg) vacuum. A leakage rate In ex-
cess of 4% of the average sampling rate of
0.0057 mVmln. (0.02 cfm), whichever Is less.
Is unacceptable.
The following leak check Instruction for
the sampling train described In APTD-0676
and APTD-0581 may be helpful. Start the
pump with by-pass valve fully open and
coarse adjust valve completely closed. Par-
tially open the coarse adjust valve and slow-
ly close the by-pass valve until 380 mm Hg
(15 In. Hg) vacuum Is reached. Do Not re-
verse direction of by-pass valve. This will
cause water to back up into the filter holder.
If 380 mm Hg (15 in. Hg) Is exceeded, either
leak check at this higher vacuum or end the
leak check as described below and start over.
When the leak check is completed, first
slowly remove the plug from the inlet to the
probe or filter holder and Immediately turn,
off the vacuum pump. Tills prevents the
water In the Impingers from being forced
backward into the filter holder (if placed
before the Impingers) and silica gel from.
being entrained backward Into the third
implnger.
Leak checks shall be conducted as de-
scribed whenever the train is disengaged, e.g.
for silica gel or filter changes during the test,
prior to'each test run, and at the completion
of each test run. If leaks are found to bo In
excess of the acceptable rate, the test will be
considered Invalid. To reduce lost time due to
leakage occurrences, It Is recommended that
leak checks be conducted between port
changes.
7.1.5 Partlculate train operation—During
the sampling run, an Isokinetic sampling
rate within 10%, or as specified by the Ad-
ministrator, of true isokinetic shall be main-
tained.
For each run, record the data required on
the example data sheet shown In Figure
13A-3 (Method ISA). Bo sure to record the
Initial dry gas meter reading. Record the
dry gas meter readings at the beginning and
end of each sampling time Increment, when
changes In flow rates are made, and when
sampling Is halted. Take other data point
readings at least once at each sample point
(luring each time Increment and additional
readings when significant changes (20%
variation In velocity head readings) ncces-
FEDERAL REGISTER, VOL. 40, NO. 152—WEDNESDAY, AUGUST 6, 1975
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RULES AND REGULATIONS
.'W1C5
Bllato additional adjustments In now rate. Bo
sure to level and zero the manometer.
Clean the portholes prior to the test run
to minimize chance of sampling deposited
material. To begin sampling, remove the
nozzle cap, verify (if applicable) that the
probe heater la working und niter heater Is
up to temperature, and that the pltot tube
and probe are properly positioned. Position
the nozzle at the nrst traverse point with
the Up pointing directly into the gas stream.
Immediately start the pump and adjust the
How to Isokmcllc conditions. Nomographs are
available for sampling trains using typo S
pltot tubes with 0.85 + 0.02 (cocfllclouts (C»),
and when sampling in air or a stack gas with
equivalent density (molecular weight, Md.
equal to 29±4), which aid in the rapid ad-
justment of the isokljietlc sampling rate
without excessive computations. APTD-0576
details the procedure for x\slng those nomo-
graphs. It Cp and M< are outside the above
stated ranges, do not use the nomograph un-
less appropriate steps ore taken to compen-
sate for the deviations.
When the stack is under significant neg-
ative pressure (height of Implnger stein),
take care to close the coarse adjust valve
before inserting the probe into .the stack to
avoid water backing into the filter holder. If
necessary, the pump may be turned on with
the coarse adjust valve closed.
When the probe is in position, block off
the openings around the probe and porthole
to prevent unrepresentative dilution of the
gas stream.
Traverse the stock cross section, as re-
quired by Method 1 or us specified by the Ad-
ministrator, being careful not to bump the
probe nozzle Into the stack walls when
sampling near the walls or when removing
or Inserting the probe through the port-
holes to minimize chance of extracting de-
posited material.
During the test run, make periodic adjust-
ments to keep the probe and (If applicable)
filter temperatures at their proper values.
Add more ice and, If necessary, salt to the
Ice bath, to maintain a temperature of less
than 20'C (68"F) at the Implnger/slllca gel
outlet, to avoid excessive moisture losses.
Also, periodically check the level and zero
of the manometer.
If the pressure drop across the filter be-
comes high enough to make Isokinetlc sam-
pling difficult to maintain, the filter may be
replaced in the midst of a sample run. It is
recommended that another complete filter as-
sembly be used rather than attempting to
change the filter itself. After the new filter
or filter assembly is Installed, conduct a
leak check. The final emission results shall
be based on the summation of all filter
catches.
A single train shall be used for the entire
sample run, except for filter and silica gel
changes. However, if approved by the Admin-
istrator, two or more trains may be used for
a single test run when there are two or more
ducts or sampling ports. The final emission
results shall be based on the total of all
sampling train catches.
At the end of the sample run, turn off the
pump, remove the probe and nozzle from
the stack, and record the final dry gas meter
reading. Perform a leak check.1 Calculate
percent Isokinetlc (see calculation section) to
determine whether another test run should
be made. If there Is difficulty in maintaining
Isokinetlc rates due to source conditions, con-
sult with the Administrator for possible
.variance on the Isokinetlc rates.
»With acceptability of the test run to be
based on the same criterion as in 7.1.4.
7.2 • Sample recovery. Proper cleanup pro-
cedure begins as soon as the probe la re-
moved from the slack at the end of the
sampling period.
When the probe can bo safely handled,
wipe off all external purtlculate matter near
the Up of the probe nozzle and place a cap
over It to keep from losing part of the sam-
ple. Do not cap off the probe tip tightly
while the sampling train Is cooling down,
as this would create a vacuum In the filter
holder, thus drawing water from -the 1m-
plngors Into the filter.
Before moving the sample train to the
cleanup site, remove the probe from the
sample train, wipe off the slllcono grease,
and cap the open outlet of the probe. Bo
careful not to lose any condens.ito, if pres-
ent. Wipe off the slllconc grease from the
filter inlet where the probe was fastened
and cap it. Remove the umbilical cord from
the last Implnger and cap the imptnger. After
wiping off the slllcone grenso, cap ofT the
filter holder outlet and Implnger inlet.
Ground glass stoppers, plastic caps, or seruui
caps may be used to close these openings.
Transfer the probe and fllter-lmplnger as-
sembly to the cleanup area. Tills area should
be clean and protected from the wind so that
the chances of contaminating or losing the
sample will bo minimised.
Inspect the train prior to and during dis-
assembly and note any abnormal conditions.
Using a graduated cylinder, measure and re-
cord the volume of the water in the first
three Implngers, to the nearest ml; any con-
densate in the probe should be Included In
this determination. Treat the samples as
follows:
No. 71778, Pauley, J. E., 8-5-75
7.2.1 Container No. 1. Transfer the Im-
plnger water from the graduated cylinder
to this container. Add the filter to this
container. Wash all sample exposed sur-
faces, Including the probe tip, probe, first
three implngers, Implnger connectors, filter
holder, and graduated cylinder thoroughly.
with distilled water. Wash each component
three separate times with water and clean
the probe and nozzle with brushes. A max-
imum wash of 500 ml is used, and the wash-
Ings are added to the sample container
which must be made of polyethylene.
7.2.2 Container No. 2. Transfer the silica
gel from the fourth irapinger to this con-
tainer and seal.
7.3 -Analysis. Treat the contents of each
sample container as described below.
7.3.1 Container No. 1.
7.3.1.1 Filter this container's contents, in-
cluding the Whatman No 1 filter, through
Whatman No. 641 filter paper, or equivalent
Into a 1500 ml beaker. NOTE: If filtrate vol-
ume exceeds 900 ml make filtrate basic with
NaOH to phenolphthatcin and evaporate to
less than 000 ml.
7.3.1.2 Place the Whatman No. 541 filter
containing the insoluble matter (Including
the Whatman No. 1 filter) in a nickel cru-
cible, add a few ml of water and macerate
the filter with a glass rod.
Add 100 mg CaO to the crucible and mix
the contents thoroughly t.o form a slurry. Add
a couple of drops of phonolphthaleln Indi-
cator. The indicator will turn red in a basic
medium. The Blurry should remain basic
during the evaporation of the water or
fluoride Ion will bo lost. If the indicator
turns colorless during the evaporation, an
arldlc condition is Indicated. If this happens
add CaO until the color turns red nnnln.
Place the crucible In a hood under in-
frared lumps or on a hot plate at low heat.
Evaporate ,tho water completely.
After evaporation of the water, place the
crucible on a hot plate under a hood and
slowly increase the temperature until the
paper chars. It may take several hours for
complete charring of the filter to occur.
Place the crucible in a cold mufllo furnace
and gradually (to prevent smoking) increase
the temperature to COO'C, and maintain until
the contents are reduced to an ash. Remove
the crucible from the furnace and allow it to
cool.
7.3.1.3 Add approximately 4 g of crushed
NaOH to the crucible and mix. Return the
crucible to the muffle furnace, and fuse the
sample for 10 minutes at 600'C.
Remove the sample from the furnace and
cool to ambient temperature. Using several
rinsings of warm distilled water transfer
the contents ol the crucible to the beaker
containing the filtrate from container No.
1 (7.3.1). To assure complete sample re-
moval, rinse finally with two 20 ml portions
of 25 percent (v/v) sulfurlc acid and care-
fully add to the beaker. Mix well and trans-
fer to a one-liter volumetric flask. Dilute
to volume with distilled water and mix
thoroughly. Allow any undlssolved solids to
settle.
7.3.2 Container No. 2. Weigh the spent
silica gel and report to the nearest 0.5 g.
7.3.3 Adjustment of add/water ratio in
distillation flask—(TTUltee a protective shield
when carrying out this procedure). Place 400
ml of distilled water in the distilling flask
and add 200 ml of concentrated H,SO<. Cau-
tion: Observe standard precautions when
mixing the HJ3O( by slowly adding the acid
to the flask with constant swirling. Add some
soft glass beads and several small pieces of
broken glass tubing and assemble the ap-
paratus as shown In Figure 13A-2. Heat the
flask until It reaches a temperature of 175"C
to adjust the acid/water ratio for subsequent
distillations. Discard the distillate.
7.3.4 Distillation—Cool the contents of
the distillation fast to below 80°C. Pipette
an aliquot of sample containing less
than 0.0 mg P directly Into the dlsllUing
flosk and add distilled water to make a total
volume of 220 ml added to the distilling
flask. [For an estimate of what size aliquot
does not exceed 0.6 mg P, select an aliquot
of the solution and treat as described in
Section 7.3.6. Tills will give an approxima-
tion of the fluoride content, but only an ap-
proximation since Interfering ions have not
been removed by the distillation step.]
Place a 250 ml volumetric flask at the con-
denser exist. Now begin distillation and
gradually increase the heat and collect sill the
distillate up to 175"C. Caution: Heating the
solution above 175*C will cause sulfuric acid
to distill over.
The acid in the distilling flask can be
vised until there Is carryover of interferences
or poor fluoride recovery. An occasional
check of fluoride recovery with standard
solutions is advised. The acid should
bo changed whenever there is less than 90
percent recovery or blank values are higher
than 0.1 vig/ml.
7.3.5 Determination of concentration—
Bring the distillate in the 250 ml volumetric
flask to the mark with distilled water and
mix thoroughly. Pipette a 25 ml aliquot from
the distillate. Add an equal volume of TISAB
and mix. The sample should be at the
same temperature as the calibration stand-
ards when measurements are made. If
ambient lab temperature fluctuates more
than ±2*C from the temperature at which
tho calibration stiuicinrdu were measured,
condition samples and standards in a con-
stant temperature bath measurement. Btlr
tho sample with a magnetic stlrrcr during
measurement to minimize electrode response
FEDERAL REGISTER, VOl. 40, NO. 1S2—WEDNESDAY, AUGUST 6, 1975
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33166
RULES AND REGULATIONS
time. IT the stlrrcr generates enough heat to
change solution temperature, place a piece
of Insulating material uuch as cork
between the sllrrer find the beaker. Dilute
samples (below 10-» W fluoride Ion content)
should be held In polyethylene or poly-
propylene beakers during measurement.
Insert the fluoride and reference electrodes
Into the solution. When a steady millivolt
reading Is obtained, record It. This may take
several minutes. Determine concentration
from the calibration curve. Between elec-
trode measurements, soak tho fluoride sens-
Ing electrode in distilled water for 30 seconds
and then remove and blot dry.
8. Calibration.
Maintain a laboratory log of all
calibrations.
8.1 Sampling Train.
8.1.1 Probe nozzle—Using a micrometer,
measure the Inside diameter of the nozzle
to the nearest 0.025 mm (0.001 in.). Make
3 separate measurements using different
diameters each time and obtain tho average
of the measurements. The difference between
the high and low numbers shall not exceed
0.1 mm (0.004 in.).
When nozzles become nicked, dented, or
corroded, they shall be reshaped, sharpened,
and recalibrated before use.
Each nozzle shall be permanently and
uniquely identified.
8.1.2 Pltot tube—The pilot tube shall be
calibrated according to tho procedure out-
lined In Method 2.
8.1.3 Dry gas meter and orifice meter.
Both meters shell be calibrated according to
the procedure outlined in APTD-OS76. When
diaphragm pumps with by-pass valves are
•used, check for proper metering system
design by calibrating the dry gas meter at an
additional flow rate of 0.0057 mVmin. (0.2
cfm) with tho by-pass valve fully opened
and then w'.th it fully closed. If there is
more than ±2 percent difference In flow
rates when compared to the fully closed posi-
tion of the by-poss valve, the system is not
designed properly and must be corrected.
8.1.4 Probe heater calibration—Tho probe
heating system shall be calibrated according
to the procedure contained in APTD-0576.
Probes constructed according to APTD-0581
need not be calibrated if the calibration
curves ITI APTD-0576 are used.
3.1.6 Temperature gauges—Calibrate dial
and liquid filled bulb thermometers against
mercury-in-glass thermometers. Thermo-
couples need not be calibrated. For other
devices, check with tho Administrator.
8.2 Analytical Apparatus.
8.2.1 Fluoride Electrode—Prepare fluoride
Btandardlzing solutions by serial dilution of
the 0.1 M fluoride standard solution. Pipet
10 ml of 0.1 M NaF into a 100 ml volumetric
flask and make up to the mark with distilled
water for a 10-° M standard solution. Use 10
ml of 10-J M solution to make a 10-° M solu-
tion in the same manner. Reapt 10-' and 10-'
M solutions.
Plpet 50 nil of each standard into a sep-
arate beaker. Add 50 ml of TISAB to each
beaker. Place the electrode in the most dilute
standard soHition. When a steady millivolt
reading Is obtained, plot the value on the
linear axis of semi-log graph paper versus
concentration on tho log axis. Plot the
nominal value for concentration of the
standard on the log axis, e.g., when 60 ml of
10-' M standard Is diluted with 50 ml TISAB,
the concentration Is still designated "10-a M",
Between measurements soak the fluoride
eenslng electrode In distilled water tor 30
seconds, and then remove and blot dry.
Analyze the standards going from dilute to
concentrated standards. A straight-line cali-
bration curve will be obtained, with nominal
concentrations of 10P, 10P, 10-", 10-', 10-'
concentrations of 10-6, 10-'. 10-', 10-', 10-«
concentrations of 10-5, 10-«, 10-", 10f, 10f»
fluoride molarity on tho log axis plotted
versus electrode potential (in millivolts) on
the linear scale.
Calibrate the fluoride electrode dally, and
check it hourly. Prepare fresh fluoride stand-
ardising solutions daily of 10-" M or less.
Store fluoride standardizing solutions In
polyethylene or polypropylene containers.
(Note: Certain specific ion meters have been
designed specifically for fluoride electrode
iise and give a direct readout of fluoride ion
concentration. These meters may be used in
lieu of calibration curves for fluoride meas-
urements over narrow concentration ranges.
Calibrate the meter according to manufac-
turer's instructions.)
9. Calculations.
Carry out calculations, retaining at least
one extra decimal figure beyond that of the
acquired data. Round off figures after final
calculation.
9.1 Nomenclature.
Xn=Cross sectional area of nozzle, m' (ft2).
Ai = Aliquot of total sample added to still,
ml.
B«j=:Water vapor in the gas stream, propor-
tion by volume.
Ci = Concentration of fluoride in stack gas,
mg/m', corrected to standard conditions
of 20° C, 760 mm Hg (68° F, 29.92 in. Hg)
on dry basis.
Ft —Total weight of fluoride in sample, mg.
1 = Percent of isokinetic sampling.
M — Concentration of fluoride from calibra-
tion curve, niolarlty.
m/>=Total amount of partlculate matter
collected, mg.
Mv — Molecular weight of water, 18 g/g-mole
(18 Ib/lb-mole).
mo = Mass of residue of acetone after evap-
oration, mg.
Pnar=: Barometric pressure at the sampling
site, mm Hg (in. Hg).
Pi --= Absolute stack gas pressure, mm Hg (In.
Hg).
f>,ti=standard absolute pressure, 760 mm
Hg (29.92 in. Hg).
jR = Ideal gas constant, 0.06236 mm Hg-ni'/
°K-g-molo (21.83 in. Hg-ftV°R-lb-mole).
Tm — Absolute average dry gas meter tem-
perature (seo flg. 13A-3), "K (°R).
3', = Absolute average stack gas temperature
(see flg. 13A-3). °K (°R).
r»ni—-Standard absolute temperature, 293°
K (528° R).
Vo=Volume of acetone blank, ml.
VCo«; — Volume of acetone used in wash, ml.
Vi=Volume of distillate collected, ml.
Vio~-Total volume of liquid collected in 1m-
pingcrs and silica gel, ml. Volume of water
in silica gel equals silica gel weight in-
crease in grams times 1 ml/gram. Volume
of liquid collected In impingcr equals final
volume minus initial volume,
Vm—-Volume of gns sample as measured by
dry gas meter, dcm (dcf).
V»,(»ta> — Volume of gas sample measured by
tho dry gas meter corrected to standard
conditions, dscm (d.scf).
V«(na>=Volumo of water vapor In tho gas
sample corrected to standard conditions,
scan (ecf).
Vi=Total volume of sample, ml.
«. = Stack gas velocity, calculated by Method
2, Equation 2-7 using data obtained from
Method 5, m/sec (ft/sec).
W. = Weight of residue in acetone wash, mg.
A//=Average pressure differential across the
orlfico (see flg. 13A-3), meter, mm HaO
(in. H»0).
p0=Density of acetone, mg/ml (seo label on
bottle) .
pw=Density of water, 1 g/ml (0.00220 lb/
ml).
0=Total sampling time, mln.
13.6=Speclflo gravity of mercury.
60=Sec/mln.
100 = Conversion to percent.
9.2 Average dry gas meter temperature
(and average orifice pressure drop. See data
sheet (Figure 13A-3 of Method ISA) .
9.3 Dry gas volume. Use Section 9.3 of
Method 13A.
9.4 Volume of Water Vapor. Use Section
9.4 of Method 13A.
9.5 Moisture Content. Use Section 9.5 of
Method 13A.
9.6 Concentration
9.6.1 Calculate the amount of fluoride In
the sample according to equation 13B-1.
Vi
A,
(M)
where:
K = 10 mg/ml.
9.6.2 Concentration of fluoride In stack
gas. Use Section 0.6.2 of Method 13A.
9.7 Isokinetic variation. Use Section 9.7
of Method 13 A.
9.8 Acceptable results. Use Section 9.8 of
Method ISA.
10. References.
Bellack. Ervln, "Simplified Fluoride Distil-
lation Method," Journal of the American
Water Works Association #60: 530-8 (1958).
MacLeod, Kathryn E., and Howard L. Crist,
"Comparison of the SPADNS — Zirconium
Lake and Specific Ion Electrode Methods of
Fluoride Determination ill Stack Emission
Samples," Analytical Chemistry 45: 1272-1273
(1973).
Martin, Robert M. "Construction Details of
Isokinetic Source Sampling Equipment,"
Environmental Protection Agency, Air Pol-
lution Control Office Publication Wo. APTD-
0581.
1973 Annual Book of ASTM Standards, Part
23, Designation: D 1179-72.
Pom, Jerome J., "Maintenance, Calibration,
and Operation of Isokinetic Source Sampling
Equipment," Environmental Protection
Agency, Air Pollution Control Office Publica-
tion No. APTD-0578.
Standard Methods for the Examination of
Water and V/aate Water, published Jointly by
American Public Health Association, Ameri-
can Water Works Association and Water Pol-
lution Control Federation, 13th Edition
(1971).
(Sections 111 and 114 of the Clean Ah- Act,
as amended by section 4(a) of Pub. L. 91-604,
84 Stat. 167B (42 U.S.O. 1857 c-8, c-9))
(PR Doc.75-20478 Filed 8-5-76;8:45 am]
FEDERAL REGISTER, VOL 40, NO. 15!—WEDNESDAY, AUGUST 6, 1975
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
340/1-77-009
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Phosphate Fertilizer Plants
Inspectional Manual for Enforcement of New
Source Performance Standards
6. REPORT DATE
March 1977
6. PERFORMING ORGANIZATION CODE
EPA - QE
7. AUTHOR(S)
Vladimir Boscak
Nicola Formica
8. PERFORMING ORGANIZATION REPORT NO.
Samuel Cha
9. PERFORMING ORGANIZATION NAME AND ADDRESS
lie Research Corporation of New England
..25 Silas Deane Highway
Wethersfield, Connecticut
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-3173
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. EPA
Stationary Source Enforcement Division
401 M Street, S.W.
Washington,D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
One of a series of enforcement inspection manuals
16. ABSTRACT
The document presents guidelines to enable enforcement personnel to determine
whether new or modified phosphate fertilizer production facilities comply with
New Source Enforcement Standards. Key parameters identified during the
performance test are used as a comparative base during subsequent inspections to
determine the facility's compliance status. ihe several regulated processes,
their atmospheric emissions and emissions controls are described. Inspection
methods and types of records to be kept are discussed in detail.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
Fertilizers
Inorganic Phosphates
Performance Tests
Performance Standards
New Source Performance
Standards
13B
7A
7B
2A
18. DISTRIBUTION STATEMENT
Unclassified
19. SECURITY CLASS (ThisReport)
21. NO. OF PAGES
IoT
20. SECURITY CLASS (Thispage)
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
* U.S. GOVERNMENT PRINTING OFFICE : 1977 0-241-037/55
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