SELECTED ANNOTATED BIBLIOGRAPHY
ON THE
CENTRAL FLORIDA PHOSPHATE INDUSTRY
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UNITED STATES
ENVIRONMENTAL PROTECTION AGENCY
REGION IV
345 COURTLAND STREET, N.E.
ATLANTA, GEORGIA 30308
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SELECTED ANNOTATED BIBLIOGRAPHY
on the
CENTRAL FLORIDA PHOSPHATE INDUSTRY
PREFACE
This bibliography is a selection of publications
regarding the Florida Phosphate Industry. It is by
no means all inclusive, but instead is a sampling
of publications emphasizing environmental and economic
effects, and potential" solutions to adverse environ-
mental effects. The bibliography was compiled by the
EPA Region IV Phosphate Study Unit.
Appreciation is extended to Barbara Fields, former
EPA Region IV Librarian, for the many hours borrowed
from her normal duties as well as personal time to
research the literature and published bibliographies
to supply the material to the Phosphate Unit.
Appreciation is also extended to the former secretary
for the Phosphate Unit, Dale Lewis. This copy
represents just one of several times she typed this
entire document. Many other references and annotations
were also typed which were later excluded from the
final document.
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CENTRAL FLORIDA PHOSPHATE INDUSTRY
SELECTED ANNOTATED BIBLIOGRAPHY
Page
I. Geology 1
A. Description of Geologic Formation 1
B. Resources and Reserves 6
II. Mining and Beneficiation 10
A. Description of Processes 10
B. Environmental Effects 16
1. Land 16
2. Water 17
3. Air 23
C. Resource Depletion Effects 26
D. Available Technology for Mitigation 28
of Adverse Effects
1. Land 28
2. Water 37
3. Air 40
4. Resource Depletion & By-Product 41
Recovery
III. Chemical Processing 44
A. Description of Processes 44
B. Environmental Effects 46
1. General 46
ii
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Page
2. Water 47
3. Air 52
4. Resource Depletion Effects 65
C. Available Technology for Mitigation 70
of Effects
1. Land 70
2. Water 70
3. Air 73
4. Resource Depletion and By-Product 78
Recovery
IV. Marketing Practices and Economics 102
A. Economics & Pricing 102
B. U.S. Supply & Demand 112
C. World Supply & Demand 113
V. Laws & Regulations 124
VI. General 134
iii
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CENTRAL FLORIDA PHOSPHATE INDUSTRY
SELECTED ANNOTATED BIBLIOGRAPHY
I. Geology
A. Description of Geologic Formation
RESULTS OF GEOLOGIC EXPLORATION BY CORE DRILLING,
1953, LAND-PEBBLE PHOSPHATE DISTRICT, FLORIDA. James
B. Cathcart and Lawrence J. McGreevy. Geological
Survey Bulletin, 1046-K, 1959.
A program of core drilling to delimit the uranium
and phosphate-bearing strata (the aluminum and calcium
phosphate zones) of the land-pebble phosphate district,
and to study the stratigraphic relations of the Bone
Valley formation, was carried out in the fall of 1953.
The Bone Valley formation of Pliocene age was deposited
by a transgressing sea. In most of the district,
the Bone Valley overlies limestone or dolomite of
the Hawthorn formation (middle Miocene); but in the
northern part of the district in northern Polk County,
where the Hawthorn thins to an erosional featheredge,
the Bone Valley overlies the Tampa formation (early
Miocene), and farther to the north, in Pasco County,
clayey sand of the upper part of the Bone Valley
overlies the Suwannee limestone (Oligocene). To the
east and south, however, the Bone Valley overlies
unnamed sand and limestone that contains fossils of
late middle Miocene age. This material in turn
overlies the limestone or dolomite of the Hawthorn
formation.
In the northwestern part of the land-pebble district,
the aluminum phosphate zone extends beyond the limits
of the calcium phosphate zone. To the east and south,
the calcium phosphate zone extends beyond the limits
of the aluminum phosphate zone. In the northern part
of'the area where the phosphate deposition was thinnest
the entire Bone Valley formation may have been leached,
whereas to the south, where the formation was thicker,
only the top part of the formation was leached, and
both zones are present. Still farther to the south,
in Hardee and Manatee Counties, the Bone Valley
formation may not have been exposed to subaerial
weathering, and the aluminum phosphate zone was not
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formed. The present limit of the aluminum phosphate
zone is the result of a combination of erosion after
the zone was formed, and the possibility that to the
east and south, phosphatic sediments were not exposed
to weathering in the Pliocene. The aluminum phosphate
zone and the calcium phosphate zone both cut across
stratigraphic units. This is clearly shown in some
of the cross sections where, for example, aluminum
phosphate minerals have formed in the Bone Valley,
the Hawthorn, and the Tampa formations. The calcium
phosphate zone may be entirely within the Bone Valley
formation, entirely within the Hawthorn formation
or most commonly, it includes the bottom part of the
Bone Valley, and the weathered top of the Hawthorn
formation. The phosphate deposits of the land-pebble
district are thus complex-partly residual, partly
marine re-worked, and partly phosphatized clay.
ECONOMIC GEOLOGY OF THE LAKELAND QUADRANGLE, FLORIDA.
James B. Cathcart. Geological Survey Bulletin, 1162-
G, 1964.
The Lakeland quadrangle, in west-central peninsular
Florida, lies at the northern and eastern edges of
the land-pebble phosphate district. Loose quartz
sand of Pleistocene and Recent age covers the
quadrangle; outcrops are confined to the mined areas
in the southern part of the quadrangle. Most of the
geology is known from drilling. Thin formations of
Tertiary age dip very gently to the southeast away
from the Ocala uplift and the Hillsborough high
northwest of the quadrangle. The Tampa Limestone
of early Miocene age, the Hawthorn Formation of middle
Miocene age, and the Bone Valley Formation of Pliocene
age crop out in the mining pits. Older formations
including the Ocala Limestone of Eocene age, and the
Suwannee Limestone of Oligocene age are known only
from drilling.
«
The Ocala Limestone underlies all of the Lakeland
quadrangle, and it is close to the surface only on
the upthrown side of the Polk City fault in the
northeast part of the quadrangle. The formation ranges
in thickness from 160 to 265 feet and probably thickens
to the south. The Ocala is overlain unconformably
by the Hawthorn Formation on the east side of the
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Polk City fault and elsewhere by the Suwannee Limestone
or the Tampa Limestone. The Suwannee Limestone ranges
in thickness from 0 to 170 feet; it is thickest in
the southern part of the quadrangle, and the upper
surface of the formation dips to the south. The
Suwannee Limestone is unconformably overlain by either
the Tampa Limestone or the Hawthorn Formation. The
Tampa Limestone ranges in thickness from 0 to 105
feet and is thickest over low spots on the surface
of the Suwannee Limestone, but the formation tends
to thicken toward the south and its upper surface
dips toward the south and southwest. The Tampa forms
the bedrock at the Tenoroc mine, where the Hawthorn
and Bone Valley Formations are thin and is the bedrock
of the drillers in the northwestrn part of the
quadrangle. All these pre-Hawthorn formations are
limestone, but each stratigraphically higher formation
contains more impurities than the one below. Only
the Tampa Limestone contains phosphate and only in
trace amounts.
The Hawthorn Formation consists of two parts-a
calcareous lower part which ranges in thickness from
0 to about 120 feet, and a clastic upper part, which
is present only in the southeastern corner of the
quadrangle and ranges in thickness from 0 to 10 feet.
The Hawthorn Formation thins to the north, and it
is missing in the northwestern corner of the
quadrangle. Phosphate nodules, mostly fine grained,
brown, and amber, are present in the Hawthorn. Minable
concentrations are present only in calcareous clay,
residual from the limestone of the formation.
The Bone Valley Formation, of Pliocene age, consists
of a lower and an upper unit. The lower unit
unconformably overlies the Hawthorn Formation except
in the northern and eastern parts of the quadrangle
where the upper unit overlies the Hawthorn Formation
or the Tampa Limestone.
The lower unit of the Bone Valley Formation ranges
in thickness from 0 to 35 feet and averages about
10 feet; it consists of unconsolidated sand, clayey
sand, and sandy clay-all containing abundant phosphate
nodules. The basal bed of the unit tends to be
conglomeratic, and the lower unit is bedded, cross-
bedded, and shows well-developed graded bedding.
The lower unit is not present in the northern and
eastern thirds of the qudrangle except as scattered
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outliers. The lower unit pinches out to the north
on the flank of the Hillsborough high. To the east,
the unit was restricted by a ridge of calcareous
material of the Hawthorn Formation.
The upper unit of the Bone Valley Formation is present
throughout the Lakeland quadrangle except where it
has been removed by erosion. The upper unit
gradationally overlies the lower unit except in the
northern part of the quadrangle where the distribution
of the lower unit indicates that erosion after
deposition removed the lower unit from a part of the
area and prior to the deposition of the upper unit.
The upper unit ranges in thickness from 0 to 25 feet
and averages 8 feet. The unit is bedded and
crossbedded gray clayey sand or sandy clay and has
only traces of phosphate.
About half a billion tons of phosphate nodules are
present in the Hawthorn Formation. This material is
very low grade and forms a potential phosphate resource
for the future.
ECONOMIC GEOLOGY OF THE FORT MEADE QUADRANGLE, POLK
AND HARDEE COUNTIES, FLORIDA. James B. Cathcart.
Geological Survey Bulletin, 1207, 1966.
The Fort Meade quadrangle, in west-central peninsular
Florida, is within the land-pebble phosphate district
and is part of the Gulf Coastal Plain. Formations
exposed in the mining pits of the area or in outcrops
along the major streams include the Hawthorn Formation
of early and middle Miocene age and the Bone Valley
Formation of Pliocene age. Formations older than
the Hawthorn-the Ocala Limestone of late Eocene age,
the Suwannee Limestone of late Oligocene age, and
the Tampa Limestone of early Miocene age-are known
only from two deep drill holes.
The Hawthorn Formation consists of an upper,
noncalcareous clastic part only a few feet thick,
and a lower part about 100 feet thick, which is
composed dominantly of limestone altered in the top
few feet to calcareous clay. Phosphate nodules, low
in P2O5 content, make up about 8 percent of the rock
of botn parts of the Hawthorn Formation. After the
deposition of the Hawthorn Formation erosion produced
a valley-and-ridge topography; ridges are modified
by a well-developed karst.
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The Bone Valley Formation unconformably overlies the
Hawthorn Formation and is divided into a lower
phosphorite unit and an upper clayey sand unit
containing little phosphate.
In the area of the higher flatwoods in the western
part of the quadrangle the lower unit of the Bone
Valley is a bedded and crossbedded sand containing
coarse brown and black phosphate nodules; near the
Peace River, in the eastern part of the quadrangle,
the unit consists of clayey sand or sandy clay
containing fine brown, amber, and white phosphate
nodules. The lower unit ranges in thickness from
0 to about 50 feet and is thickest over low areas
on the Hawthorn surface.
The upper unit of the Bone Valley is a white, gray,
or gray-green clayey sand or sandy clay containing
fine brown, amber, and white phosphate nodules. The
lower unit ranges in thickness from 0 to about 50
feet and is thickest over low areas on the Hawthorn
surface.
The upper unit of the Bone Valley is a white, gray,
or gray-green clayey sand containing small amounts
of phosphate nodules. The unit ranges in thickness
from 0 to about 30 feet. The contact between the
upper and lower units is gradational.
The Bone Valley Formation is overlain by quartz sand
of Pleistocene age. The contact is disconformable,
irregular in detail, and marked by sand-filled
channels, which in places cut through the Bone Valley.
Intense weathering, during at least three periods,
altered the phosphatic sedimentary rocks In the
quadrangle. During the first period the karst
topography on the Hawthorn Formation was formed and
most of the upper clastic part of the formation was
eroded away. Chemical weathering of the lower,
calcareous part of the Hawthorn removed calcium
carbonate and left a quartz- and phosphate-enriched
residuum that was reworked into the base of the Bone
Valley Formation. During the second period, after
deposition of the Bone Valley Formation, intense
lateritic weathering formed the aluminum phosphate
zone. During the third period, after deposition of
the loose sand, a ground-water podzol, typified by
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the Leon soil, either was formed in the surficial
materials or was superimposed on the aluminum phosphate
zone.
Mining of phosphate in the Fort Meade quadrangle began
shortly before 1892 and has continued to the present.
River-pebble phosphate was mined along the Peace River
until about 1908. The phosphate deposits are in the
calcium phosphate zone and include rocks of both early
and middle Miocene and Pliocene ages. Most of the
minable reserves are in the rocks of the lower unit
of the Bone Valley Formation of Pliocene age. Reserves
of recoverable phosphate in the area prospected total
317 million long tons. Additional reserves are present
in the unprospected areas of the quadrangle. A total
of about 40,000 long tons of metallic uranium is
present in the phosphate of the prospected area.
The aluminum phosphate zone, a potentially economic
zone, is present throughout the quadrangle; reserves
total about 250 million long tons ons of material,
which contains about 5 percent P205 and 0.009 percent
U3Og. The Hawthorn Formation contains an additional
1.5 billion long tons of phosphate nodules, a potential
resource for the future.
B. Resources and Reserves
"NEW PHOSPHATE ROCK DEPOSITS IN AFRICA", Phosphorus
Potassium, No. 86, 17, Nov.-Dec. 1976, p.17.
The South African Council for Scientific and Industrial
Research has reported that marine phosphate and
glauconite deposits have been discovered off the mouth
of Kunene river on the border between Angola and
Namibia.
FARMLAND BUYS FLORIDA PHOSPHATE ROCK. Farmland
Industries Inc. News Release. Dec. 21, 1976, 1 p.
Farmland Industries, Inc., Kansas City, Missouri,
has completed a phosphate rock reserve acquisition
in Central Florida. The announcement of the purchase
of approximately 7000 acres of phosphate rock reserves
in Hardee county, Florida, was made by Farmland.
The purchase will provide a source of phosphate rock
for Farmland's phosphate fertilizer manufacturing
facilities near Bartow, Florida. Duval Corp., Houston,
Texas, the mining subsidiary of Pennzoil Co., and
the Coca-Cola company, Atlanta, Georgia, were previous
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owners of the property.
"PHOSPHATE DEPOSIT STUDY IN SAUDI ARABIA.", Chem. Aqe
(London), Vol. 113, No. 16, Sept. 17, 1976, p. 2683.
Granges, the Swedish mining and metals group, has
reached an agreement with Petromin, Saudi Arabia's
state-owned petroleum agency. Under the agreement,
Granges will investigate a large phosphate deposit
in Northern Saudi Arabia. The reserves in the area
are estimated at between 150 and 300 million mt of
phosphate ore. Upgrading methods have been tested
at the Granges mineral laboratory at Straassa in
Sweden. These tests show that a high quality
concentrate can be produced from the ores.
"PHOSPHATE ROCK DEPOSIT IN MICHIGAN.", Chem. Eng. News,
Vol 55, No. 1, January 17, 1977, p. 34.
Rich ancient deposits of phosphate have been discovered
in northern Michigan by researchers from the U.S.
Geological Survey. Deposits of the mineral apatite
are located about 40 miles northwest of Marquette
and contain about 15% phosphate, possible of minable
grade. They are about 2 billion years old and appear
to be the oldest and richest sedimentary accumulations
of phosphate in the U.S. They indicate that phosphate
did accumulate in large concentrations that long ago
and that other old deposits may deserve further
exploration.
LETTER BY WILLIAM F. STOWASSER Division of Nonmetallic
Minerals, Bureau of Mines, U.S. Dept. of the Interior,
to R.E. McNeill, Feb. 11, 1977.
Measured reserves and resources are listed by county#
with a total of 1,722 million tons of recoverable
phosphate rock in the five county study area. Of
this, 685,000 tons would not be economical to mine
and process in today's market and are thus resources.
PHOSPHATE ROCK, THE PRESENT AND FUTURE SUPPLY AND DEMAND.
W.F. Stowasser. Bureau of Mines, Feb. 1977.
This paper lists past, present, and projected
quantities produced, and demand for the U.S. and the
world. The projected production curve shows Florida
to continue to produce the majority of phosphate rock
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in the United States through the year 2000. Florida
production of phosphate rock is currently 38 million
short tons per year, and is projected to peak at
approximately 45 million tons per year in 1985,
reducing to current production by 2000. Total U.S.
production was 49 million short tons in 1976 and is
projected to increase to 65 million short tons by
2000.
WORLD SURVEY OF PHOSPHATE DEPOSITS. Third Edition.
The British Sulphur Corporation Limited, London, 1971.
Reserves of Florida phosphate are generally taken
to be 25,390 million tons product, of which 2,040
million tons are considered mineable under present
conditions. These estimates are taken from data
published by Mansfield in 1942 and up-dated in 1958
by Federal Geological Survey investigations into pebble
reserves.
Minable under present conditions:
Land pebble-matrix 1,000 million tons
Hard rock, soft rock 1,040 million tons
Total 2,040 million tons
Minable under changed conditions:
Land pebble-matrix 2,000 million tons
Land pebble-leached zone 800 million tons
River pebble 50 million tons
Hard rock, soft rock 500 million tons
Hawthorn Formation 20,000 million tons
Total 23,350 million tons
Although the levels recorded, for land pebble reserves,
might be thought to require adjustment, to allow for
the tonnage of matrix extracted over the past ten
years, it is probable that the results of recent
exploration in both north and central Florida will
have more than balanced the effects of depletion.
Land pebble reserves were estimated by Mansfield in
1942 at almost 3,100 million tons, made up as follows:
North Florida
Hamilton County 50 million tons
Bradford County 55 million tons
Clay County 90 million tons
Central Florida
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Lake, Orange Counties 100 million tons
Hillsborough, Polk,
Manatee, Hardee, and
Highlands Counties 2,800 million tons
Total 3,095 million tons
The occurrences and deposits of phosphates in Florida
are examined. The exploitation of deposits by mining
concerns is catalogued for individual mine sites.
Sale of Florida phosphate rock is also listed from
1955-1969:
Sales of Florida Phosphate Rock
('000 tons product)
1955 8,677
1960 11,114
1965 17,412
1966 25,440
1967 27,063
1969 26,854
"WORLD PHOSPHATE RESERVES; ARE THERE REALLY ENOUGH?",
G.D. Emigh. Engineering and Mining Journal, Vol. 173,
April 1972, pp. 90-95.
Where the Institute of Ecology (10E) Workshop on Global
Ecological Problems in "Man in the Living Environment"
published late in 1971 puts phosphate rock reserves-
recoyerable today-at 25,000 million tons, the reliable
British SulphurCorp.•s "World Survey of Phosphate
Deposits" estimates 143,000 million tons.
Where the IOE Report states that prospecting will
do no better than double reserves to 50,000 million
tons, catalogs additional quantifiable reserves of
1,155,000 million tons-bringing reserves for the future
to 1,298,000 million tons. The additional reserves
are detailed below.
Florida Hawthorne
Australia
Sea floor
Tennessee limestones
Colombia
Saudi Arabia
Western US
Southeast US
Estimated total
200,000 million tons
200,000 million tons
300,000 million tons
3,000 million tons
80,000 million tons
150,000 million tons
172,000 million tons
50,000 million tons
1,155,000 million tons
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In addition, the following areas contain known reserves
which cannot be quantified now, but all of which are
probably large. All these occur in sedimentary
deposits. There are also reserves in igneous
phosphates.
Iran
India
California
Utah-Idaho
Spanish Sahara
Morocco
Peru
People's Republic
of China
Baja California, Mexico
Zacatecas area, Mexico
Alaska
Iraq
Jordan
Turkey
Libya
Syria
Tunisia
Algeria
IX, Mining and Beneficiation
A. Description of Processes
"FLORIDA PHOSPHATE MINING METHODS.", W.C. Cross, Mining
Congr. J. Vol. 3, No. 10, 1967, pp. 27-31.
Methods of mining phosphate rock in central Florida
are discussed. The ore zone varies in thickness
from 20-40 ft. and consists generally of 1/3 each
of clay, sand, and phosphate rock. Draglining methods
including both strip and mining operations are
described. An overall plant recovery is said to be
approximately 85%.
"DIHYDRATE PROCESSES.", In: Phosphoric Acid, Part
_I, A.V. Slack, Marcel Dekker, New York, 1968. pp. 157-
284.
This chapter discusses the technology of the dihydrate
process of wet-process phosphoric acid manufacture.
Section I covers the principles of design and operation
of phosphoric acid plants using the dihydrate process.
Section II provides an overview of various commercial
processes including Dorr-Oliver, Fisms, Prayon, PSG-
UCB, Singmaster and Breyer, and Taki.
"CHEMISTRY OF WET-PROCESS PHOSPHORIC ACID MANUFACTURE.",
Sven-Eric DAhlgren. In: Phosphoric Acid, Part I, A.V.
Slack, Marcel Dekker, New York, 1968. pp. 91-156.
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This chapter discusses the chemistry of wet-process
phosphoric acid manufacture in detail. The reaction
between phosphate rocks and acids is essentially a
surface reaction in which the rate is largely
controlled by reaction temperature, hydrogen ion
concentration, diffusion through liquid films at the
surface, and the surface area of the rock available
for reaction. The principal chemical reactions and
physical properties of wet-process manufacture are
discussed and related to process control.
ENVIRONMENT FACT SHEET 1976. Florida Phosphate Council.
Lakeland, FL.
Research, development, and use of systems and equipment
for the purposes of air quality control, water quality,
control, water conservation, and land reclamation
are summarized for 1976.
URANIUM IN PHOSPHATE ROCK. Vincent E. McKelvey U.S.
Geol. Survey Profess. Paper 300, pp. 477-81.
A review with 22 references. Marine phosphorites
generally contain 0.005-0.03% U, probably as an
isomorphous substituent for Ca in carbonate-
fluorapatite and crandallite. Such U concns. may
be recoverable as a by-product of the manuf. of triple
superphosphate.
URANIUM IN THE PHOSPHORIA FORMATION. Vincent E. McKelvey
and Louis D. Carswell. U.S. Geol. Survey Profess. Paper
300. pp. 483-7.
The Permian Phosphoria formation contains marine
phosphorites over an area of about 135,000 sq. miles.
The U content ranges from 0.001 to 0.065%; most beds
more than 3 ft. thick that contain more than 31% P
2O5 contain 0.01-0.02% U. The U content is inversely
proportional to the C02 content and roughly
proportional, with some exceptions, to the P205
content. Weathered rock is lower in U content.
DISTRIBUTION AND OCCURRENCE OF URANIUM IN THE CALCIUM
PHOSPHATE ZONE OF THE LAND-PEBBLE PHOSPHATE DISTRICT
OF FLORIDA. James B. Cathcart (U.S. Geol. Survey,
Washington, D.C.). U.S. Geol. Survey Profess. Paper
300. pp. 489-94.
The material mined contains nearly equal amts. of
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quartz sand, pebble phosphate contg. 29-34% P2°5
and 0.008-0.050% U^Oo ; and slimes contg. an av. of
15% P9O5 and 0.005% 830g. The U content decreases
and the P content increases as the size of the
fluorapatite nodules decreases. It is believed that
the U was absorbed by the phosphate particles as they
formed on the ocean floor.
THE ALUMINUM PHOSPHATE ZONE OF THE BONE VALLEY FORMATION
AND ITS URANIUM DEPOSITS. Zalman S. Altschuler,
Elizabeth B. Jaffe, and Frank Cuttitta (U.S. Geol.
Survey, Washington, D.C.) U.S. Geol. Survey Profess.
Paper 300. pp. 495-504.
The upper part of the Ca phosphate zone has been
leached with the formation of a discontinuous A1
phosphate zone averaging 6-7 ft. thick. Reserves
exceed 800 million tons averaging 0.01-0.02% U. U
is enriched in this zone, particularly in the Ca
phosphates. Apatite is replaced by crandallite,
wavellite, and millisite. Chem. analyses of 7 samples
are given. The A1 phosphate zone was probably formed
by lateritic alteration, U being dissolved and repptd.
as the Ca Al phosphates at lower levels.
RADIOCHEMICAL POLLUTION FROM PHOSPHATE ROCK MINING AND
MILLING. J.V. Rouse In: Water Resources Problems
Related to Mining; Proceedings No. 18, American Water
Resources Association, Minneapolis, Minnesota, June
1974. pp. 65-71.
Phosphate mining and milling is a major segment of
the U.S. mining industry. The United States produces
45% of the world's supply of phosphate fertilizer.
This mining and milling of phosphate rock has been
responsible for major water pollution problems of
a conventional nature in the past. Recent data
indicate that the industry is also responsible for
major, unrecognized radiochemical pollution of water
and air, and the generation of radioactive solid waste.
The untreated liquid effluents from phosphoric-acid
plants are 30 times the Maximum Permissible
Concentration for r^dium-226. The byproduct gypsum
generated by the industry contains approximately 25
picocuries of radium-226 per gram. Use of this
material for building products would expose the
population to radon decay products. Seepage of
contaminated water from process ponds has contaminated
large areas of groundwater. Treatment and
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stabilization measures exist to control the surface
water discharge and the solid waste. Problems still
exists with respect to seepage. Failures of slime
ponds constitute a massive release of radium, measured
in curies, to the aquatic environment.
RECONNAISSANCE STUDY OF RADIOCHEMICAL POLLUTION FROM
PHOSPHATE ROCK MINING AND MILLING. EPA National Field
Investigations Center-Denver, Colo, Dec. 1973. 106
pp.
A reconnaissance study of the phosphate mining and
milling industry was necessary to investigate the
magnitude of radiochemical pollution to receiving
waters. This report describes the findings of the
study and other related problems associated with
processing of phosphate fertilizers, such as air
pollution, groundwater contamination, possible
deleterious consequences of fertilizer use, effects
on other receiving water uses, including shellfish
and drinking water supplies, and the use of by-product
material in the construction industry. Throughout
the report a comparison has been made of reconnaissance
sampling results with promulgated radiochemical
standards and guidelines. Pollution control and
analysis and water quality data are also discussed.
RADIOACTIVITY DISTRIBUTION IN PHOSPHATE PRODUCTS, BY-
PRODUCTS, EFFLUENTS, AND WASTES. EPA Office of Radiation
Programs, ORP/CSD-75-3, Aug. 1975.
Phosphate rock throughout the world contains uranium
in concentrations ranging from a few ppm to a few
hundred ppm. In the United States, phosphate rock
normally contains between 100-150 ppm uranium. Mining
and processing of these ores redistributes much of
the uranium daughters among the various products,
by-products> and wastes. These materials are then
widely dispersed throughout the environment. This
redistribution may lead to increased exposure of the
public to these naturally-occurring radionuclides.
In determining the magnitude of the population exposure
caused by this redistribution and in developing
environmental standards and controls to prevent
contamination of the biosphere from these naturally-
occurring radionuclides it is necessary to determine
the concentrations and total quantities of these
radionuclides in the products, by-products, effluents
and wastes of phosphate mining and manufacturing.
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Samples of phosphate ores, products, by-products,
effluents, and wastes were obtained and analyzed for
their radioactivity content. Calculations were made
to quantify the partitioning of the radionuclides
in the processing steps from mining through the wet
and thermal production techniques. Laboratory studies
were made to establish the effectiveness of various
treatments in controlling radioactivity in liquid
effluents. Field studies were conducted to verify
the laboratory results and assess liquid effluent
control effectiveness in actual facility operations.
Quantities of radioactivity entering the environment
through various products, by-products, effluents,
and wastes were estimated.
A PRELIMINARY EVALUATION OF THE CONTROL OF INDOOR RADON
DAUGHTER LEVELS IN NEW STRUCTURES. J.E. Fitzgerald,
R.J. Guimond, and R.A. Shaw. EPA-520/4-76-018, Nov.
1976, 61 pp.
As part of its assessment of the radiological impact
of the phosphate industry in Florida, the U.S.
Environmental Protection Agency has surveyed residences
built atop uraniferous reclaimed phosphate mining
land. These surveys have shown elevated radon daughter
levels to exist in structures built on this land.
In order to allow safer use of this land for
residential construction, various state-of-the-art
radon daughter control technologies were evaluated
by the Agency. These included forced ventilation,
polymeric sealants, excavation, crawl space
construction, and improved slab quality. From a cost-
effectiveness evaluation, crawl space construction
was determined to best satisfy the criteria for
"optimal" radon daughter control. These criteria
were established as: (1) operative passivity (i.e.,
requiring no occupant responsibilities); (2) uniform
effectiveness over the lifetime of a structure; (3)
a one-time reasonable cost upon implementation; and
(4) not having a significant impact on the lives of
future occupants.
THE RADIOLOGICAL ASPECTS OF FERTILIZER UTILIZATION.
Richard J. Guimond. EPA Office of Radiation Programs,
1977.
Phosphate ores throughout the world contain
concentrations of uranium varying from 3 to 400 ppm
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(.0003 to .04%). In the United States, the ores
normally contain between 50-200 ppm uranium. In
general, the radionuclides are in equilibrium with
their decay products, at least through radium-226.
Approximately 80 percent of the phosphate rock mined
and consumed in the United States is used for the
manufacture of fertilizers. Depending on the process
used to produce various phosphate fertilizers, the
resulting products may contain substantial
concentrations of radium-226 and other radionuclides.
To examine the significance of the radioactivity in
these materials, samples of various fertilizer products
were obtained from several manufacturers and analyzed
for their radium-226, thorium, and uranium content.
The transfer of radioactivity from the fertilizers
was estimated based upon uptake information presented
in the literature. The overall potential health impact
of the fertilizer use due to increased activity in
crops was-discussed. Other potential problems such
as radioactivity in soil runoff and workers' exposures
in storage areas were discussed.
THE RADIOLOGICAL IMPACT OF THE PHOSPHATE INDUSTRY-A
FEDERAL PERSPECTIVE. Richard J. Guimond. EPA Office
of Radiation Programs, , May 1976.
The Office of Radiation Programs began its national
study of the phosphate industry in June, 1974. This
study has been directed toward comprehensively
characterizing the radioactivity source terms,
assessing the resultant public health and enviromental
impact, and determining the adequacy of existing
standards and controls. The phosphate industry
annually redistributes massive quantities of naturally-
occurring radionuclides through its products, by-
products, and wastes. Although the industry
redistributes only naturally-occurring radionuclides,
whether the resultant environmental levels should
be considered normal background and whether it is
controllable are areas where a new perspective is
needed nationwide.
RADIATION EXPOSURES IN THE FLORIDA PHOSPHATE INDUSTRY.
(Draft) W.A. Mills, R.J. Guimond, and S.T. Windham.
EPA Office of Radiation Programs, 1977.
The radioactivity of phosphate rock was probably first
observed in 1908 when the British physicist R. Strutt
found that samples of phosphorite were several times
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more radioactive than the average rocks of the earth's
crust. Mor recent studies of the concentrations of
natural Uranium and thorium in phosphate ores produced
in the United States indicate that concentrations
of these natural materials range from about 10 to
400 ppm and 2 to 20 ppm, respectively. In the rich
marine phosphate deposits of Florida, uranium is
present in concentrations in the range 100-150 ppm.
Uranium daughters in the phosphate ores, at least
through radium-226, are usually in secular equilibrium.
The purpose of present studies of this industry by
the U.S. Environmental Protection AGency is to assess
the radiological impact of phosphate mining,
processing, use, and related activities. The study
includes an evaluation of the effectiveness of controls
and in areas where controls appear to be insufficient,
the development of appropriate standards and guides.
The overall study has been sub-divided into tasks
involving the evaluation of effluents, emissions,
products, by-productsoccupational exposures, and
reclaimed land uses. This paper summarizes findings
to date.
B. Environmental Effects
1. Land
PRELIMINARY FINDINGS RADON DAUGHTER LEVELS IN
STRUCTURES CONSTRUCTED ON RECLAIMED FLORIDA PHOSPHATE
LAND. EPA Office of Radiation Programs, ORP/CSD-
75-4, Sept., 1975.
To determine the significance of radium-226 in
reclaimed land on the radon daughter levels in
structures built on the land, a limited field
study was conducted. In general, the data from
this study coupled with existing information
indicates that radium-226 concentrations in soil
beneath structures significantly affects the radon
daughter levels within the structures. The data
collected over a five-week period suggests that
structures built on reclaimed land have radon
daughter levels significantly greater than
structures not built on reclaimed land.
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2. Water
PROBLEMS AND MANAGEMENT OF WATER QUALITY IN
HILLSBOROUGH BAY, FLORIDA. Hillsborough Bay
Technical Assistance Project Technical Programs.
Southeast Region Federal Water Pollution Control
Administration, Tampa, FL, December 1969.
The objectives of these studies were: to identify
and quantify key sources of waste in Hillsborough
Bay and to determine their effect on water use;
to determine the cause or causes of noxious odors
in Hillsborough Bay and; to recommend means of
modifying conditions in Hillsborough Bay to
eliminate the causes of obnoxious odors and make
possible other desirable uses.
Sixty-eight municipal and industrial waste sources
were identified and investigated. The major
contributor of carbonaceous organic material to
Hillsborough Bay is the primary sewage treatment
plant of the city of Tampa which discharges about
28 million gallons per day at the southern tip
of Hookers Point. This effluent contains
carbonaceous organic material equivalent to a
population of 290,000 and represents more than
85% of all carbonaceous waste from point sources.
The plant is also the major contributor of
unsatisfied nitrogenous material, discharging
7300 pounds per day or more than 40% of the total
input to the Bay from point sources. The other
major contributors of pollution to the Bay are
the MacDill Air Force Base sewage treatment plant,
U.S. Phosphoric Products Company, Nitram Chemical
Company, Palm River (Sixmile Creek), Hillsborough
River and the Alafia River. The Alafia River
which has fourteen phosphate processing plants
near its headwaters contributes more than 43,000
pounds per day (as phosphorus,P) or 78% of the
total phosphorus input to Hillsborough Bay from
point sources. U.S. Phosphoric Products and the
Alafia River contribute 94% of the total
phosphorus. The Alafia River, Nitram Chemical
Company and U.S. Phosphoric Products together
discharged nearly 50% of the total unstisfied
nitrogenous material to the Bay. Another major
source of nitrogen and phosphorus to Hillsborough
Bay at intermittent periods during the survey
was the flushing of water hyacinths from the Tampa
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water supply reservoir down the Hillsborough River.
METHOD FOR RAPID SEDIMENTATION OF FINE PARTICLES
FROM SUSPENSIONS. Annie G. Smelley, Charles
Spruiell, Jr. Department of the Interior,
Washington, D.C., Patent Application, Rept No:
PAT-APPL-688 659, Docket/Min-2443.
This Government-owned invention available for
U.S. licensing and, possibly, for foreign
licensing. Copy of application available NTIS.
$3.50.
Suspensions of fine particles such as phosphate
ore slimes are caused to settle by reaction with
hydrofluoric acid or equivalent F-containing
material in order to effect rapid settling of
particles from the aqueous suspensions. This
patent application can be used for water pollution
control.
CHARACTERIZATION STUDIES OF FLORIDA PHOSPHATE SLIMES.
W.E. Lamont. Bureau of Mines, Tuscaloosa Metallurgy
Research Lab. Rept. of investigations #8089, Nov.
1975, 29 pp.
The Federal Bureau of Mines, in cooperation with
phosphate companies in the Florida land pebble
area, made a comprehensive study of the phosphate
slimes, or waste clays, produced in the mining
of phosphate rock in Florida. The slimes, or
waste clays, represent a significant ecological
problem and a major deterrent to effective land
recovery in the phosphate mining areas. Physical,
chemical and mineralogical studies were made of
samples of slimes submitted by each of the 15
plants operating in Florida in an effort to
identify any factors that prevent successful
consolidation of the slimes and subsequent recovery
of the mined lands. Results of these studies
indicated that the clay mineral attapulgite, a
hydrated magnesium silicate, was primarily
responsible for the very poor settling
characteristics of the slimes and that the quantity
of attapulgite present in the slimes effectively
controlled the settling rate, the pulp density
of terminal solids, viscosity, percent solids
of filter cake, and the flocculant requirements.
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"THOSE NASTY PHOSPHATIC CLAY PONDS.", Environmental
Science & Technology. Vol. 8, No. 4, April 1974.
W. 315-313.
The Florida phosphate industry, which produces
approximately 80% of the domestic phosphate
fertilizer, produces tremendous volumes of
phosphatic clay bearing wastes. These slimes
represent a significant ecological hazard and
a major deterrent to effective land reclamation
in mining areas. The weight of slimes is often
in approximate 1:1 correspondence with the weight
of rock processed. The slimes also contain clays
which retain a high percentage of water for
extended periods of time. No truly practical,
economical method presently exists by which the
clay can be quickly dewatered on any appreciable
scale.
The current disposal technique involves above-
ground storage behind earthen dams, where solid
material settles over a period of 14-25 years.
As of November 1973, some 40,000 acres of active
and inactive settling areas existed, and were
surrounded by over 300 miles of earth dams. It
is estimated that about 2500 acres of new settling
pond areas are established each year, and these
ponds are also enclosed by earth dams.
Since 1942, some 20 dam failures have occurred,
resulting in extensive ecological damage. The
most recent break was on December 3, 1971 at Cities
Service Company's Ft. Meade Mine, releasing 2
billion gallons of slime into the Peace River
in Polk County, Fla. After this failure, a
comprehensive set of regulations was developed
to control the design, construction, and operation
of earth dams to minimize future failures.
In November 1972 a co-operative effort by the
U.S. Bureau of Mines and the Florida Phosphate
Council was initiated to develop a solution for
dewatering phosphate slimes. If phosphatic clay,®
are to be dewatered, unit costs of handling,
treatment, and disposal must be on the same order
of magnitude as those of damming. Costs in 1973
dollars are about $0.35/ton of slimes (dry-basis);
major cost components are dam construction and
maintenance, and slime pumping. Increased disposal
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costs would be justified if increased land
reclamation resulted, for the industry spends
an average of $650-800/acre to reclaim previously
mined land.
The Florida Phosphate Council-U.S. Bureau of Mines
study has shown two methods to be technically
feasible and economically promising: 1) mixing
slimes with sand tailings and 2) chemical
flocculation together with coagulation with
tailings sand. The possibilities of extraction
of additional phosphate values from the slimes,
as well as aluminum, iron, and uranium, have been
examined. While no great market for dewatered
slimes and their derivatives currently exists,
the long range projection for utilization of these
materials is very favorable.
Environmental concerns and increasing land values
in central Florida are creating pressures for
faster land reclamation and for phasing out
phosphatic clay settling areas. Much research
has been undertaken by numerous organizations
to solve the persistent problem of disposal of
slimes.
VARIATIONS IN CLAY MINERAL COMPOSITION OF PHOSPHATE
SLIMES WITHIN THE CENTRAL FLORIDA PHOSPHATE MINING
DISTRICT. R.G. Stevenson, Jr. Bureau of Mines,
Washington, D.C., Final rept., Dec 1975.
This report describes and identifies the clay
and other minerals found in 58 samples of primary
slimes from 16 phosphate processing plants in
Florida. The major clay minerals found are
smectite, kaolinite, and palygorskite. The major
nonclay minerals found are apatite, quartz, and
dolomite.
THE FLORIDA PHOSPHATE SLIMES PROBLEM—A REVIEW AND
A BIBLIOGRAPHY. Bureau of Mines, Tuscaloosa
Metallury Research Lab., Information circular #8668,
Jan 1975.
The Florida phosphate industry,which supplies
about three-fourths of the domestic phosphate
fertilizer, produces tremendous volumes of
•phosphatic clay wastes (slimes). These clays
retain a high percentage of water for extended
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periods of time. The clays also pose an
environmental hazard because the disposal technique
involves above-ground storage behind earthen dams.
Although much research has been undertaken by
numerous organizations to dewater slime, no
completely satisfactory solution has been
developed. In June 1972, a cooperative effort
by the U.S. Bureau of Mines and the Florida
phosphate mining industry was initiated to develop
a solution for dewatering the Florida phosphatic
slimes. This report discusses various aspects
of the slimes problem, reviews past research,
makes recommendations for future research and
includes a bibliography of references and patents
dealing-with the subject.
WATER RECIRCULATION SYSTEM BALANCE OF CENTRAL FLORIDA
PHOSPHATE*MINING. Zellars-Williams, Inc., Lakeland,
Fla., Jan. 1977.
The recirculating water systems of active Central
Florida mines are utilized to convey and process
the ore, transport and store sand and clay wastes,
and reclaim the water for reuse. The system is
balanced by providing makeup water, in addition
to that naturally contributed by rainfall or
seepage, to meet the losses in the system. The •
losses are primarily due to evaporation from open
water areas and entrainment in the wastes, but
are also attributed to a number of other factors.
Ideally, an operating system would discharge no
water, utilizing all available natural resources.
This would in turn minimize the makeup wafcer
pumping requirements, reducing energy costs and
providing for resource conservation. Each mine,
in fact, has its own set of factors which dictate
the water requirements and to some extent, the
efficiency of its management. Included in these
are such considerations as production rate, amount
of pebble in the rock product, clay content of
ore, topography, surface catchment area, volume
of water impounding structures, exposed open water
area, and capability of using recirculated water
in amine flotation. Efficient system management
is a final factor affecting water utilization.
Three operating mines are modeled and a water
system balance is constructed, based on the set
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of variables provided at the mine. The balances
are constructed in the case of two different years,
to illustrate the variables subject to changes
in time.
This preliminary study highlights the complexity
and diversity of mine water systems while
explaining the basic concepts required for their
analysis. Recommendations are made for more
detailed study of system capacity, water management
techniques, and recirculating water quality.
EFFECTS OF THE PHOSPHATE INDUSTRY ON RADIUM-226
IN GROUND WATER OF CENTRAL FLORIDA. Robert F.
Kaufmann and James D. Bliss, 1977.
Principal U.S. phosphate production is from central
Florida where strip mining, dewatering of shallow
ore bodies and overburden, extraction of deep
ground water for processing, and waste disposal
intimately associate the industry with water
resources. Elevated concentrations of uranium
and radium in ore, overburden, and ground water
have prompted several Federally-sponsored studies
in the last decade to ascertain the water quality
effects of the industry, particularly with respect
to radium-226 in potable water supplies.
Using 227 analyses of radium in water samples
collected from a study area of 3000 square miles,
parametric and non-parametric statistical tests
and graphical techniques were utilized to evaluate
radium concentrations in three separate aquifer
systems (water table, Upper Floridan, Lower
Floridan), mineralized and unmineralized areas,
and two time periods: 1966 and 1973-1976.
Geometric mean radium concentration in the water
table aquifer in unmined, mineralized areas is
0.70 pCi/1 compared to arithmetic means of 0.92
and 1.00 pCi/1 in mined and background areas.
For the Upper and Lower Floridan aquifers, average
concentrations of Ra-226 are equal or higher in
the control areas relative to mineralized or mining
areas. Assessment of Ra-226 content in the
combined water table and Upper Floridan aquifers
with the Kruskal-Wallis test ( =.05) also indicates
that the mineralized but unmined area tends to
have higher Ra-226 than areas impacted by mining.
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Ad hoc testing (t test; =.05) of the Lower
Floridan aquifer in mineralized versus
nonmineralized areas also revealed significantly
higher radium concentrations in the latter,
apparently a result of natural factors not related
to mining or mineralization.
No distinct temporal trend is apparent in comparing
individual or grouped (Mann-Whitney test, =.05)
observations made in 1966 and those in the period
1973-1976. Existing radium data do not
substantiate contamination of ground water
throughout the areas of mining and processing
as a result of the phosphate industry. However,
local contamination associated with specific
operations has occurred and is likely to continue
as water development and mining expand, further
stressing the Tloridan aquifer. Natural
variability in radium content of ground water
complicates determination of background versus
contaminated conditions and underscores the need
for more intensive data collection as an integral
part of water and land management.
3. Air
POPULATION RADIATION DOSE ESTIMATES FROM PHOSPHATE
INDUSTRY AIR PARTICULATE EMISSIONS. J.E. Partidge,
T.R. Horton, and E.L. Sensintaffar. Technical Note
ORP/EERF-77-1, 1977.
The EPA Office of Radiation Programs has conducted
a series of studies to determine the radiological
impact of the phosphate mining and milling
industry. This report describes the efforts to
estimate the population radiation doses resulting
from airborne emissions of particulates from the
industry.
Two "wet-process" phosphoric acid plants and one
ore drying facility were selected for this study.
The 1976 Annual Operations/Emissions Report,
submitted by each facility to the Florida
Department of Environmental Regulation, and a
field survey trip by EPA personnel to each facility
were used to develop data for dose calculations.
The field survey trip included sampling for stack
emissions and ambient air samples collected in
the general vicinity of each plant. Population
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and individual radiation dose estimates are made
based on these sources of data.
The results of this study show small, but
measurable, increases in levels of radioactivity
surrounding the phosphate industry operations.
However, it should be noted that levels
statistically above background were measured in
only 5 of the 12 locations sampled. Dose
projections also show the small magnitude of
airborne particulate radioactivity released from
the phosphate industry operation. It appears
that drying operations are the most significant
source of airborne radioactive particulates.
"NORTH CAROLINA PHOSPHATE MINERS FACE WATER
SHORTAGE.", Eng. Min. J. , Vol. 176, No. 11,, Nov.
1975. pp. 52,55.
The prospect of two major companies mining
phosphate along the Pamlico River in Beaufort
County, North Carolina, has caused concern among
groundwater experts in the North Carolina
Department of Natural and Economic Resources.
The state government has recommended a meeting
of state officials with the companies'
representatives to seek agreement on how to divide
the vast amount of water needed in mining
operations. To keep the large pits, located in
a swampy region, from filling with groundwater,
massive large scale pumping is essential.
Texasgulf has permission from the state to pump
67 million gallons/day of water to keep the pits
dry and to carry phosphate and other materials
around its mining and chemical complex. North
Carolina Phosphate has asked for permission to
pump 45 million gallons/day when it begins
operation, and 60 million gallons/day for 12 months
during 1979 and 1980. State officials believe
that when North Carolina Phosphate begins pumping,
Texasgulf's water supply will be depleted. State
experts also say the prospect of both firms pumping
all the water they want-up to about 120 million
gallons/day-poses a danger. Meanwhile, state
officials are uncertain about the effect the new
mine and increased groundwater depletion may have
on private wells in the region, but they estimate
2000 wells might be affected.
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THE EFFECTS OF STRIP MINING UPON NAVIGABLE WATERS
AND THEIR TRIBUTARIES: DISCUSSION AND SELECTED
BIBLIOGRAPHY. Pittsburgh Univ., Graduate Center
for Public Works Administration, NTIS AD-749 802.
The principal effects of strip mining on waterways
include alterations in runoff and sedimentation,
water chemistry, stream ecology, and water
utilization. The two principal approaches to
abatement of strip mine effects are land
reclamation and treatment of contaminated
discharges. Land reclamation treats many of the
effects of strip mining while treatment considers
primarily the mine drainage problem. Strip mined
land can be regarded and revegetated to control
runoff and erosion and to reduce the formation
of acid or highly mineralized drainage. Mine
discharges which can be localized can be treated
chemically or physically to remove suspended and
dissolved solids. To reduce the concentrations
of pollutants in streams, impoundment or dilution
may be utilized. The most direct control is
limitation by location and extent of strip mining.
The several treatment methods, considered in the
literature and in some cases applied as full or
pilot scale treatment plants, include
neutralization, distillation, ion exchange, reverse
osmo'sis, electrodialysis and the physical processes
of dilution, sedimentation and impoundment. A
comprehensive bibliography of selected references
is included, especially dealing with coal strip
mining.
WASTE DISPOSAL COSTS OF A FLORIDA PHOSPHATE
OPERATION. J.R. Boyle. Bureau of Mines, Knoxville
Office of Mineral Resources.
The waste disposal method used at the International
Minerals and Chemical Corporations's Noralyn
Phosphate Operations in Polk County, Fla., was
studied to develop cost estimates, provide better
knowledge of current practices, guide consideration
of alternative methods and identify possible areas
of research. Cost estimates were based on
capacities of existing facilities, but the
phosphate production and slime generation
statistics used in the calculations were estimated
rather than data drawn from company records.
Cost estimates represent a basis for calculating
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waste disposal costs Cor other phosphate plants
which utilize the same method of disposal. Total
operating cost of disposal is estimated to be
33.0 cents per ton of product based on an assumed
4.5 million tons of slime per year. Net operating
cost is estimated to be 24.5 cents per ton of
product after credit of 8.5 cents per ton for
recirculated water from the settling ponds to
the plant. To conserve mineral resources and
to improve environmental conditions, research
should be directed to developing alternative
methods of disposal, including the recovery of
the P2®5 values from the slimes and the dewatering
of the slimes.
C. Resource Depletion Effects
"THE PHOSPHATE CONNECTION.", David Laing. Ecologist
Vol. 5, No. 7,, Aug.-Sept. 1975. pp.240-1.
Since 1940 U.S. marketable phosphate production has
increased exponentially'with time. If the trend
continues, exhaustion of identified U.S. phosphate
reserves will occur by about 2011, and total reserves
(identified plus hypothetical) will run out by about
2060. Eventual depletion of concentrated phosphate
reserve, coupled with the prohibitive expenditure
of money and energy necessary to reconcentrate the
resources, will necessitate a reduction of world
population to the 1-2 billion level, which the globe
can reportedly support without the use of phosphate
fertilizer on submarginal cropland.
ECONOMIC IMPACT OF SHORTAGES ON THE FERTILIZER INDUSTRY.
Arthur D. Little. Cambridge, Mass., Federal Energy
Administration, Washington, D.C., Jan. 1975,
This study represents an effort to provide information
on the basic structure, characteristic and problems
of the fertilizer industry. Particular emphasis is
placed on fuel use and substitutability as'well as
the impact of fertilizer on farm production.
"THE FUTURE FOR LOW QUALITY PHOSPHATE ROCK MINING AND
PROCESSING.", A.P. Kouloheris 5(Cardinier Inc. Tampa,
Fla.). Phosphorus Potassium No. 82, Mar.-Aor. 1976
pp. 32-4:
There is no shortage of phosphate rock in the world;
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but so much of the high-grade, high-quality reserves
are gone that much of the remainder will be less
convenient to process. The industry has very little
time left to evolve the necessary technology for
processing. The problems that arise in transferring
from high-grade to low-grade, low-quality rock are
summarized and recommendations for research are given.
WATER USE IN THE MINERAL INDUSTRY. Alvin Kaufman and
Mildred Nadler. Bureau of Mines, Inform Circ No 8285,
1966.
To aid industry and Government in planning water
developments the Bureau of Mines in 1963 convassed
mineral producers to determine water use in 1962.
Water used by the mineral industry is only 2% of the
water withdrawn by all industry. The major water-
using mineral industries are natural gas processing,
phosphate rock, sand and gravel, and iron ore. Total
water use and new water intake is dependent on the
quantity of material processes and the process water
requirements of the particular industry or commodity.
Recirculation is dependent on the processing
requirements of the particular commodity, the manner
in which the water is used, cooling and condensing
requirements in large industries, the quality of new
water intake, and the need to treat new discharged
water. Consumed water is dependent on the quantity
of water recirculated, the temperature and humidity
in the area, and the proportion of water used for
cooling and condensing. A threefold increase in water
use by the mineral industry by 1985 is forecast.(Knapp-
USGS) .
DRY BENEFICIATION OF PHOSPHATE ORE. Joseph F. Haseman
{to Armour Agricultural Co.). U.S.Patent 3,375,067,
Mar. 26, 1968.
Phosphate ores containing carbonate minerals are
calcined at 1200-1700°F. to convert the carbonates
to oxides. The ore is cooled rapidly and is then
subjected to attrition to form dust. The dust is
separated from the coarse fraction, thereby removing
appreciable non-phosphate, acid-consuming, material.
For example, fine Florida phosphate ore of 60.6% BPL
grade, containing 6.0% CO2 was calcined at 1700°F.
for 1 hr. in a muffle furnace. The calcined material
was air-cooled, placed in a jar, and agitated by hand
27
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shaking for 3 min. The resulting dust was separated
by screening. The residual material was 67.7% BPL
grade, and the recovery was 95.4%, p2°5 ^as^s*
AVAILABILITY AND POTENTIAL UTILIZATION OF BYPRODUCT
GYPSUM IN FLORIDA PHOSPHATE OPERATIONS. John W. Sweeney
and Bobby J. Timmons. In: Proceedings, Eighth Forum
on Geology of Industrial Minerals, Public Information,
Number 5, Iowa City, Iowa, April 12-14, 1972, February
1973.
The generation rate and availability of byproduct
gypsum in Florida is assessed to determine the
magnitude of the situation and to stimulate the
utilization of this gypsum resource. Past trends
are projected to determine the future availability
of these materials.
Several new uses of byproduct gypsum could utilize
large volumes of the material. The projected annual
generation rates of byproduct gypsum from wet-process
phosphoric acid manufactured in Florida far exceeds
domestic gypsum demand.
Known, potential, and new uses of byproduct gypsum
are reviewed and discussed in this paper.
Local Committee Sponsoring
Organizations Fred H. Dorheim, Chairman
Iowa Geological Survey Wayne I. Anderson
University of Iowa Donald L. Biggs
Iowa State University Kenneth F. Clark
University of Northern Iowa Keene Swett
D. Available Technology for Mitigation of Adverse Effects
1. Land
"NEW MINING METHODS REHABILITATE FLORIDA'S STRIP
MINES.", U.K. Custred. Mining Engineering, April
1563. pp. 50-52.
Early in 1960, American Cyanamid Co. developed
the "simultaneous reclamation" technique which
permits all land mined, except that needed for
settling basins, to be restored at a fairly
reasonable cost. In so doing, American Cyanamid
became the first of Florida's phosphate companies
to make land reclamation an integral part of mine
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planning and mining operations.
The system involves deciding before mining begins
what the land should look like after mining is
completed.
Factors to be considered in this type of planning
include total depth mined, ratio of overburden
to total depth, reach of dragline, contour of
area and adjacent property such as highways, lakes,
homes and farms.
This new method has not increased mining costs
and has slashed reclamation costs more than 40%.
WASTE CLAY DEWATERING AND DISPOSAL. Leslie G.
Bromwell and Thomas P. Oxford. A.S.C.E. Specialty
Conference, Geotechnical Practice for Disposal of
Solid Waste Materials, June 1977.
The Florida phosphate industry has been engaged
in an extensive research program since 1972 with
the objective of developing improved methods for
dewatering and disposal of the waste clays from
ore beneficiation. These clays are currently
being produced at the rate of 40 million tons
per year (dry weight). Traditional disposal
involves the construction of large settling areas,
using overburden soils for dam construction.
Over 50,000 acres of settling areas are in
existence, surrounded by some 300 miles of earth
dams.
The clay settling areas make large tracts of land
unavailable for reclamation and reuse for many
years, and represent an environmental hazard in
the event of a dam failure.
This paper discusses the nature of the disposal
problem and the variety of approaches that may
be taken to sand-clay mixing, with emphasis on
those processes that appear to represent acceptable
solutions.
SEDIMENTATION-CONSOLIDATION BEHAVIOR OF PHOSPHATIC
CLAYS. Berg Keshian, Jr., Charles C. Ladd, and
R.E. Olson. A.S.C.E. Specialty Conference,
Geotechnical Practice for Disposal of Solid Waste
Materials, June 1977.
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Laboratory and field tests have been made to
determine the sedimentation and consolidation
characteristics of waste clays from Florida
phosphate mining operations. The results are
compared with theoretical analyses utilizing a
computer program based on large strain theory,
with variable soil properties and various boundary
conditions.
Field tests were run at an active phosphate mine
by placing plant effluent in 20-inch diameter
steel pipes ranging from 4 to 35 feet in height.
Boundary seepage conditions and hydraulic head
were varied in the tests.
The rate of consolidation and total settlement
in the field tests generally agreed with
predictions based on laboratory tests. Constant
head and falling head seepage situations produced
very similar rates of consolidation, with the
constant head case yielding slightly larger final
strains and higher solids contents. Terzaghi
theory predicts that tg0 should vary with H«
squared; however, the analyses using variable
soil properties showed that tgg is roughly
proportional to Hq.
The results of the field tests have been used
to evaluate alternative methods of waste clay
disposal, including sandwich construction with
tailings sands and stage filling of impoundments.
The technical feasibility of these methods is
discussed.
FIELD TESTS OF PHOSPHATIC CLAY DEWATERING. R.
Torrence Martin, L.G. Bromwell, and John H. Sholine.
A.S.C.E. Specialty Conference, Geotechnical Practice
for LDisposal of Solid Waste Materials, June 1977.
Typical phosphate mining operations in Florida
produce about 54 million gallons per day of waste
clay slurry at approximately 3.5% solids by weight.
The slurry is placed in large retention ponds
or "settling areas" where gradual sedimentation
and consolidation occurs . There are several
reasons for the slow increase in solids content
with time: (1) the density of the slurry is so
low that the applied stress is also low, (2)
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the excess pore water pressures dissipate very
slowly, and (3) the waste clay forms a gel
structure that resists consolidation stresses.
Virtually zero effective stress (total stress
minus pore water pressure) is shown in a 4-month
old settling pond. After five years, throughout
the greater proportion of total depth, the clay
still has very low effective stresses. Laboratory
testing has shown (Roma, 1976) that an effective
consolidation stress of 400 to 600 lbs/sq. ft.
(200 to 300 g/cm ) will result in a clay solids
content on the order of 35%. At this solids level,
all waste clay can be placed below original ground
surface in mined out areas, eliminating the need
for above-ground retention areas.
This investigation examined the effects of improved
drainage and of increased confining stresses on
dewatering of waste ohosphatic clays. Drainage
was improved by sandwiching layers of clean sand
between clay lavers and by having the water table
locate-:! below the nit bottom. The sand layers
also resulted in higher consolidation stresses.
Separate experiments were also made in which sand
was mixed into pre-thickened flocculated clay
slurry in order to nroduce higher confining
stresses.
PLANNING FOR PHOSPHATE LAND RECLAMATION. Thomas
P. Oxford and Leslie G. Bromwell. A.S.C.E. Specialty
Conference, Geotechnical Practice for Disposal
of Solid Waste Materials, June 1977.
Phosphate mining in Florida is conducted by surface
stripping with draglines positioned at natural
ground level. The ore beneficiation process yields
two waste materials: clean sand tailings and
a dilute clay slurry. At the conclusion of mininq,
the land is marVed by parallel or scattered banVs
of overburden spoil and by large above-ground
impoundments used for the storage of waste clays.
Waste 'Hsnosal and land reclamation are major
concerns in the Planning of a Florida Phosphate
mining operation. Handling the large quantities
of waste clays and tailings sands that are produced
necessitates careful forethought to minimize
adverse economic impacts on mining and reclamation.
Compliance with strict regulatory requirements
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set by governmental agencies demands detailed
and effective planning for new mining projects.
Moreover, less well-defined concerns regarding
society and the environment must also be satisfied.
This paper describes considerations involved in
the development of a life-of-mine plan for the
disposal of wastes and the restoration of land
to beneficial use for a future mining tract in
Central Florida. The arrangement and cost of
waste clay settling areas, minimization of
disturbance to unmineable areas, the interface
between the operation and the surrounding
community, the presence of wetland areas, and
the selection of reclamation techniques are among
the concerns that are addressed.
LANDFILLS FROM WASTE SLIMES AND TAILINGS. Charles
Calvin Cook, Erwin Mathew Haynsworth (American
Cyanamid Co.). U.S. Patent 3,718,003(CI. 61-35;
E 02d), Feb. 27, 1973, Appl. 24,090, 31 Mar 1970.
12 pp.
Beneficiation of ores such as phosphate rock
produce both slimes (slurries contg. solids of
particle size < approx. 105 ) and tailings (waste
solids of particle size > approx. 105 ).
Dewatering of the slimes is promoted by mixing
with tailings in a preferred ratio of 6-40 parts
by wt. of slimes to 60-94 parts of tailings (both
on a dry basis). Such mixts. deposited in suitable
excavations dewater at an accelerated rate and
produce a fertile and firm land-fill.
FLOCCULATION OF PHOSPHATE ORE SLIMES. J.C.
Davidtz(to Mobil Oil Corp.). U.S. Patent 3,996,696
, Dec. 14, 1976, Appl. Nov. 19~ 1975; 6pp. Division
of U.S. 3,956,119(FA 10,681).
A method is described for reclaiming arable land
in areas hydraulically mined to recover phosphate
rock. Phosphate slimes are flocculated by mixing
with the extractable organic matter of fertile
topsoil. The flocculated mixture is deposited
in a mine pit and the H2O separated to produce
a layer of dewatered floe. A layer of > 1 ft
of quartz sand tailings is deposited on the
dewatered floe and additional H20 separated.
Then overburden is deposited on top of the
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dewatered floe to restore the original stable
soil profile consisting of an uppermost sandy
layer having good drainage supported on a lower
clay-rich layer having poor drainage.
CHARACTERIZATION STUDIES OF FLORIDA PHOSPHATE SLIMES.
W.E. Lamont. U.S. Bur. Mines. Rep. Invest. 8089,
1975. 24 pp.
Characterization studies of samples of Florida
phosphate slimes showed that the physical,
chemical, and mineraological composition of slimes
are highly variable. Attapulgite was determined
as a common factor controlling the physical
characteristics, including the settling rate,
terminal solids, viscosity, amount of solids in
the filter cake1, and flocculant requirements.
No other parameter studied, including size
analysis, surface area, chemical analysis of the
solids, the supernatant H20 or other mineral
species, showed a strong correlation with the
settling characteristics of any of the samples.
The parameters affecting land recovery in the
phosphate mining area are discussed.
DEWATERING OF PHOSPHATE SLIMES USING COARSE
ADDITIVES. P. Somasundaran, E.L. Smith, Jr., and
C.C. Harris. Proc. 11th Intern, Mineral Processing
Congr., Seminar on Beneficiation on Lean Phosphates
Witn Carbonate Gangue(held Apr. 23-4, 1975),
Cagliari, Italy. Instit. Arte Mineraria, Univ.
Cagliari. pp. 231-49.
Slimes produced during phosphate rock operations
are usually contained in settling ponds occupying
thousand of acres of land. Because of the very
slow settling of these slimes they remain as a
serious environmental hazard for decades. It
was found that small additions of relatively coarse
material such as tailings and sand enhance the
initial settling rate by as much as 30 to 50 times,
leaving a clear supernatant. The mechanism of
the settling of this slurry and of the enhancement
of settling due to the additives has been studied.
Results obtained for the effect of various
materials with a wide range of specific gravity,
surface property, shape and quantity of additives
have been examined. Studies were also conducted
for different initial slime concentration, diameter
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and height of the container, vibration, and pH;
zeta potential was determined as a function of
pH. Results suggest a three dimensional network
model for the system. Soon after mixing, gelling
occurs; but coarser particles and smaller air
bubbles entrapped move and thereby create tears,
fissures, and channels in the slurry structure.
Water seeps through these paths and causes enhanced
settling. Denser or hydrophobic particles, reach
the bottom before the gelling and thus have less
effect on settling. Seepage flow under low
pressure gradient through vertical porous medium
holds promise for dewatering the slimes.
FLOCCULATION OF PHOSPHATE ORE SLIMES. J.C.
Davidtz(Mobil Oil Corp.). U.S. Patent 3,956,119
May 11, 1976, Appl Feb. 19, 1974. p. 6.
A method is described for flocculating phosphate
slimes formed in the hydraulic mining of phosphate
minerals. Topsoil and f^O are slurried and allowed
to settle. The aqueous extract contains H2O-
soluble organic matter from the slurried topsoil.
This extract is decanted and adjusted until it
contains > 50 ppm of organic matter. Phosphate
slimes with a solids content of > 2 wt % is mixed
at ambient temperature with the extract to form
a flocculated mixture from which H2O is separated.
RAPID SEDIMENTATION OF PHOSPHATE ORE SLIMES. A.G.
Smelley and C.E. Spruiell(to the United States of
America as represented by the Secretary of the
Interior). U.S. 4,000,067, Dec. 28, 1976, Appl.
May 21, 1976. p.5.
A method is described for enhancing the settling
of phosphate ore slimes. A fluoride is added
to the slimes at a fluoride to solids wt ratio
of 1:1. The fluoride is selected from HF, NH4
F, H2SiFg, and mixtures thereof at pH 0.5-5.0.
POLLUTION CONTROL IN PHOSPHATE SLIME DISPOSAL.
Howard Patrick Ledden and Klaus Muller (American
Cyanamid Co.). U.S. Patent 3,707,523 (CI. 260-41R;
E02d), Dec. 26, 1972, App. 65,284, Aug. 19, 1970.
Partially hydrolyzed polyacrylamide is added to
waste sand from phosphate mining. The treated
sand is added to the phosphate slime with min.
34
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agitation just before deposition in the settling
basin. The treated slime compacts readily,
releases water, and forms a firm surface within
a few months.
COMPACTION OF SLIMES AND SAND TAILINGS BY THE ENVIRO-
CLEAR THICKENER. L.J. Barreiro, R.D. Austin, A.P.
Kouloheris (Gardinier, Inc., Tampa, FL) Paper
presented to the January 26, 1977 Seminar of the
Phosphatic Clays Project.
Investigations concluded that the best approach
to Gardinier's phosphate slimes problem was the
one that served all of the following objectives:
dewatering and compaction of slimes, separate
expensive pumping of slimes and sand tailings,
sand tailings disposal costs, reclamation of mined
areas, large slime ponds, and conversion of
reclaimed land "to agricultural land.
A detailed pilot plant program of flocculation
and thickening utilizing a 3 ft. diameter Enviro-
clear thickener was initiated. The pilot program
demonstrated that, technically, flocculation and
settling of "combined slimes" with sand tailings
at the beneficiation plant site is feasible.
Results obtained show that a scheme for a 30,000
gpm stream is possible with the following results:
Optimum thickener design rate: 2.8 gpm/ft
In plant water recovery: 87.1%
Optimum flocculant consumption: 0.81bs/ton
dry slimes
Thickener compaction with a 1:1
slimes to tailings ratio: 27.7% solids
Pit compaction is 2 weeks: 40% solids
An economic analysis of the pilot plant scheme
will be conducted. Capital investment as well
as operating costs and savings will be correlated
and compared to the present scheme of separate
treatment of slimes and tailings, pumping and
reclamation.
DEWATERING AND STABILIZATION OF WASTE CLAYS, SLIMES,
AND SLUDGES. Leslie G. Bromwell. June 1976.
The problems of disposal and stabilization of
waste clays, slimes, and sludges are complex,
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chemical engineering, geotechnical engineering,
and clay technology, to name a few. Only in recent
years have geotechnical engineers begun to play
a major role in developing improved methods for
handling these materials.
For waste clays, those processes that have
demonstrated effectiveness include the following:
1. Freeze-Thaw
2. Spherical Agglomeration
3. Electroosmosis
4. Chemical Coagulation
5. Admixing with Coarse Material
6. Drainage Systems
Of these, only chemical coagulation, admixing
with coarse material, and use of drainage systems
have been shown to be both technically and
economically feasible.
The most pressing problems caused by the use of
settling areas for clay disposal are: 1) the
ever-present threat of a dam failure releasing
large quantities of semi-fluid clays, resulting
in extensive water pollution; 2) the unavailability
of large land areas for reclamation; 3) the loss
of water that remains in the clay. Another problem
that is likely to become more serious in the future
is the loss of significant mineral values in the
slimes.
Several potential solutions to the problem of
waste slurry disposal are being evaluated, and
the likelihood of finding feasible alternatives
to above-ground impoundments appears very good.
VEGETATIVE STABILIZATION OF MINERAL WASTE HEAPS.
EPA Industrial Environmental Research Lab., Research
Triangle Park, N.C., EPA 600/2-76-087, Apr. 1976.
The report reviews the establishment of vegetative
cover as a candidate method for reclaiming mineral
ore waste heaps. It begins by describing the
location and properties of spoils and tailings
from mining and ore beneficiation, and briefly
reviews present methods for controlling dust
emissions from them. Most of the report develops
fundamentals for establishing vegetative cover,
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and gives a detailed review of case histories
of both successful and unsuccessful revegetation.
The report contains a catalog of individual plant
species which can be used to provide general
guidelines for establishing vegetative cover.
UTILIZATION OF PHOSPHATE SLIMES. Srini Vasan.
International Minerals and Chemical Corp. Skokie,
111. NTIS as PB-203 191, $0.95. Environmental
Protection Agency Water Pollution Control Research
Series, August 1971.
Small scale tests of the slimes were made to assess
the feasibility of their use as building materials.
A process was developed and demonstrated to be
capable of producing a pelletized, light-weight
aggregate, and finally a light-weight concrete
from the slimes. The four major processing steps:
(1) pumping of clay slurries of 3 tp 30% solids
(2) slime drying in a fluid bed dryer; (3)
pelletizing the dried product and (4) kilning
the produpt to a .suitable aggregate, were
investigated in batch and suitable equipment was
selected. Aggregrate production could use up
to 6-8 million tons of clay solids annually,
releasing up to 5 billion gallons of water to
the environment.
2. Water
FLOCCULATION PROCESS. J.C. Davidtz. U.S. Patent
Ho. 3,956,119, Official Gazette of the United state
Patent Office, Vol. 94 6, No. 2, May 11, 1976. p.
729.
The dilute clay-containing slimes waste, formed
in the hydraulic mining of phosphate mineral,
is flocculated by mixing with an aqueous extract
of fertile topsoil or with fertile topsoil which
is the uppermost two feet or more of overburden
that contains at least 200 parts per million
organic matter extractable by water. Water is
recovered from the flocculated mixture. The
dewatered floe is preferably disposed at a land
reclamation site and covered with overburden to
restore the original stable soil profile, i.e.
an upper layer of soil with good drainage and
a lower layer having poor drainage. One manner
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of utilizing the flocculated mixture of this
invention is to store it in a quiescent state,i.e.,
without deliberate agitation other than that caused
by wind, for a period of from 24 hours to about
one month, in a pond or settling area. During
such storage very effective sedimentation will
occur with the copious formation of supernatant
clear water than can be separated and returned
for use in the mining process, or discharged to
a river.
ELIMINATION OF WASHER SLIMES FROM THE PRODUCTION
OF PHOSPHATE CHEMICALS. EPA Industrial Environmental
Research Lab., Research Triangle Park, EPA/600/2-
76/045, Mar. 1976.
The report gives results of laboratory studies
to determine the feasibility of a new phosphoric
acid process involving dry mining of the matrix,
calcination, and digestion with phosphoric/sulfuric
acid mixtures (five types of Florida phosphate
matrices were used). Process steps included
upgrading the matrix by dry methods, calcination
in a static bed, and digestion comparable to
commercial dihydrate processes. The matrix samples
were upgraded by removing clay by selective
grinding and air classification, and by separation
of the sand fraction electrostatically. Typical
clay removal values were 80-90% at a phosphate
loss of 15-25%. Calcination produced an acceptable
phosphoric acid from good quality matrix, but
failed to reject metal impurities sufficiently
to permit processing of poor-to-average matrix.
Calcination eliminated the interference of clay
in the digestion and filtration steps. Addition
of mineralizers had only marginal effect on metal
solubility.
THE FLORIDA PHOSPHATE SLIMES PROBLEM-A REVIEW AND
A BIBLIOGRAPHY. Bureau of Mines, Tuscaloosa
Metallurgy Research Lab, Information circular 8668,
Jan. 1975. 46 pp.
The Florida phosphate industry, which supplies
about three-fourths of the domestic phosphate
fertilizer, produces tremendous volumes of
phosphatic clay wastes (slimes). These clays
retain a high percentage of water for extended
periods of time. The clays also pose an
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environmental hazard because the disposal technique
involves above-ground storage behind earthen dams.
Although much research has been undertaken by
numerous organizations to dewater slime, no
completely satisfactory solution has been
developed. In June 1972, a cooperative effort
by the U.S. Bureau of Mines and the Florida
phosphate mining industry was initiated to develop
a solution for dewatering the Florida phosphatic
slimes. This report discusses various aspects
of the slimes problem, reviews past research,
makes recommendations for future research and
includes a bibliography of references and patents
dealing with the subject.
ELECTROPHORETIC AND FILTRATION STUDIES OF A FLORIDA
PHOSPHATE SLIME. Oleg Terichow, G.V. Sullivan,
and E.K. Landis. Bureau of Mines, Tuscaloosa
Metallurgy Research Lab, Report of Investigations
8028, May 1975.
The disposal of slimes generated in processing
Florida phosphate rock is a persistent problem
that has not yet been resolved. The settling
of solids in ponds, however, requires a very long
time, sometimes extending over a decade.
Furthermore, the danger of dam failures with the
resulting ecological damage is a real problem
to the phosphate industry. This report contains
results of a Bureau of Mines investigation of
the optimum conditions for mutual coagulation
and settling of phosphate slime with anthra.cite
addition based on alteration of physicochemical
and electrokinetic properties. Electrophoretic
mobility was altered by addition of aluminum
sulfate, and settling character was determined
by filtration.
SEDIMENTATION OF PHOSPHATE SLIMES. Oleg Terichow.
Patent Application, Mar. 19, 1973. PAT-APPL-342
921, DOCKET/MIN-2023. Government-owned invention
available for licensing. Copy of application
available NTIS.
The invention relates to dewatering phosphate
slimes. A preselected colloidal particle system
is added to slime suspension in presence of
predetermined flocculaht concentrations to settle
out the slime.
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PROCESS OF REMOVING WATER FROM SLIMES. C.C. Cook,
and E.M. Haynsworth. American Cyanamid Co.,
Stamford, Conn. U.S. Patent No. 3,763,041, Official
Gazette of the United States Patent Office, Vol.
915, No. 1, October 2, 1973. 274 pp.
A means is provided for eliminating the substantial
waste disposal problems in disposing of slimes
and tailings and, in particular, for eliminating
the safety hazards as well as land and water
pollution hazards. When slimes are admixed with
tailings there is a substantial enhancement in
the rate at which the water is released from the
waste slimes of phosphate rock processing.
Virtually useless slimes can be transformed into
fertile soil having acceptable bearing strength
so as to render such suitable for purposes of
land reclamation and pollution control.
3. Air
"WET GRINDING OF PHOSPHATE ROCK HOLDS DOWN DOLLARS,
DUST, AND FUEL," S.V. Houghtaling. Engineering
and Mining Journal, January 1975, p. 94.
A wet rock grinding process developed for the
phosphate industry by Davy Powergas Inc. of
Lakeland, Fla., can reduce capital costs, eliminate
dust emissions, and save fuel and power
consumption, thereby reducing operating costs.
Total savings achievable through wet rock grinding
are presently estimated at $3 to $4.25 per ton
of P2O5.
An estimated 1 million bbl of fuel oil could be
saved annually by phosphoric acid producers in
Florida alone if wet phosphate rock grinding were
utilized throughout the industry. Florida's
phosphate industry accounts for more than 60%
of the phosphoric acid produced in the US.
The advantages of wet rock grinding include: a
30-40% reduction in horsepower in the grinding
area, with a corresponding reduction in mill size;
elimination of rock drying (for a savings of about
2.5 gal of fuel oil per ton of rock, or 8-9 gal
of fuel oil per ton of PjO^); open wet storage
for all rock; and the elimination of all air
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for all rock; and the elimination of all air
classification equipment and its housing. The
result is a reduction in operating costs in the
grinding and attack areas.
The elimination of rock drying saves $0.60 to
$1 per ton of rock or $2.10 to $3.50 per ton of
P2O5. With the new process, power in the grinding
and attack area is reduced by 35 kwh per ton of
P2O5. At 1.2-mill power, this is equivalent to
a savings of $0.42 per ton of P2O5. Overall
operating costs at a Florida location can be
reduced by a total of $3 to $4.25 per ton of P
2°5 *
POLLUTION PROBLEMS IN PHOSPHORIC ACID PRODUCTION.
K.K. Huffstutler. In: Phosphoric Acid, Vol. 1,
Part II. A.V. Slack, Marcel-Dekker, Inc., 1968.
pp. 727-739.
The dust resulting from drying and grinding
phosphate rock contains 3 to 4% water-insoluble
fluoride. Insofar as pollution by fluorides is
concerned, this dust is of little concern except
for occasional effect on animals; research has
shown that cows will assimilate about 50% of any
water-insoluble fluorides they consume. With
respect to effects on plants and human beings,
the fluorides are not a problem. However, the
dust is a troublesome nuisance.
A dryer handling 100 tons of rock per hour will
emit from 15 to 30 lb. of dust per hour, even
with a modern scrubbing unit made up either of
wet scrubbers (single or double stage) or
electrostatic precipitators preceded by dry cyclone
dust removers.
Raymond mills and ball mills of up to 20-ton/hr
capacity will emit as little as 3 to 4 lb/hr of
dust. Dust is usually removed in bag filters
but wet scrubbers have proved successful.
4. Resource Depletion and By-Product Recovery
UTILIZATION OF FLORIDA PHOSPHATE SLIMES. Srini
Vasan(Environ. Prot. Agency, Chicago, 111.). Proc.
41
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Miner, Waste Util. Symp., 3rd, 1972. pp. 171-7.
Edited by Murray A. Schwartz, IIT Res. Inst.:
Chicago, 111.
A novel method for converting phosphate slime
(contg. clay minerals, quartz, and fluorapatite)
into building materials by a fluidized bed drying
system is described. Two main problems in the
com. use of the phosphate slimes are a lack of
a technique for retrieving slimes from the pond
and the need for an efficient method for drying
the slimes. Two types of pumps can easily handle
the continuous pumping of the slimes. A cross-
flow fluid dryer is selected. In this way
phosphate slimes contg. 30% solids are continuously
dried to a powder contg. 95-9% solids and the
dryer works in the range of 75% fuel efficiency.
Dried slimes thus become a potentially useful
raw material for conversion into ceramic products
like brick, pipe, tile, and aggregate.
RECOVERY OF PHOSPHATES FROM PHOSPHATE SLIMES. Eric
Siemers. U.S. 3,450,633 (CI. 210-54), June 17,
1969, Appl. Jan. 05, 1968. p. 2.
Ag. suspensions of fines from the com. washing
of phosphate rock are acidified to pH 4.5-5.0,
heated at 150-200°F. with H20-insol. org. material,
and neutralized with a base. The resulting mixt.
is dewatered by filtering or centrifuging. The
H2O is recycled to the phosphate washer. " The
solids are calcined to burn off the org. material
and can be used as a source of phosphate raw
material. Thus, 1 gal. phosphate slimes contg.
12% solids was acidified to pH 5 with concd. HC1.
Sawdust equal to the wt. of solids was added and
the mixt. was agitated at 160°F. for 1 hr.. The
mixt. was then brought to pH 7 by addn. of NH^
OH and filtered through a centrifuge.
ULTIMATE DISPOSAL OF PHOSPHATE FROM WASTE WATER
BY RECOVERY AS FERTILIZER. EPA Water Pollution
Control Research Series 17070 ESJ-01/70, January
1970.
Many of the proposed processes that reduce
orthophosphate in the effluents from sewage
treatment plants result in the extracted phosphate
42
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being concentrated in the digester supernatant.
This phosphate must be removed prior to disposal
of the supernatant or its recycle back to the
head of the treatment plant. Digester supernatant
was treated in two ways. The first was to add
magnesia and elevate the pH to 9 to cause
precipitation of the phosphorus. The other
technique was to apply heat and/or vacuum to the
digester supernatant which caused precipitation
of the soluble orthophosphate. A 90% removal
of orthophosphate can be achieved by either
approach. The heat and/or vacuum process also
yields a supernatant substantially lower in BOD,
COD, and nitrogen concentration. The precipitated
phosphorous (primarily a mixture of calcium
phosphate and magnesium ammonium phosphate) was
found available^for plant food according to
AOAC(i.e., Association of Official Agricultural
Chemists) procedures. Work was conducted by bench
and pilot plant studies on digester supernatant
from the Lake Zurich, Illinois sewage treatment
plant and from the Libertyvi1le, Illinois sewage
treatment plant. •
WATER USE IN THE MINERAL INDUSTRY. Alvin Kaufman,
and Mildred Nadler. Bureau of Mines, Washington,
D.C. Div. of Economic Analysis, Bur Mines Infrom
Circ No R285, 1966.
To aid industry and Government in planning water
developments the Bureau of Mines in 1963 canvassed
mineral producers to determine water use in 1962.
Water used by the mineral industry is only 2%
of the water withdrawn by all industry. The major
water-using mineral industries are natural gas
processing, phosphate rock, sand and gravel, and
iron ore. Total water use and new water intake
is dependent on the quantity of material processed
and the Process water requirements of the
particular industry or commodity. Recirculation
is dependent on the processing requirements of
the particular commodity, the manner in which
the water is used, cooling and condensing
requirements in large industries, the quality
of new water intake, and the need to treat new
discharged water. Consumed water is dependent
on the quantity of water recirculated, the
temperature "and humidity in the area, and the
proportion of water used for cooling and
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condensing. A threefold increase in water use
by the mineral industry by 1985 is forecast.
DISPOSAL AS WASTE MATERIAL. I.A. U.S. PRACTICE.
Q.D. Bowers. In: Phosphoric Acidf Vol. I, by A.V.
Slack, New York: Marcel Dekker, 1968. pp. 505-
510.
Only very limited uses have been found for by-
product gypsum in the U.S. The relatively low
cost of sulfur and the ready availability of good
quality native calcium sulfate have discouraged
interest in recovery processes such as those
practiced in other countries. Hence, the gypsum
must be discarded and the large amount produced,
about 4.5 tons/ton of P2*^5' Presents a major
disposal problem.
The gypsum filter cake is washed with water and
discharged from the filter as a wet cake containing
about 18-35% free moisture. In the majority of
wet-process phosphoric acid plants, water sprays
sluice the material into a receiving vessel from
which the slurry is pumped or allowed to flow
by gravity to a disposal area where it settles
out and surplus water is collected for reuse.
Approximately 1 acre-ft. of disposal area is
required per year for each daily ton of P2°5*
Water circulating with the gypsum contains
appreciable quantities of fluorine and P2C>5.
The practices of diked gypsum pond systems,
recovery and reuse of water, and neutralization
and clarification of pond water are discussed.
III. Chemical Processing
A. Description of Processes
CONCENTRATED PHOSPHORIC ACID FREE OF FLUORINE. Rudolf
Batrla, Jaroslav, Karel Klein, Vaclav Bolech, Jaroslav
Bartos, Vladimir Lakota. Czech. 146,619 (CI. C 01b),
Dec. 15, 1972, Appl. 1801-69, Mar 13, 1969. p. 2.
Decompn. of crude phosphates with HNO3 gives a
relatively pure H3PO4 useful for the manuf. of
chemicals and feed additives. The crude decompn.
mixt, is chilled to sep. >85% of the Ca(N03)2 and
the Ca^+ remaining in the liquors is converted to
CaS04 with H2S04 which is filtered. The filtrate
44
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is evapd. and the vapors, contg. HNO3, n oxides, and
H2f5^F6' are traPPed in Tnilk of lime. The pptd. CaF
2 and CaSiF^ are seed, and the Ca(N03)2 converted
to a fertilizer. The redisula concd. soln. is used
to prep, a product contg. 70-100% H3PO4.
STATUS OF MODERN WET-PROCESS PHOSPHORIC ACID TECHNOLOGY.
W.C. Scott, G.G. Patterson and C.A. Hodge. Process
Engineering Branch, Division of Chemical Development,
Tennessee Valley Authority.
The production of wet-process phosphoric acid has
been practiced commercially since 1870. The acid
is used mainly as an intermediate in producing
fertilizers. Most of the wet-process acid plants
operating today are dihydrate process plants because
of the relative simplicity of design and operation
afforded by this process. Other processes employed
commercially are classified as hemihydrate, combination
hemihydrate/dihydrate, or anhydrite processes.
The basic scheme of operations for all wet acid
processes is about the same. Phosphate rock is
acidulated with sulfuric acid and the resulting calcium
sulfate, together with other insoluble impurities,
is separated from the phosphoric acid by filtration.
The various types of processes are compared in this
article.
Recent research and development has been concentrated
mainly on dihydrate and hemihydrate nrocesses, or
combinations of the two, and on acid purification
processes, such as solvent extraction. A summary
of plant construction during the past five years is
presented also, and announced plans for further
construction are discussed.
T-Jet-process superphosphoric acid became an important
intermediate for high-analysis fertilizer production
during the 1960's. Production of wet-process
superphosphoric acid by the vacuum and direct-fired
concentration processes is described and future
considerations are discussed. Some of the Problem
areas in current uses of phosphoric acid are
delineated.
Installed capacity for production of wet-process aci<^
in the U.S. was estimated at about 5,200,000 tons
of P2°5 oer Year 1971. Projected capacity increases
45
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to January 1976 would brinq the total to about
3 ,170 ,000 tons at that time-an increase of /about 57
percent over the five-yeat. wtriod. With the inclusion
of oreviouslv closed plants which may be restarted
during this period, actual production could increase
by as mucn as 63.5 percent.
B. Environmental Effects
1. General
REVIEW OF EFFLUENT PROBLEMS IN FERTILIZER
MANUFACTURE. F.W. Bennett and B.C. Spall In Symp.
Fertilisers and the Environment London, England.
(held Apr. 29, 1976, London, England). Fert. Soc.,
Proc. No. 156. pp. 5-54.
Gaseous effluents are best treated by modifying
the process to reduce the level of emission.
Where this is not possible or uneconomic, the
effluent can be scrubbed to produce a liquid
effluent which, if possible, should be recycled
or stripped to recover the pollutant. Liquid
effluents are likely to receive increasing
attention in the future as emission limits are
imposed or tigncened. Methods of recovering the
pollutant or recycling the liauid effluent will
probably be favored solutions to the problem.
Rising raw material costs add iniuecus to this
approach. The only solid effluent of major
importance discharged from fertilizer works is
gypsum. Where disposal to sea or river, or use
as land-fill* is not possible, its conversion to
plaster, plasterboard, or gypsum blocks may Drove
economically attractive. The construction of
gypsum ponds with re-use of pond water is an
alternative where markets for the plascet products
are not available.
RADIOCHEMICAL POLLUTION FROM PHOSPHATE ROCK MINING
AND MILLING. J.V. Rouse. In: Water Resources
Problems Related to Mining; Proceedings No. lT7
American Water Resources Association, Minneapolis,
Minnesota, June 1974. pp. 65-71.
Mining and milling of phosphate rock has been
responsible for major water pollution problems
46
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of a conventional nature in the past. Recent
data indicate that the industry is also responsible
for major, unrecognized radiochemical pollution
of water and air, and the generation of radioactive
solid waste. The untreated liquid effluents troru
phosphoric-acid plants are 30 times the Maximum
Permissible Concentration for radium-226. The
byproduct gypsum generated by the industry contains
approximately 25 picocuries of radium-226 per
gram. Use of this material for building products
would expose the population to radon decay
products. Seepage of contaminated water form
process ponds has contaminated large areas of
groundwater. Treatment and stabilization measures
exist to control the surface water discharge and
the solid waste. Problems still exist with resDect
to seepage. Failures of slime ponds constitute
a massive release of radium, measured in curies,
to the aquatic environment.
ENVIRONMENT FACT SHEET 1976. Florida Phosphate
Council, Lakeland, Fla.
Research, development, and use of systems and
equipment for the purposes of air quality control,
water quality control, water conservation, and
land reclamation are summarized for 1976.
2. Water
PROBLEMS AND MANAGEMENT OF WATER QUALITY IN
HILLSBOROUGH BAY, FLORIDA. Hillsborough Bay
Technical Assistance Project Technical Programs,
Southeast Region Federal Water Pollution control
Administration, Tampa, FL, Dec. 1969.
The objectives of these studies were: to identifv
and quantify key sources of waste in Hillsborough
Bay and to determine their effect on water use;
to determine the cause or causes of noxious odors
in Hillsborough Bay and; to recommend means of
modifying conditions in Hillsborouqh ^ay to
eliminate the causes of obnoxious odors and make
possible other desirable uses.
Sixty-eight municipal and industrial waste sources
were identified and investigated. The major
contributor of carbonaceous organic material to
Hillsborough Bay is the primary sewage treatment
47
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plant of the city of Tampa which discharges about
28 million gallons per day at the southern tip
of Hookers Point. This effluent contains
carbonaceous organic material equivalent to a
population of 290,000 and represents more than
85% of all carbonaceous waste from point sources.
The plant is also the major contributor of
unsatisfied nitrogenous material, discharging
7300 pounds per day or more than 40% of the total
input to the Ray from point sources. The other
major contributors of oollution to the Bay are
the MacDill Air Force Base sewage treatment plant,
U.S. Phosphoric Products Comoany, Nitram Chemical
Company, Palm River (Sixmile Creek), Hillsborough
River and the Alafia River. The Alafia River
which has fourteen phosphate processing plants
near its headwaters contributes more than 43,000
pounds per day (as phosphorus,P) or 78% of the
total phosphorus input to Hillsborough Bay from
point sources. U.S. Phosphoric Products and the
Alafia River contribute 94% of the total
phosphorus. The Alafia River, Nitram Chemical
Company and U.S. Phosphoric Products together
discharged nearly 50% of the total unsatisfied
nitrogenous material to the Bay. Another major
source of nitrogen and phosphorus to Hillsborough
Bay at intermittent periods during the survey
was the flushing of water hyacinths from the Tampa
wat§r sunply reservoir down the Hillsborough River.
EFFECTS OF THE PHOSPHATE INDUSTRY ON RADIUM-226
IN GROUND WATER OF CENTRAL FLORIDA. Robert F.
Kaufmann and James D. Bliss, 1977.
Principal U.S. phosphate production is from central
Florida where strip mining, dewatering of shallow
ore bodies and overburden, extraction of deep
ground water for processing, and waste disoosal
intimately associate the industry with water
resources. Elevated concentrations of uranium
and radium in ore, overburden, and ground water
have prompted several Federally-sponsored studies
in the last decade to ascertain the water Quality
effects of the industry, particularly with respect
to radium-226 in potable water supplies.
Using 227 analyses of radium in water samples
collected from a study area of 3000 square miles,
48
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parametric and non-parametric statistical tests
and graphical techniques were utilized to evaluate
radium concentrations in three separate aquifer
systems(water table, Upper Floridan, Lower
Floridan), mineralized and unmineralized areas,
and two time periods: 1966 and 1973-1976.
Geometric mean radium concentration in the water
table aquifer in unmined, mineralized areas is
0.70 pCi/1 compared to arithmetic means of 0.92
and 1.00 pCi/1 in mined and background areas.
For the Upper and Lower Floridan aquifers, average
concentrations of Ra-2 26 are equal or higher in
the control areas relative to mineralized or mining
areas. Assessment of Ra-226 content in the
combined water table and Upper Floridan aquifers
with the Kruskal-Wallis test ( = .05) also
indicated that the mineralized but unmined area
tends to have higher Ra-226 than areas impacted
by mining. Ad hoc testing (t test; .05) of the
Lower Floridan aquifer in mineralized versus
nonmineralized areas also revealed significantly
higher radium concentrations in the latter,
apparently a result of natural factors not related
to mining or mineralization.
No distinct temporal trend is apparent in comparing
individual or grouped (Mann-Whitney test, =.05)
observations made in 1966 and those in the period
1973-1976. Existing radium data do not
substantiate contamination of ground water
throughout the areas of mining and processing
as a result of the phosphate industry. However,
local contamination associated with specific
operations has occurred and is likely to continue
as water development and mining expand, further
stressing the Floridan aquifer. Natural
variability in radium content of ground water
complicates determination of background versus
contaminated conditions and underscores the need
for more intensive data collection as an integral
part of water and land management.
THE POTENTIAL CONTRIBUTION OF FERTILIZERS TO WATER
POLLUTION. L.A. Douglas. Water Resources Research
Institute, Rutgers University, New Brunswick, N.J.,
June 1976.
49
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Field studies were undertaken to determine, the
magnitude of leaching of fertilizer NO^, NH4 and
PO4. The effect of N-SERVE on these reactions
was observed, N-SERVE had little effect on leaching
because most leaching takes nlace during the fall
and winter when precipitation exceeds
evapotranspiration. No leaching of NH, or PO^
was observed. The common fertilizer efficiency
measure of N in crop/N applied in fertilizer may
be used as an indication of the amount of
fertilizer N that will be leached. Studies of
nutrients in streams were undertaken to relater
land use to NO3, NH^ and P04 concentrations in
surface waters. Sewage treatment plants and
'illegal drains' were major sources of all three
ions. In order of decreasing contribution of
NOo: urban land contributes more than cropland
which contributes more than woodlands, Urban
lands, croplands and woodlands contribute equal
amounts of and P04 to streams. The 'background
level' of PO4 in central New Jersey streams is
many times highter than the 0.01 ppm level often
advocated. Although very high concentrations
of NO, were found in the soil solution in the
subsoil the concentration of NO^ found in streams
was rather low. Denitrification must be an active
process in subsoils, and probably in the
groundwater.
BEHAVIOUR OF SOME PHOSPHATIC FERTILIZERS IN WATER.
n.S. Gupta. Khatauli Manure Mills, Khatauli(India),
J Indian Soc Soil Sci., Vol. 21, No. 4, 1973. po.
413-420.
The behavior of raw bone meal, steamed bone meal,
calcined bone meal, rock phosphate, calcined rock
phosphate and high grade basic slag in water at
different conditions was studied. Water plays
an important role in the decomposition of these
phosphates; it remains active 50-60 days in the
case of calcined rock, bone phosphates, basic
slag and rock nhosohate. In the case of raw and
steamed bone meals, water is also responsible
to,form organic acids which increase the rate
of -decomposition and improve the ohosnhate status
in aqueous solutions. C02 decomposed these
phosphatrc materials; its efficiency was
pronounced at low concentration. The relative
solubility in CO2 and water followed the order:
50
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raw bone raeal> steamed bone meal> calcined bone
meal> high grade basic slag> calcined rock
phosphate> rock phosphate. The suitability of
these phosphatic fertilizers for different soil
conditions is discussed.
URANIUM IN RUNOFF FROM THE GULF OF MEXICO
DISTRIBUTIVE PROVINCE: ANOMALOUS CONCENTRATIONS.
R.F. Spalding, and w.M. Sackett. Science, Vol.
175, No. 4022, February 11, 1972. pp. 629-631.
That uranium concentrations in North American
rivers are higher than 20 years ago is attributed
to increased agricultural use of phosphate
fertilizers with high uranium concentration.
Experiments have been designed to determine the
chemical behavior of uranium during fertilizer
production and weathering of fertilized soil and
to evaluate the pollution potential of uranium.
Uranium concentrations for 22 samnles from 15
different rivers flowing into the Gulf of Mexico
were determined by a delayed neutron technique
and tabulated. Those rivers flowing through
uranium-bearing strata and highly agricultural
regions show the highest concentrations of the
metal. Experiments on 27 commercial fertilizer
samples (0-46 percent of p2^5' varyin9
concentrations of Nand K show: (1) a linear
relationship of uranium to the percentage of P
2O5 and (2) extremely high concentrations of
uranium in the triple superphosphates (0-46-0).
Analysis of different fertilizer processing steps
showed a step-by-step increase of uranium per
increased percentage of PoOs* When a small plot
of land treated with 10-20-10 commercial fertilizer
had an equivalent of 0.5 inch of rain apnlied,
uranium in the runoff was 28 times that in a
similar blank application. Little uranium uptake
was found to occur in alfalfa, corn, and soybeans;
however, the absorption radioactive decay products
of uranium by plants make it a potential
environmental hazard.
THE ACCELAERATION OF THE HYDROGEOCHEMICAL CYCLING
OF PHOSPHORUS. W. Stumm. Water Research, Vol 7,
Nosl/2, January/February 1973. op. 131-144.
By mining phosphorus in progressively increasing
quantities, man disturbs ths ecological balance
51
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and creates undesirable conditions in inland
waters, estuaries and coastal marine waters.
The civilizatory increase in phosphorus supply
to the oceans although of little consequence to
the oxygen reserves of the deep sea, augments
markedly the marine environments with intermittent
or permanent oxygen deficient conditions. Because
most aquatic food resources are produced in
estuaries and coastal areas, the deterioration
in water quality of these regions decreases the
potential harvest of marine animal protein.
Present agricultural practice of excessively
fertilizing land needs to be reexamined; present
agricultural technology must not without
modification be exported to tropical areas.
Present drainage systems for sewage, industrial
wastes and storm water runoff accelerate the
transport of nutrients and other pollutants to
the rivers and the sea; waste plants are remarkably
inefficient in mitigating this civilizatory flux.
INORGANIC FERTILIZER AND PHOSPHATE MINING INDUSTRIES
WATER POLLUTION AND CONTROL. Water Pollution
Control, Research Series No 12020 FPD, September
1971.
A state-of-the-art survey was made of the water
pollution problems which result from the production
of inorganic fertilizers and phosphate rock.
98 plants representing 33 different companies
were surveyed. Production figures since 1940
and estimates of production through 1980 were
accumulated for phosphate rock and the major
fertilizer products. The specific production
operations which are the principal generators
of contaminated waste waters were identified,
and the waste water volumes and compositions for
each operation were determined wherever possible.
The capability of current technology to treat
and control the contaminated waste waters generated
by the fertilizer industry was evaluated. Problem
areas where additional research and development
effort is needed to provide adequate control of
waste water discharge were identified.
3. Air
POPULATION RADIATION DOSE ESTIMATES FROM PHOSPHATE
INDUSTRY AIR PARTICULATE EMISSIONS. J.E., Partridge,
52
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T.R. Horton, and E.L. Sensintaffar. Technical Note
ORP/EERF-77-1.
The EPA Office of Radiation Programs has conducted
a series of studies to determine the radiological
impact of the phosphate mining and milling
industry. This report describes the efforts to
estimate the population radiation doses resulting
from airborne emissions fo particulates from the
industry.
Two "wet-process" phosphoric acid plants and one
ore drying facility were selected for this study.
The 1976 Annual Operations/Emissions Report,
submitted by each facility to the Florida
Department of Environmental Regulation, and a
field survey trip by EPA personnel to each facility
were used to develop data for dose calculations.
The field survey trip included sampling for stack
emissions and ambient air samples collected in
the general vicinity of each olant. Population
and individual radiation dose estimates are made
based on these sources of data.
The results of this study show small, but
measurable, increases in levels of radioactivity
surrounding the phosphate industry operations.
However, it should be noted that levels
statistically above background were measured in
only 5 of the 12 locations sampled. Dose
projections also show the small magnitude of
airborne particulate radioactivity released from
the phosphate industry operation. It appears
that drying operations are the most significant
source of airborne radioactive particulates.
HISTOLOGICAL AND CHEMICAL STUDIES IN MAN ON EFFECTS
OF FLUORIDE. R.A. Call. Public Health Rents. Vol.
30,. No. 6, 1965. pp. 529-38.
The presence of elevated concns. of fluorides
in the atm. has been assocd. with changes in
certain plants and an increase in the fluoride
content of forage in certain areas in Utah. Long-
term ingestion of such forage by some animals
has produced changes characteristic of fluorosis
in some of them. It seemed important to det.
if man was also being adversely affected. In
this investigation, 127 human bodies were autopsied
53
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and studied for gross, histol., and chem. evidence
of fluoride intoxication. Eighty-eight of these
deceased persons came from geographic areas known
to have had elevated fluoride levels in the atm.
and forage. Analyses for F, Ca, P, and ash were
made on the calvarium, sternum, rib, iliac crest,
and lumbar vertebrae. Detns. for F and dry matter
were made on the brain, heart, lungs, thyroid,
aorta, liver, spleen, pancreas, and kidney. The
highest F levels were observed in older adults
showing the end-stage kidney of bilateral
pyelonephritis and polycystic disease. Av. levels
were found in subjects with unilateral
pyelonephritis and in subjects with pyelonephritis
with only slight to moderate disease. The highest
F levels found, in subjects with the most severe
kidney disease, were within the normal range,
and no disease assocd. with F was evident.
UTILIZATION OF VEGETATION AS DETECTOR OF FLUORIDE
POLLUTION AROUND A PLANT EJECTING GASEOUS FLUORIDE
EFFLUENTS. Francoise Teulon(Commis. Energ. At.,
Pierrelatte, Fr.). Report 1971, CEA-R4207, NTIS
(U.S. Sales Only), CEA. 31 pp.
F pollution (chronic or occasional) around a plant
ejecting gaseous fluroide effluents can be detected
from vegetation samples by chem. anal. Systematic
monitoring allows the effects and qra.vity of the
pollution to be estd. The anal, method used
consists of a double distn. (in H3PO4 and HC10
a ) followed by a spectrocolorimetric anal.
(alizarine-complexon-lanthane). This method of
control allows both the efficiency of the trapping
installations and also the aonearance of effluents
at unexpected places to be checked. In the event
of an accident, it is possible to det. the
advisability of prohibiting the consumption of
locally gtDwn produce by humans or fodder by
cattle. The relation between visible damage to
certain vegetables (tomatoes, haricot beans, and
sorghum) and their F contents was most marked
at the level of the leaves; chem. anal, may thus
be used to confirm or reject information obtained
on the basis of visual evidence.
RESULTS OF TEN YEARS' WORK (1951-1960) ON THE EFFECT
OF FLUORIDES ON GLADIOLUS. A.E. Hitchcock, P.W.
Zimmerman, and R.R. Coe. Contrib. Boyce Thompson
54
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Inst. 21, 1962. pp. 303-44.
Plants in the 5-7 leaf stage exhibited more tip
burn and accumulated more F from fumigation with
HF than plants in the 3-leaf stage. Middle-aged
leaves generally exhibited more tip burn, but
the older leaves accumulated more F than younger
leaves. In general, the more resistant varieties
accumulated the most F irrespective of flower
color. This applied both to fumigated plants
and controls. Increase in tip burn was correlated
with dosages 2-4 times the threshold level. There
was no relation between susceptibility and no.
and location of stomata. At levels of HF up to
2 p.p.b. which caused 5-8 cm. of tip burn, there
was no significant effect on dry wt. of tops in
corm yield in the varieties Snow Princess and
Elizabeth the Ouien, but the production of flower
spikes was decreased. Within 1 week after
fumigation with HF, above-ground parts lost from
10-50% of their F content, while control plants
gained F.
EFFECT OF ATMOSPHERIC FLUORINE POLLUTION ON THE
LIVING ORGANISM. C. Balazova, A. Rippel, e. Hluchan.
Mutr., Proc. Int. Congr., 8th, 1969(Pub. 1970).
op. 709-ll(Eng) .
Edited by Nasek, Josef. Excerpta Med.: Amsterdam,
Neth. Data accumulatd in the neighborhood of
an Al factory for 8 vears showed av. F values:
in air 0.02-014 mg/m^; in drinking water 0.2 mg/1.•
in the food of plant origin 0.5-10.0 mg/kg; and
in food of animal origin 0.5-1.2 mg/kg (fresh
wt.). The F in the bones of sparrows and frogs
was 2-14 times that of controls. The F in milk
was up to 2 times that from control areas. No
significant difference was noted in a comoarison
of pigeon bones and eggs from exposed and control
areas. Among exposed children there was a decrease
in the hemoglobin and an increase in the
erythrocytes. The F was 2-3 times higher in the
teeth, nails, hair, and urine of exposed children
than those in the control area. Based on the
effect of the F emissions, controls were instituted
to improve the living environment.
EFFECT OF FLUORINE EMISSIONS Of1! ANIMALS IN THF
SURROUNDINGS OF AN ALUMINUM PLANT. G. Balazova,
55
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and Eugen Hlucban. Air Pollut., Proc. Eur. Congr.,
1st, Apr 22-21 , 1968(Pub. 1969). pp. 175-9(Ger).
Measurements of the F contents of air and fallout
dust were made in the immediate surroundings of
an A1 plant over an 8-year period. A control
noncontaminated area was used as comparison to
det. the effect of the Al plant's emission on
the F content in animals, esp. in bones, eggs,
and milk. The F content of the bones of sparrows,
frogs, and rats was 2-14 times as high as these
same animals in the control area. In milk, F
concns. in the exptl. area were twice as high.
No significant differences were obsd. between
exposed and control areas in the F content of
pigeon bones and hen eggs. F was found to be
taken in by the animals by lung inhalation as
well as direct body contact with the nolluted
atm. Weather conditions were also found to nreatly
affect the F content of the atm. During calm
weather (30.5% of the year) the highest concns.
of F in the atm. varied from 0.02 to 0.14 mg F/m
. In dust, the highest concns. of F were 7.34
tons/km^-year.
"FLUORIDE EXPOSURE AND WORKER HEALTH." 0.PT.
Derryberry, M.D. Bartholomew, and P.B.L. Fleming,
Archives of Environmental Health, Vol. , No. 4,
1963, pp. 503-11.
Comparison of workers in a phosphate fertilizer
plant with a control group showed no significant
difference in incidence of a no. of diseases which
might be attributed to fluoride ingestion.
Albuminuria was significantly more frequent in
the exposed group, suggesting a relation between
excretion of F and renal function. Dental health
was generally better in the exoosed nroup than
in the controls. Seventeen individuals showed
bone d. changes of minimal or auestionable degree.
Av. urinary excretion of F ranged from 4.53 p.o.m.
in exposed subjects with no increase in bone. d.
to 5.18 in those with increased bone d. Medical
history showed slightly higher incidence of
respiratory diseases, probably due to acid gases
rather than to ingestion of F, and musculoskeletal
conditions which were not correlated with bone
d. increases.
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RESPONSES OF VEGETATION TO ATMOSPHERIC FLUORIDES.
Harris M. Benedict, James M. Ross, and Robert H.
Wade. J. Air Pollution Control Assoc. Vol. 15.
No. 6, 1965. pp. 253-5. ~ ~
Alfalfa plants fumigated with HF at night
accumulated F~ as rapidly as plants fumigated
during the day. Most of the F~ accumulated at
night could be washed off the plants, indicating
surface adsorption rather than internal absorption.
Most of the F~ accumulated from day fumigation,
when the stomata were oper, entered into the plant.
With night fumigation, the F~ total content, both
on and in the plant tends to reach a plateau after
24 hrs. of fumigation, while with day fumigation
the F~ content after 40 hrs. on or in the plant
is about twice that after 24 hrs. Seedlings of
alfalfa, orchard grass, chard, and Romain lettuce
were transplanted to a hydroponic soln. and grown
for 2 months in a greenhouse atm. contg. 0.3
of F~/m . The roots of one set of plants were
maintained at 20°, a 2nd set at 25°, and a 3rd
set at 30°. The F~ content of the root systems
at 30° was always more than double that at 20°,
whereas the F~ content of the tops was inversely
related to root temp., suggesting that high root
temp, favors translocation of the F~ from the
tops exposed to the atm. F~ to the roots. However,
previous work (Leone, et al.,CA 51, 2130g) provided
strong evidence of no such translocation. The
permeability of cell walls to solutes was measured
by the effect of time of immersion in conductivity
water, of fumigated and non-fumigated plant
tissues, on the conductivity. Fumigating plants
with HF may increase the permeability.
FLUORIDE EMISSIONS FROM PHOSPHORIC ACID PLANT GYPSUM
PONDS. W.R. King and J.K. Ferrell, North Carolina
State Univ., Raleigh, Oct. 1974, NTIS P3 241144,
329 pp.
A study is reported of fluroide emissions from
•ponds receiving process H2O from wet-process
phosphoric acid plants. Volatile F compounds
accumulate in H2O used in the manufacture of
phosphoric acid by the wet-process method. This
process H2O is routed to ponds for cooling and
eventual reuse. r,7hile in the ponds, some of the
F compounds evaporate, becoming air pollutants.
57
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Emission estimates were developed from the pond-
to-air mass transfer coefficient and the vapor
pressure of F over pond H^O. These estimates
were tested by measurements of ambient-air, F
compound concentrations downwind of the ponds.
Comparing the measured ambient air concentrations
with concentrations predicted from the emission
estimates and a standard atmosphere pollutant
dispersion model demonstrated the validity of
the emission estimates.
SULFURIC ACID PLANT EMISSIONS DUPING STARTUP,
SHUTDOWN, AND MALFUNCTION. E.L. Calvin and F.D.
Kodras. Catalytic, Inc., Charlotte, North Carolina,
NTIS, PB 249508, 353 pp.
Dual-absorption contact H^SO^ plants, as well
as single-absorption plants equipped with vent
gas cleaning systems for the removal of SO2, were
studied to determine the relationship between
process parameters and air emissions. Processes
studied were dual-absorption acid plants and single
absorption acid plants equipped with Na scrubbers,
NH3 scrubbers, and molecule sieve absorbers.
The SO2 and acid mist emissions and vent gas
opacity were considered. Relationships were
developed for normal operations and compared to
off-normal operations such as shutdown, start-
up, malfunction, and misoperation. Process
parameters and emission relationships are presented
in statistical, tabular, and graphic form.
Converter bed operating temperature ranges were
established and the causes of SO^ and acid mist
emissions are illustrated from plant operating
data.
"NEW DEVELOPMENTS IN FLUORIDE EMISSIONS FROM
PHOSPHATE PROCESSING PLANTS." Air Pollution Control
Association. Journal, Vol. 19, No. 1, Jan. 1969.
pp. 15-17.
The problem of monitoring for ambient fluoride
emission near a phosphate fertilizer processing
plant in Manatee County, Fl.f are discussed.
Results of a study conducted to determine the
emission of fluorides from the surface of a gypsum
settling pond at the Borden Chemical Company plant
are given. Conclusions reached as a result of
the study are: (1) That fluorides are emitted
58
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from such a pond at a minimum rate of about 0.16
pound per acre of surface area per day, (2) that
a breakpoint of about one-half mile from the pond
occurs in concentration of fluoride in the ambient
air, (3) that concentrations of fluorides in excess
of 7 5 ppm were found in young citrus leaves in
groves near the gypsum pond, and (4) that, although
a one-mile protective buffer zone for a phosphate
plant might be considered adequate for citrus
groves, it would not necessarily be adequate for
row crops or ornamental flowers such as gladiolas.
FLUORIDES AND SULFUR DIOXIDES AS CAUSES OF PLANT
DAMAGE. H. Bohne* Fluoride Quarterly ReDort, Vol.
3, No. 3, 1970. pp. 137-152.
Fluoride (F~) and sulfur trioxide (SO^) levels
were determined in 3 polluted industrial areas
where the 2 pollutants damaged vegetation. The
appearance of the leaves was typical of F~ injury
whereas no lesions indicated toxicity by sulfur
oxides. Fluoride levels in gladiolus ranged from
3.44 o 8.7% and those of SO3 from 0.77 to 1.15%.
The greatest damage from gaseous combustion to
horticulture, farming and forestry is caused by
F~ containing compounds, primarily hydrogen
fluoride.
FLUORIDE EMISSIONS FROM TREATMENT OF NATURAL
PHOSPHATES IN THE PRODUCTION OF FERTILIZER. R.
Truhaut, P. Bourbon, J. Alary. Fluoride 1975, Vol.
8, No. 1, pp. 25-33.
In producing HjPO^ with 31% P2O5 by the action
of H5SO4 on natural phosphate minerals contg.
3.72% F, there are emissions to the atm. of 5.5
mg F/m^. With a prodn. of 192 tons P905/day and
a gaseous effluent of 10,000 m3/hr, this
corresponds to 1.33 kg F/day. The emitted F is
80% SiF* and 20% HF. In the prodn. of H3PO4
of 54% P2O5 by evappn. in vacuum, no F is emitted
to the atm. In the prodn. of triple
superphosphate, the emission of F is 0.4 kg/ton
P2 Oc. The emissions are mainly SiF4 with a small
amt. of HF. In producing 500 tons/day of
diammonium phosphate, emissions of 1.4 mg F/m
or 5 kg F/day occur.
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EFFECT OF AIR-BORNE FLUORIDES ON 'VALENCIA' ORANGE
YIELDS. C.D. Leonard, and H.B. Graves, Jr. Proc
Fla State Hort Soc 79. 1966. pp. 79-86.
A fiel experiment with bearing 'Valencia' orange
trees on rough lemon rootstock was carried out
to study the effects of different levels of air-
born fluorides on yield, fruit quality , and leaf
growth. The experimental trees were in a grove
exposed to relatively high levels of air-borne
fluorides. Six trees were enclosed in individual
plastic greenhouses. Fluorides were removed from
the air entering 3 greenhouses by dry calcium
carbonate filters, while unfiltered ambient air
was moved through the other 3 greenhouses. Three
additional trees were not enclosed and were used
as outdoor checks. The leaves of trees in the
unfiltered greenhouses absorbed much less fluorine
than those of outdoor checks, even though there
was little difference in the fluorine content
of the air. This appears to be due to.the fact
that the leaves were kept dry inside the
greenhouses. Greenhouse trees receiving unfiltered
air produced significantly less fruit in 1965-
66 than those receiving filtered air, and the
outdoor check trees yielded significantly less
fruit than the unfiltered greenhouse trees. Leaf
size decreased as leaf fluorine increased. There
was a trend toward higher acid and lower Brix/acid
ratio of the juice with increasing fluorine in
the leaves, but these differences were not
significant.
LONG-TERM EFFECT OF FLUORIDE EMISSION UPON CHILDREN.
G. Balazova. Fluoride, Vol. 4, No. 2, 1971. pp.
85-8.
A controlled 8-year study of children living near
an A1 smelter showed no evidence of skeletal
fluorosis. A decrease in av. hemoglobin count
and increases in the F content of teeth, nails,
hair, and urine were obsd. Impairment of general
health was suggested by statistically significant
increases in incidence of anorexia, alopecia,
rhinitis, pharyngitis, tonsillities,
conjunctivitis, and excessive perspiration.
Incidence of dental decay was slightly less in
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the study group than in the control group.
ATMOSPHERIC EMISSIONS FROM WET-PROCESS PHOSPHORIC
ACID MANUFACTURE. U.S. Public Health Service
National Air Pollution Control Association, AP-
57, April 1970. 96 pp.
The Manufacturing Chemists' Assoc., Inc., and
US PHS, HEW, began a study in 1962 of emissions
from selected processing plants and to publish
data helpful to air pollution control and planning
agencies and to chemical industry management.
Background information is given on basic
characteristics of the wet-process phosphoric
acid industry, growth rate, uses for products,
and number and location of producing sits. The
process involves treatment of Phosphate rock with
sulfuric acid. Descriptions are given of commonly
used process variations. Emission data represent
about 20% of the operating plants. Range of
emissions under normal operations and the
performance of established methods and devices
for controlling emissions are described. In 1966,
about 3.5 tons of phosphoric acid (P9°5^ was
produced, mostly for various phosohate fertilizer
products. Dust from phosphate rock grindings
and fluoride compounds liberated by sulfuric acid
are a potential source of air and water oollution.
Total particulate emissions amount to about 0.20
lb per ton of acid for filter operation, and as
much as 11 lb per ton for digester operation.
Gypsum ponds contribute fluoride emissions
depending on pH, temperature and wind speed—one
pond studied showed a range of 0.4 to 1.8 lb of
fluoride per acre per day, varying with
temperature.
FLUORIDE POLLUTION. E. Groth, III. Environment
Vol 17, No 3, 1975. pp. 29-38.
Fluoride has received low priority in research
and regulatory control efforts. There is evidence
that accumulated levels of fluoride in plant and
animal life have caused a major increase of
fluoride in plant and animal life have caused
a major increase of fluoride in aquatic and land
food chains. Reduction in fluoride emissions
by control regulations may be offset by the rapid
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growth of the phosphate fertilizer and aluminum
industries which emit fluoride. While fluoride
pollution mainly occurs from industrial sources,
there are more sources of fluoride in the aquatic
environment. Although fluoride is present in
natural water sources, industrial and domestic
sewage discharge accounts for most fluorides.
The chemical is best known for its ability to
prevent tooth decay and is added to water systems
in about one half the communities in the United
States. It is likely that fluoride interacts
with other oollutants to produce a more toxic
effect. Calcium may act to reduce fluoride
concentrations. The lack of solid experimental
data on the toxic effects of fluoride demonstrates
that this chemical should be given higher priority
in future environmental research nrojects.
DISPERSION AMD EFFECTS OF AIR-BORNE FLUORIDES IN
CENTRAL FLORIDA. E.R. Hendrickson. J. air Pollution
Control Assoc., Vol. 2 32, No. 11, 1961, no. 2 20-
The ohoshate fertilizer industry and the orocesses
used are described briefly. The industry may
liberate as much as 3 tons of gaseous fluoride
oer day as HF, SiF4, or HoSiFg, but most of the
factories are reducing this emission. Practicallv
all vegetation of com. value is damaged by some
of the active gaseous fluorides at concns. below
1 D.p.m.; gladiolas are injured by exoosure for
a few days to 3 narts oer billion. Chronic
ooisoning of cattle bv feeding on pastures
contaminated with fluorides, esn. sol. fluorides
has been noted.
THE INFLUENCE OF FLUORINE EMISSIONS ON THE NUTRITION
OF CATTLE. . D. Or under. Berlin Munchen Tier-Arztl
Wochenschr, Vol. 80, No. 4, 1967. pp. 61-63. ~
The writer undertook research on 12 cattle aged
from 3/4 to 9 years which were kept for 3 1/2
years within an area where they were under the
influence of a factory emitting fluorine and a
further year outside this area, keeping the feeding
normal to the district. Fluctuating fluorine
content from 1..0-9.5 mg F/kg body weight per day
at an average value of 3.4 F/kg caused, in addition
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to the typical fluorosis in teeth and bones,
periodic severe disturbance in nutrition, which
reached within a period of 1-2 mo. 50-100 kg
decrease when the fluorine intake was increased
to 3.0-9.5 mgF/kg body weight. The nutritional
standard became normal again when there were
periods of decreased fluorine administration and
when the animals were removed from the emission
area, this process taking 2-3 mo. The decrease
in weight was caused partially by temporary
lessening of feeding, but is considered in general
as the result of primary fluorine toxicity.
AIR QUALITY CRITERIA FOR THE EFFECTS OF FLUORIDES
ON MAN. Harold C. Hodge, and Frank A. Smith.
Journal Air Pollution Control Assn., Vol. 20, No.
T, 1970. pp. 226-232.
Since some types of vegetation are highly
susecptible to the effects of fluoride, an air
quality standard that would protect vegetation
would be far below the air concentrations that
could possibly have an effect on human health.
The 7 major effects of fluoride in man are listed
in a table. Since in all likelihood a standard
to protect vegetation will be set somewhere below
10 ppb, this level was used for purposes of
illustration. If an air quality standard is set
at less than 10 ppb F, and the total intake by
man from this source is calculated as less than
0.2 mg/day, the increase in intake might not be
detectable even by good analytical procedures.
The normal range of F intake from the diet and
the drinking water combined, even in areas where
the water contains only a trace of.F, lies between
0.5 and 1.5 mg.
EFFECT OF FLUORIDE AIR POLLUTION ON FLORIDA CITRUS.
C.D. Leonard, and H.G. Graves, Jr.Fluoride, Vol.
5, No. 3, 1972.. pp. 145-63.
Airborne fluorides produced leaf chlorosis and
burn and decreased leaf size, tree growth, fruit
yield, and photosynthetic efficiency of Florida
citrus trees. In the citrus fruit, the highest
F levels were found in the peel. There was
slightly more F in the juice than in the pulp.
Sprays contg. a mixt. of hydrated lime* manganese
sulfate [7785-87-7], and urea [57-13-6] greatly
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reduced fluoride absorption by the leaves and
regreened F-chlorotic leaves. Young citrus leaves
were much more susecptible to fluorine [7782-41-
4] chlorosis than old leaves.
"Animal Indicators of Air Pollution: A Peview and
Recommendations", J.R. Newman, Huxley College of
Environmental Studies, Western Washington State
College, Billinghan, Washington, 98225. Soonsored
by the Environmental Protection Agency, Corvallis
Environmental Pesearch Laboratory, Corvallis, Oregon,
97330. Contract Mo. G4-729, May 1975. op. 52-59.
The use of animals as biological monitors of air
pollution is essentially non-existent. Besides
being used as general measures of environmental
quality, animals give more precise information
on the quality of the environment as it relates
to human and other animal systems. This study
reviews the existing information on the effects
of industrial air pollutants on animals for the
purpose of suggesting animal indicators of a4r
pollutants and various monitoring approaches based
on their responses of animals to air pollutants.
The amount of information varies on the effects
of specific air pollutants on animals. In general,
laboratory investigations have been conducted
at conditions not found in the environment. A
significant number of episodes involving the
effects of air pollutants on free-living animals
have been reported. They indicate the widespread
effect of air pollutants on animals. Numerous
animal indicator systems and approaches to
development of the animal indicator systems are
discussed.
"Fluorosis in Black-Tailed Deer", James R. Newman
and Ming-TIo Yu, J. of Wildlife Diseases, 12, Jan.
1976, pp 39-41.
Marked dental disfigurement and abnormal tooth
near patterns were observed in black tailed deer
(Odocoileus hemionus columbianus) taken from an
area near an industrial fluoride source in
northwestern Washington. Fluoride levels in the
bones of these deer were from 10 to 35 times higher
than levels in the bones of normal animals. These
levels are similar to those associated with
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fluorosis of cattle.
"Effects of Elevated Levels of Fluoride on Deer
Mice (Peromyscus Maniculatur)", J.R. Newman and
D. Markey, Fluoride 9, (1), Jan. 1976, pp. 47-53.
Information on the effects of fluoride on wildlife
is essentially non-existent. Much of the research
has been conducted on domestic farm animals and
laboratory rats and mice. Among the known effects
of fluoride on domestic farm animals are dental
disfigurement, especially in developing teeth.
Ingestion of high levels of fluorides causes
mottling, pitting, and weakening of teeth resulting
in excessive tooth wear. In addition, structural
bone changes such as general thickening, change
in shape of leg bone, and even mineralization
of tendons are often observed.
This study investigated the effects of elevated
levels of fluoride (NaF) on the diet of deer mice,
a widespread small mammal known to accumulate
fluoride. Deer mice were found to be more tolerant
to fluoride in the diet than laboratory mice and
rats. At concentrations above 1300 ppm fluoride,
deer mice exhibited marked weight loss, mortality,
changes in femur size and dental disfigurement.
"Sensitivity of the House Martin, Delichon Urbica,
to Fluoride Emissions", J.R. Newman, Fluoride, pp.
73-76.
The nesting patterns of the House Martins, Delichon
urbica, were found to be affected by fluoride
emissions. In an area of high fluoride concentration
the birds were rare while other species of birds
were common. In areas of moderate fluoride pollution
the population of House Martins were similar to
control areas.
4. Resource Depletion Effects
SULFUR SHORTAGE FORECAST BY 1985. Chem. Eng. News,
Vol. 54, No. 25, June 14, 1976. p. 10.
Demand for sulfur worldwide could outpace availability
by 8.3 million mt, about 15% of potential need. The
situation could trigger a tightening in sulfuric acid
supply also, according to a comprehensive survey just
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completed by Westinform Service, London. Global
sulfuric acid demand likely will grow from this year's
121.5 million mt level to 197 million mt in 1985.
PHOSPHORIC ACID MANUFACTURE WITH MINIMIZED ENVIRONMENTAL
IMPORTS. R.S. Ribas and J.D. Nickerson(to U.S. Steel
Corp.). U.S. Patent 3,932,591, Jan. 13, 1976, Aopl
Apr. 19, 1972. 8 pp.
An improvement is described in the process for
producing H-,P04 wherein phosphate rock is mined and
beneficiated, the beneficiated product separated into
a slimes stream, one or more pebble streams, and a
concentrate stream, the slimes stream discarded, and
the pebble streams digested with mineral acid and
filtered to remove impurities. The improvement
consists of dewatering the slimes stream to >40 wt%
of solids, calcining the dewatered slimes at
2200°F, combining the calcined fines with
beneficiated pebble prior to its digestion wit e
mineral acid, and filtering the resultant s urry o
remove the solids. Alternately the dewatere s lmes
are added to the beneficiated pebble prior o
calcination and the mixture then calcined. In another
embodiment, the phosphate slimes are dewatered,
calcined and used directly without other phosphates
to produce the H3PO4.
TREATMENT OF PHOSPHATE POCK IN SOIL TO PROVIDE FERTILIZER
AND GYPSUM. D.D. Collins and F.W. Laver, Jr.(to Chemsoil
Corp.). U.S. Patent 3,979,199, Sept. 7, 1976, Appl.
June 20, 1973. p. 4.
A method is described for the title process.
Pulverized phosphate rock is spread onto or nixed
into the soil, which is then treated with a solution
of H2S03 formed by dissolving in water S02 produced
by burning S in air. The H20 may be irrigation Ho
0. Phosohate values in the rock are solubilized by
the aqueous solution of H^Oo at pH 2.0-6.5 and gypsum
is formed in situ in the soil.
AMMONIA REMOVAL AND RECOVERY OF INDUSTRIAL WASTES.
R.W. Pretty/nan and L.G. Kepple ASHRAE J., Vol. 18,
No. 9,, 1976. pp. 41-6.
The NH-j removal process, using a closed air cycle
striDping and acid, for example H2S04, absorption
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system, treates industrial wastes containing NH-*.
It eliminates problems with air stripping such as
CaCOg scaling, temperature limitations, and air
pollution. Pilot plant studies are described.
CLOSED LOOP SYSTEM FOR THE ELIMINATION OF FLUORINE
POLLUTION FROM PHOSPHORIC PLANTS. William R. Erickson.
U.S. Patent 3,811,246 (CI. 55/71; B Old), Mav 21. 1974.
Appl. 324,227, Jan. 16, 1973. p. 6.
Vapors contg. HF [7664-39-3] and SiF4 [7783-61-11
obtained from the concn. of aq. H3P04 by evapn. were
condensed by contacting with an aq. soln. contg. H
oSiFg [16961-83-4]. The resultant soln. was cooled
by indirect heat exchange and a portion of the
condensate was removed as a 15% HjSiFg soln. The
remaining soln. was concd. in barometric condensers
and recycled to condense addnl. vapor. The recovery
unit was operated so that no atm. pollution by F was
possible.
CLOSED POND SYSTEM FOR WET PROCESS PHOSPHATE PLANTS>
Rufus G. Hartig. U.S. Patent 3,859,423 (CI. 423-472;
C 01b), Jan. 7, 19 75, Apple. 60,226, Aug. 1970, p. 6.
Continuation-in-part of U.S. Patent 3,720,757 (CA 79:
33203c).
Waste waters from wet process H3PO4 complexes,
including scrubber liquor, are cooled and clarified,
and the liq. from the clarifier recycled to the
phosphate complex, the sludge or slurry being filtered
to remove solids which are then calcined to remove
F-contg. gases. The calcined solids consist
principally of NaF which is recycled to the clarifier
overflow to be mixed with the liq. returned to the
complex. In the phosphate complex the liq. from the
clarifier is used to scrub plant gases, and is mixed
with other scrubber liquors and recycled to the cooling
tower and clarifier. The HF in the waste liquors
is converted to SiF^ by excess Si02 and the NaF reacts
with the SiF^ to form Na2SiFg. The Na2SiFg is calcined
to produce NaF and gaseous S1F4, the latter being
scrubbed with water to form I^SiFg.
"PHOSPHORIC ACID BY DIRECT SULFURIC ACID DIGESTION OF
FLORIDA LAND-PEBBLE MATRIX". J.C. White, A.J. Fergus,
and T.N. Goff. U.S. Bur. Mines, Rep. Invest. 8086,
1975. p. 12.
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A study was made to determine the technical feasibility
of the direct digestion of Florida land-pebble
phosphate matrix with H2SO4. Preliminary tests in
a continuous digestion circuit indicated that 92-96%
of the P205 in the matrix was extracted. The PoOc
concentration in the product acid ranged from 21-30%.
The waste filter cake contained 1% of P5O5 and <
18% of H9O. This sandy compact filter cake, comprised
mostly of quartz and gypsum, appeared to be suitable
for the backfilling and reclamation of mined lands.
"FLOATING AMMONIA PLANTS PROMISE FERTILIZER FUTURE".
Farmland News, Vol. 4 2, No. 19, Sept. 30, 1976. o. 9.
1
Ammonia plants, on giant ships, could produce up to
40% of ammonia requirements of the United States using
solar energy and relieving the drain on natural gas,
according to a recent reoort. Ammonia used for
fertilizer and chemicals could be manufactured aboard
sea-going liner-sized ocean thermal conversion plants
using only the free, nearly inexhaustible solar energy
stored in the world's tropical oceans, explains a
feasibility report prepared for the U.S. Maritime
Administration by the Johns Hopkins University Applied
Physics Laboratory. Twenty-one such sea-going plants,
each manufacturing 56S,000 short tons of ammonia/yr.,
could be operating within a decade, says the report.
The plants would help conserve dwindling supplies
of natural gas which is today the feedstock in
conventional manufacture of ammonia. With the schedule
proposed by this study, for ammonia plant ship
implementation, the projected shortfall in ammonia
production in the mid-1980's and beyond would be filled
and natural gas required in ammonia production on
shore could be held at near the 1975 allocation.
INCREASING FLUOSILICIC ACID EVOLUTION FROM PHOSPHATE
ROCK BY DIGESTION WITH PHOSPHORIC ACID. Henry E. Blake,
and Boyd D. Nash. Bureau of Mines, Albany Metallurgy '
Research Center. RI-7980, Dec. 1974.
The Bureau of Mines has conducted research to develop
processes or modifications to existing processes for
increasing the recovery of fluorine from phosphate-
rock. Preliminary batch-testing has shown that over
98 percent of the F and P205 in phosphate rock can
be extracted by excess phosphoric acid in the presence
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of water vapor at 150 to 180C, with over 80 percent
of the fluorine being volatilized and recovered as
fluosilicic acid. When this method was applied in
a semicyclic system, fluoride recovery was maintained
at about 80 percent and P2O5 recovery was about 90
percent.
PHOSPHORIC ACID BY DIRECT SULFURIC ACID DIGESTION OP
FLORIDA LAND-PEBBLE MATRIX. Jack C. White, Andrew J.
Ferguson, and Thomas N. Goff. Bureau of Mines, Twin
Cities Mining Research Center. BuMines-RI-8086, 1975.
The purpose of this research was to determine the
technical feasibility of direct sulfuric acid digestion
of Florida land-pebble phosphate matrix. In addition
to the disposal^ problem, slimes may contain up to
30 percent of the phosphate contained in the original
matrix, which is unfortunate in view of the increasing
demand for fertilizer. Preliminary tests in a
continuous digestion circuit showed that 92 to 96
percent of the P2OC contained in the matrix was
extracted, while the P2O5 concentration in the product
acid ranged from 21 to 30 percent. The waste filter
cake contained about 1 percent P2O5 and up to 18
percent water. These sandy compact filter ckkes,
comprised mostly of quartz and gypsum, appeared to
be suitable for backfilling and reclamation of rained
lands.
FLUOSILICIC ACID ACIDULATION OF PHOSPHATE ROCK. Lloyd
H. Banning. Bureau of Mines, Albany Metallurgy Research
Center, BuMines-RI-8061, July 1975.
Both high-grade deslimed phosphate rock and low-grade
phosphate rock samples were treated by the 5-step
cyclic procedure. The most promising results were
obtained in treating the deslimed high-grade material.
In a series of 7 cyclic tests, 85.4 percent of the
p2°5 was recovered in a phosphoric acid-monocalcium
phosphate solution containing as much as 175 grams
of P9O5 per liter and as little as 0.4 grams of F
per liter. The residues had an average F content
of 30.7 percent and contained 83.9 percent of the
fluorine and 8.4 percent of the phosphate in the charge
materials. Some fluorine was lost by volatilization.
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c. Available Technology for Mitigation of Adverse Effects
1. Land
2. Water
A STUDY ON THE EFFLUENT DISPOSAL OF SUPERPHOSPHATE
FERTILIZER FACTORY. H.C. Arora(Cent. Public Health
Engineering Res. Inst., Kanpur, India) and S.N.
Chattopadhya. Indian J. Environ. Health, Vol. 16,
No. 2, April 1974. no. 140-50.
Existing waste F?20 treatment units of a
superphosphate fertilizer factory are described.
The effluent quality is analyzed and modifications
are proposed for improvements in the quality of
the final effluent. The use of the waste
containing HF for the manufacture of H2SiFg, an
insecticide, or for further conversion to Na or
Mg silico fluoride, a preservative for portland
cement surfaces, is suggested.
WASTE DISPOSAL AT A PHOSPHORIC ACID AND AMMONIUM
PHOSPHATE FERTILIZER PLANT. W.E. Jones and R.L.
Olmsted. Purdue Univ., Eng. Bull., Ext. Ser. No.
112, 1962. pp. 198-202. " "
Excess NH3 is removed bv acid scrubbers at the
NH4 phosphate plant. A dry recovery system
followed by a wet scrubber is used for the removal
of dust particles 0.5-500 . Filtered gypsum cake
is slurried with H2O and pumped to the diked
disposal area and allowed to settle. H2O from
the slurry is recycled to the process and becomes
part of the product H3PO4. F is discharged into
a large amt. of H2O and discarded.
RECOVERY AND REUSE OF AQUEOUS EFFLUENT FROM A MODERN
AMMONIA PLANT. J.A. Finneran, and P.H. Whelchele.
Ammonia Plant Saf., Vol. 13, 1971. pp. 29-32.
A discussion on the degree of cleanup and reuse
attainable on combined water treatment and process
condensate effluents of a modern large scale (1000
ton/day) NH3 plant contg. suspended solids 170,
dissolved solids 1200, NH3 1000, and orgs. 2000
npm. The overall cleanup results in a 10 and
30% abs. redn. of suspended and dissolved solids,
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resp., and a total elimination of NH3 and orgs,
from the effluent. Pilot plant tests show that
stripped process condensate effluents contg. NH
2 20, CO? 40, orgs. 50, metals 0.6, and SiC^ 0.01
ppm can be cleaned up by cation exchange resin
to a total solids content of 0.1 ppm and an
effluent nearly free of heavy metals useful as
boiler feed water.
PURIFICATION! OF WASTE WATERS CONTAINING AMMONIUM
NITRATE AND/OR AMMONIA. Arie Zlota et al (to
Combinatul de Ingrasaminte Chimice Tirgu Mures).
Rom. Patent 57,934, Dec. 28, 1974, Appl. ADr. 4,
1972, p. 3. CA 85,98785.
Waste F^O containing TIH4NO3 and (or) NH3 was
pretreated with an alkali or alkaline earth
hydroxide at 45° for 5-30 min, treated with steam
to carry off the NH3, and the vapors condensed.
The residual mixture containing < 10 opm of NH
3 was disposed directly to H^O streams. The
treatment column .is described.
AMMONIA NITROGEN REMOVAL BY STRIPPING WITH AIR.
Joseph 3. Farrell. In: EPA Advan. Waste Treat.
Water Reuse Symp., [Proc.] 1971.
Waste water contg. 15-25 mg NH4+/1. is treated
by converting NH^+ to NH3 by raising the pH and
stripping the NH3 by contacting the waste water
with air in a countercurrent salt-filled tower,
such as is used for cooling water to contact water
with air.
REMOVAL OF FLUORINE FROM WASTE WATERS. I. LIME
ADDITION AND EFFECT OF ALUMINUM IONS. Jumpei Ando,
Masai Mori, and Yasuo Ohno. Sekko To Sekkai, 1974.
pp. 133, op. 216-21.
Waste waters from ^3P04 and phosphate plants were
treated with lime. Fine crystals of CaF? < 200A
and gel-like fluorapatite pptd. The filtrate
usually contained F> 20 ppm, while soly: tests
showed that F content of satd. solns. of CaF2
and fluorapatite was 8 ppm and < 1 ppm, resp.
The high concn. of F in the filtrates is mainly
due to the small size of the F compds., a portion
of which pass through filter papers. Coagulation
of the particles is important and is affected
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by the concn., impurities, etc. of waste watetb.
F was considerably reduced by adding Al salts
but the effect was less with waste water containing
H3PO4. A 2-stage filtration, addn. of lime to
pH 4-7, filtration, addn. of Al salt and lime
and filtration, reduced P to <10 ppm.
WAYS OF LOWERING THE AMOUNT OF FLUORINE-CONTAINING
WASTE WATERS IN THE PRODUCTION OF WET-PROCESS
PHOSPHORIC ACID. N.F. Khripunov, A. Ya Abramovich,
and V.A. Kopylov(USSR). Khim. Prom-st. (Moscow)
, Vol. 2, 1975. pp. 110-12.
The wet-process unit (capacity 5.5 x 104 metric
t°ns P205/year) requiresw200 m^ H^O/hr. Most
of it is discharged from the scrubbers of tail
gases as waste water contg. 30-150 mg F/l.
Introduction of a tubular cooler, cooled by water
from the vacuum evaporator, and recirculation
of water that runs the vacuum filter pump, reduced
the water demand of this unit to 15-20 m3/hr.
TREATMENT OF WASTE WATER CONTAINING FLUORINE AND
ALKALI. Kanzo Kawahara, Hideo Watanabe, and Tadao
Takahashi(to Sun Chemicals Co., Ltd.) Japan, Rokai
75 15,355, Feb. 18, 1975, Appl. June 12, 1973, p.
4. CA 83, 197604.
•f
Waste waters containing F and alkalis from
phosphoric acid plants and Al manufacturing are
treated with inorganic acids or their Ca salts.
The treated waste waters are neutralized with
Ca(OH)2 and the precipitate is removed to obtain
the supernatant liquid containing < 50 ppm of
F. Thus, a waste H20 containing 477 mg of F/l.
was mixed with 1.5 equivalent of HC1 per equivalent
of alkali present and was adjusted to oH 3.3.
The mixture was allowed to stand to separate the
supernatant liquid and sludge. The supernant
liquid was adjusted to pH 7.0 with Ca(0H)2 and
the sludge formed was removed. The treated
0 contained 9 ppm of F, whereas when the control
waste H2O was treated by the same process except
no HC1 was added the effluent contained 388 ppm
of F.
PREVENTION OF SURFACE WATER CONTAMINATION AND AIR
POLLUTION BY FLUORINE COMPOUNDS FROM PHOSPHATE
PLANTS. Rufus G. Hartig. U.S. Patent 3,642,438(CI.
72'
-------
23/153, C 01b)fFeb. 15, 1972, App. 816,206, Apr
15, 1969. p. 5.
Combined waste gas streams from phosphate rock
processing, contg. HF, SiF4, H20 vapor, S02, and
phosphate dusts, are prescrubbed with recirculated
aq. liquor contg. Si02 and * 25% HoSiFg. The
SiF4 is not absorbed and leaves with the offgases.
The HF reacts with the Sio^, forming H2SiFg which
decomps. to SiF4 vapor. The gases are then
scrubbed with an aq. slurry contg. excess NaF
which reacts with residual HF to ppt. NaHF2 and
with SiF4 to ppt. Na2SiFg. The scrubber liquor
is filtered, and the filter cake is dried and
heated to 600°F which decomps. the NaHF2 to from
NaF and gaseous HF which can be removed as product
or recycled to the prescrubber. The solids, contg.
NaF and Na2SiF6 is decompd. to form NaF and gaseous
SiF4. The NaF is recycled to the scrubber liquor.
The gases are scrubbed with water to prep, a soln.
contg. H2SiF6 and pptd. Si02. The Si02 is filtered
off and a portion is recycled to the prescrubber
liquor. The filtrate consists of a 15-25% H2SiF
g soln. which is removed as product.
REMOVAL OF PHOSPHATE FROM WASTE WATER. Osanai
Mutsuko, Toya Yasunori, and Kazuo Shimada(to Ebara-
Infilco Co., Ltd.). Japan, Kokai 75 88,851, July
16, 1975, Appl. Dec. 7, 1973, CA 84, 65046. p.
6.
Phosphates are removed from waste waters by
contacting the waters with Ca phosphate rock at
pH>6. The phosphate-removal efficiency of the
rock is much greater than that of active C. Thus,
to a waste H20 containing 10 ppm of orthophosphate
was added Florida phosphate rock powder of 200-
300 mesh to a final concentration of 4000 ppm.
The mixture was stirred at 120 rpm and 25 for
2 hr and filtered. The filtrate thus obtained
•contained 0.1 mg/1. of H3PO4, compared with 2.42
mg/1.* when the waste H2o was treated with an
equal concentration of active C.
3. Air
PLUME-FREE STACKS ACHIEVED IN H3P04 production.
R.D. REA. CHEM. PROCESSING , Vol. 34, No. 1, Jan.
73
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1971. pp. 13-14.
At the thermal-process H3PO4 plant of the Mansanto
Company at Trenton, Michiqan, the electrostatic
precipitators used for collecting H^po^ mist from
the hydrator were replaced by qlass fiber (Brink)
mist eliminators. In a survey by the National
Air Pollution Control Administration covering
25 HoPO* plants, the Trenton plant was the only
one listed as having zero plume opacity, with
no visible discharge. Maintenance costs and
unscheduled downtime are lower than for the
electrostatic precipitators for which electrode
and leakage repairs had averaged about $35,000/yr.
PREVENTION OF SURFACE WATER CONTAMINATION AND AIR
POLLUTION BY FLUORINE COMPOUNDS FROM PHOSPHATE
PLANTS. Rufus G.. Hartig. U.S. Patent 3,642,438
(CI. 23/153, Colb), Feb. 15, 1972, Appl. 316,206,
Apr. 15, 1969. o. 5.
Combined waste gas streams from phosphate rock
processing, contq. HF, SiF^, H20 vapor, S02, and
phosphate dusts, are prescrubbed with recirculated
aq. liquor contg. ^©2 an(^ H2SiFg. The SiF
4 is not absorbed and leaves with the offgases.
The HF reacts with the ^iO?, forming H2SiFg which
decomps. to SiF^ vapor. The gases are then
scrubbed with an aq. slurry contg. excess NaP
which reacts with residual HF to ppt. NaHF^ and
with SiF4 to pot. Na2SiFg• The scrubber liquor
is filtered, and the filter cake is dried and
heated to 600°F which decomps. the NaHF2 to from
NaF and gaseous HF which can be removed as product
or recycled to the prescrubber. The solids, contg.
NaF and Na2SiFg, are heated to 1300°F whereby
Na2SiFg is decompd. to form NaF and gaseous SiF
The NaF is recycled to the scrubber liquor.
The gases are scrubbed with water to prep, a soln.
contg. H2SiFg and pptd. Si02. The Si02 is filtered
off and a Portion is recycled to the prescrubber
licuor. The filtrate consists of a 15-25% H 2 S i F
c soln. which is removed as product.
¦j
FLUORIDE EMISSION CONTROL COSTS. T.R. Osag. Chem.
Eng. Prog. , Vol. 12, No. 2, Dec. 1976. pp. 33-6.
Each of the processes for making the five major
74
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fertilizers from phosphate rock involves chemical
treatment of a fluoride-bearing material. The
gaseous fluoride emissions that result consist
mainly of HF and SiF4, the particulate emissions
consist of silicofluoride and mechanical carryover.
The range of industry-wide fluoride control is
compared with that of the best-controlled segment
of the industry. The former is characterized
by extensive use of spray towers and ventrui
scrubbers, and the latter by spray crossflow packed
bed scrubbers of by venturi scrubbers in series.
The cost for adding efficient scrubbers to existing
phosphate fertilizer plants is < $11 ton of product
of four out of .the five major fertilizers.
RECOVERING FLUORIDES FROM VAPORS. William E. Rushton
and George Kleinman (Whiting Corp.). U.S. Patent
3,415,039 (CI. 55-51), Dec. 10, 1968, Appl. Nov.
3, 1965.
Fluoride-contg. vapors from the evapn,-concn.
of dil. wet-process H3PO4 are scrubbed with an
aq. soln. of f^SiFg at a pressure lower than that
in the evapn. chamber whereby larger amts. of
the gaseous fluorides are absorbed than by usual
methods. Thus, in a 3-stage evaporator system
for producing H3PO* contg. 54% P205 the 1st stage
was operated at 155°F and 8.56 in. Hg abs. to
pro'duce 25% H^SiFg. The loss of F in the scrubbed
vapors was 0.u04 lb. F/lb. H2O vapor, compared
with 0.025 lb. F/lb. f^O vapor by usual methods.
Similarly, a loss of 0.0085 lb. F/lb. H2O vapor
was obtained when producing 30% f^SiFg compared
with a loss of 0.06 lb. F/lb. H2O vapor by usual
methods.
CLOSED POND SYSTEM FOR WET-PROCESS PHOSPHATE PLANTS.
Rufus G. Hartig. U.S. Patent 3,720,757 (CI. 423-
341), Mar. 13, 1973, Appl 60,226, Aug. 03, 1970.
p. 6.
A process for eliminating the conventional pond
systems of wet process H^PO^ (WPA) plants removes
F from process gas streams. Liq. effluents from
the WPA plant, including scrubber liquor from
gas scrubbing operations of the plant, are cooled
and clarified, and the liq. from the clarifier
recycled to the WPA plant. The sludge or slurry
is filtered to remove solids. The solids are
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calcined to drive off F-contg. gases. The calcined
solids consist principally of NaF which is recycled
to the clarifier overflow to be mixed with the
liq. returned to the WPA plant. In the plant,
the liquid from the clarifier is used to scrub
plant gases, and is mixed with other scrubber
liquors from the plant and recycled again to the
cooling tower and clarifier. The HF in the
effluent plant liqs. are converted to SiF4 by
maintaining an excess of Si02 according to the
equation: 4HF + Si02 = SiF4 + 2HoO. The NaF
reacts with the SiF4 to form Na2SiFg according
to the equation: 2NaF + 5iF4 = SiF4 + 2H?0.
The Na2SiFg is calcined to produce NaF ana gaseous
SiF^, the latter being scrubbed with H20 to form
I^SiFg of com. quality.
ENGINEERING AND COST EFFECTIVENESS STUDY OF FLUORIDE
EMISSIONS CONTROL. VOLUME I. TRW Systems Group,
McLean, Va., Jan. 1972, APTD-0945.
Industry by industry descriptions of each
production and control process of significance
from a fluoride emission control standpoint;
discussions of production trends extrapolated
to the year 2000; process flow diagrams and mass
balances for typical current plants; estimates
of current and projected fluoride emissions;
analysis of production and control process
economics; descriptions, cost estimates, priority
assignments and schedules for the additional
research and development programs recommended
as the result of this study; environmental and
ecological effects of the emitted fluorides; and
techniques for sampling, and measurement of
fluoride pollutants in the various effluent
streams.
ENGINEERING AND COST EFFECTIVENESS STUDY OF FLUORIDE
EMISSIONS CONTROL. VOLUME II. TRW Systems Group,
McLean, VA., Jan. 19 72.
An appendix is presented which contains a general
discussion of fluoride emission control devices;
and inventory of pertinent industrial plants and
their location; tabulations of the physicochemical
parameters of the evolved fluorides; and a
bibliography. The appendix accompanies Volume
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1 of the study (PB-207 506) which determines
the engineering and cost effectiveness of control
of soluble fluoride emissions from major industrial
sources.
"SCRUBBING OF GASEOUS EFFLUENTS", A.J. Teller and
D. Reeve. In: Phosphoric Acid by A.V. Slack.
New York: Marcel Dekker, 1968. pp. 741-751.
Emphasis on recovery of fluorine from fertilizer
plant effluents has been intensified in recent
years, mainly because of the destructive effects
of these emissions, even in very low
concentrations, on crops and livestock. Thus
governments have imposed ever-increasing
restrictions on the quantity of emissions from
a single complex as well as limitations on fluorine
concentrations in foliage.
This section indicates the sources of fluorine
emission in fertilizer manufacture, the "state
of the art" achieved in the solution of the
problem, and the unsolved problems and possible
solutions.
Reduction in emission to the atmosphere of
pollution-contributing effluents from fertilizer
operations can be achieved by the following:
1. process modification, 2. containment, and 3.
recovery of effluents.
The gaseous pollutatns emanating from fertilizer
operations consist primarily of hydrogen fluoride
and silicon tetrafluoride. Lesser amounts of
ammonium silicofluoride and ammonium bifluoride
are encountered in diammonium phosphate production.
Solid wastes containing fluorides are also emitted
to the atmosphere as a suspension of particulates.
The process sources of these various effluents
are as follows: 1. drying and calcining phosphate
rock, 2. acidulation of phosphate rock to produce
normal superphosphate, 3. acidulation of phosphate
rock to produce phosphoric acid, 4. concentration
of phosphoric acid, 5. reaction of concentrated
phosphoric acid with neutralizing agents to
produce: a. diammonium phosphate, with ammonia,
b. triple superphosphate, with phosphate rock,
6. drying, storage, and aging of solid fertilizer
products.
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4. Resource Depletion and By-Product Recovery
"COAL-BASED FERTILIZER PLANT AT TALCHER.", A.V.
Naganathan. Chem. Eng. World , Vol. 10, No. 2,
Sect. 2, Feb. 1975. pp. 173-9.
A noncoking coal of high ash content is pulverized
to <90 and gasified at 1600° and 1 atm. The
gas obtained as product is processed to produce
CC>2 by the conversion of CO. The CO2 is sent
to a urea plant, while the C02-free gas, mostly
H and CO, is treated to remove trace C02, methanol,
and CO and mixed with N to form a synthesis mixture
for an NH-j plant. Flow diagrams are given for
the different sections of the plant, and the
various operations are described.
"SULFURIC ACID FROM POWER PLANTS MIGHT SELL.", Chem.
Enq. News , Vol. 54. No. 39, Sept. 20, 1976. pp.
14-15.
Early results from a Tennessee Valley Authority
model of the total sulfuric acid business are
reported. Sulfuric acid, the largest-volume U.S.
chemical with 1975 output at 32.4 million tons
in conventional plants, has been heading for a
potential production shakeup for some time. Behind
this shakeup is a new large source of the corrosive
liquid-by-product production from pollution control
installations at power plants. TVA is shooting
for completion in March 1977 of a massive,
Environmental Protection Agency-sponsored computer
model simulating the U.S. by-product sulfuric
acid market. Plans call for companies and other
potential users to have access to the model through
a national commercial time-shared computer network.
A number of chemical companies already have looked
in on the model. The makeup of the TVA market
model is a tremendous array of data on five key
parts of the by-product acid market. First, TVA
has its own data base on conventional sulfuric
acid producers. To this TVA has added data bases
on transportation and distribution options,
utilities' steam plant boilers, states' pollution
restrictions, and TVA's cost estimates for both
conventional and by-product acid. The model is
currently in the final stages of refining to round
78
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out the total by-product market and to bring cost
estimates up to date.
AMMONIA PRODUCTION FROM COAL. Chem. Mark. Rep.
, Vol. 211, No. 6, Feb. 7, 1977. pp. 5,36.
Continuting problems with natural gas supnlies
pose serious questions about nitrogen fertilizer
production in the future, according to the manager
of Tennessee Valley Authority's National Fertilizer
Development Center at Muscle Shoals, Alabama.
Natural gas is the nrime feedstock for producing
ammonia, and almost all nitrogen fertilizers are
made from ammonia. About half of the 49 million
tons of fertilizer used by American farmers last
yr was nitrogen materials. Nitrogen fertilizer
is absolutely essential in modern farming. In
light of the critical natural gas supply situation,
it is obvious that we can no longer depend so
heavily on natural gas for nitrogen fertilizer
production. TVA researchers have been looking
for some time at alternatives to using natural
gas in the oroduction of ammonia, and have
concluded that coal is the best bet for the rest
of this century. TVA began working on producing
ammonia from coal about 2 yr ago, and hope to
begin construction of a demonstration ammonia-
from-coal plant at Muscle Shoals in 1979. This
pilot operation, being planned by TVA, will serve
as a vital intermediate step to reduce the risks
in developing large commercial ammonia-from-coal
plants. It will also demonstrate how existing
ammonia plants can be remodeled to use gas made
from coal.
RECOVERY OF PHOSPHORUS PENTOXIDE FROM T*7 A S T E - W AT E R S
BY ADDING LIM1?. Masasi Mori Sekko To Sekkai
, Vol. 142, 1976. pp. 111-13.
Laboratory tests were made to recover P7O5 in
waste waters from wet-process H3PO4 plants by
adding lime. Prior to the precipitation of P2
Or, most of the F was precipitated as CaF2 at
pH 3™4, and then the H^PO^ was precipitated as
fine crystals of apatite. The crystal size fo
the aoatite varied with the amount of F in the
waste H20. Although citrate solubility varied
with the crystal size the apatite was entirely
soluble in 2% citric acid solution.
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CHANGE IN ENERGY COST AND SOURCES FOR AMMONIA.
J.A. Pinneran. Chem. Eng. News, Vol. 54, No. 17,
Apr. 19, 1976. p. 26.
For the nitrogen industry the effect of high-priced
energy has been to change from capital-intensive
to energy-intensive. For plants built in the
I960's and operated with the low-cost gas then
available, more than half of the cost of ammonia
production was directly related to capital cost.
For plants built in the middle 1970 s and using
natural gas costing over $1.00 per 1000 cu ft,
more than half of ammonia production cost is
related directly to energy. The U.S. produced
last yr about 17 million tons of ammonia. About
3 or 4 million tons are nominally intended for
the industrial market. Owing to the business
recession during the past 18 months, more than
1 million tons of ammonia normally destined for
industry was diverted to the fertilizer narket.
That trend has now been reversed, and in 1976
that 1 million tons of ammonia will flow to
industry, and not to fertilizer. Looking to the
near future there are numerous announced plants
and this increase in production has been viewed
with considerable alarm in some quarters, some
fear that we may face repetition of the earlier
extreme cycles that the ammonia industry has
undergone. The best estimates available indicate
that there will continue to be short supplies
of nitrogen through 1977 or 1978. There will
probably be only a slight surplus in 1979. By
1980 we will again be close to a balance in supply-
demand. On the worldwide perspective, it is
projected that a deficit will still exist at the
end of this decade. In fact, it is likely that
severe nitrogen fertilizer shortages will continue
to exist in some agricultural areas. Technology
is, of course, available and is constantly being
improved for production of ammonia synthesis gas
from heavy oil and from solid fossil suels such
as coal or lignite.
PRODUCTION OF PHOSPHATES FROM PHOSPHATIC SLIMES.
Wayne C. Hazen, Angus V. Henrickson, and Pablo
Hasdzeriga. U.S. Patent 3,425,799, Feb. 4, 1969,
Appl. Aug. 14, 1964. pp. 9.
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Waste slimes from the beneficiation of Florida
or western phosphate rock are slurried in H2O
to give a solids concentration of about 10% by
wt. The suspension is heated to 60-70° and H2
SO^ is added slowly (>2 hours) at a steady rate
in an f^SC^rPoC^ wt ratio of 2-2.8:1. The reaction
mixture is filtered, the presence of large crystals
of gypsum from the reaction serving as a filter
aid. Filtration rates are 300-400 lb wet filter
cake/sq ft/24 hours using polypropylene
multifilament twill cloth and 1'5-18 in. Hg vacuum.
The filtrate containing about 16 g P5O5/I. is
passed over a cation exchange resin in the H form
such as "Dowex 53W-X8" to remove Fe and A1
impurities that would interfere with the next
step. The solution is then extracted with an
amine solvent such as "Alamine 336" which dissolves
the P2°5* T^e P2°5 *s recovered from the solvent
by treatment with NH^ to prepare crystalline
ammonium phosphate as product.
CHEMICAL AND PHYSICAL BENEFICIATION OF FLORIDA
PHOSPHATE SLIMES. James H. Gary, I.L. Feld, and
Edward G. Davis . U.S. Bur. Mines, RI 6163, 1963.
35 pp.
The slimes are finer than 150 mesh and contain
13% P2°5* Lak* tests were made on 2 settling-
pond slimes contg. P 5.7-4.3, P5O5 13.1-9.8, bone
phosphate of lime 28.6-21.4, CaO 11.9-11.7, Al
203 16.8-7.2, Si02 29-41.8, Fe203 7.2-3.3, MgO
1.9-1.8, F 2.2-2.2, and ignition loss 16.3-12.6%.
Quartz, attapulgite, and fluorapatite were the
chief constituents. Flocculating agents did not
improve thickening properties. Dewa'tering tests
with pressure filtration showed that temp, was
more important than pressure. The filtration
rate at 165° was 10 times the room-temp. rate.
The slime could be successfully fractionated at
20 by using a hydrocyclone. In hydrometallurgical
tests 80% of the P and AI2O3 were chem. extd.
by using H2SO4. Microorganisms were present in
the slimes, and their growth was not inhibited
by F-bearing minerals.
IMPROVEMENT OF QUALITY OF BYPRODUCT GYPSUM. Taro
Yamaguchi, Hirokazu Sato, and Akira Fujimura (to
Onoda Chemical Industry Co., Ltd.). Japan. Kokai
81
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75 120,491, Sept. 20, 1975, Appl. Mar. 7, 1974,
CA 84, 119930. 4 pp.
)4 0;5H,O or CaSu4
may be rehydrated to CaS04.2H20. The ^3^04 and
F compounds present in the Ca.SO4.2H2O as
contaminants are inactivated by this method.
Thus, CaS04.2H20 100 and CaO 2 parts were mixed
at 10° for 2 min and heated to 200° to obtain
CaSO40.5H2O. An impurity, Na2SiF6, seemed to
react with CaO to form an inactive compound, CaF
2'
GYPSUM FINDS NEW ROLE IN EASING SULFUR SHORTAGE.
Raul Remirez. Chem. Bng., Vol. 75, No. 24, Nov.
4, 1968. pp. 112-4.
A process for producing H2SO^ and cement from
gypsum, developed by Osterreichische^
Stickstoffwerke A.-G. at Linz, Austria, is
described with flowsheet. The raw materials are
anhydrite, fly ash, sand, and coke. These are
ground separately and stored in separate bins.
Then they are fed by proportioning feeders to
a blender. A typical mixture consists of 82.6
anhydrite, 7.4 fly ash, 5.9 coke, and 4.1% sand.
The mixture is then calcined in a rotary kiln,
the feed entering at the cool end and reaching
a temperature of 2600-2700°F. in the firing zone.
The following reactions occur: CaS04 + 2C 2CO
2 + CaS, 3CaS04 + CaS 4CaO + 4S02 and reaction
of the CaO with the sand and fly ash to form cement
clinker. Only Type 1 clinker has been made but
no problems are anticipated in making Type II
or other ASTM tyoes of clinker if desired. The
kiln exit gases (300-900°F.) contain 8-9% S02,
&ftsi¥ectr5ita«f8spPi§fp^S€B?haflddS¥ec^filfine
scrubbed with H20 in a lead-lined tower. The
wet gas then passes through a wet electrostatic
mist-precipitator which removes acid droplets,
and then through a packed drying tower where 93%
H2304 is circulated. The dry gas then enters
a converter where SO3 is formed. This process
is licensed by the M.W. Kellogg Co, of New York.
CONVERSION OF GASEOUS EFFLUENTS CONTAINING HYDROGEN
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FLUORIDE. V.S. Kalach and L.I. Burlakova. Fr.
Demande 2.284,556, Apr. 9, 1976, Appl. Sept. 10,
1974, CA 86, 21302. 17 pp.
Waste gas containing HF, SiF4 and/or SO2 is
scrubbed with neutral or alkaline aqueous solutions
to increase the efficiency of their removal,
recover F as NaF, permit the recycling of all
liquid effluents, and avoid corrosive conditions
during treatment. The gas, which may also contain
impurities such as phosphate, cryolite, or alumina
fines, or phosphoric acid mist is passed in turn
through two absorption towers each provided with
an aqueous spray at pH 6.5-7.5, containing
dissolved NaF, NH3, NH4F, NH4HC04, and (NH4)2CO
2 to remove a magor part of the HF, SiF4, and
SC>2 from the gas by converting them, resoectively
to NH4F, Na2SiFg, and NH^SO^. The treated gas
is freed of mist and discharged to the atmosphere.
The liquid from each tower is collected in its
storage tank for recycling. Part of the first
liquid is clarified by settling, and combined
with the filtrate from the settled suspension
of Na2SiFg. The clear liquid is reacted with
Na2C0o to precipitate NaF and possible some NaHSO
2. The precipitate is settled, filtered, and
dried, and the filtrate is recycled to the first
storage tank.
THE RECOVERY OF FLUORIDE FROM SUPERPHOSPHATE
MANUFACTURE. W.E. Russell. Chem. Ind. NZ, Vol.
4, No. 11, 19 68. pp. 10-11, 13.
In the manufacture of superphosphate from phosphate
rock and sulfuric acid a small proportion of
silicon tetrafluoride is evolved as part of.a
gaseous by-product. In general these fluoride-
containing gases have been regarded as a nuisance,
and water scrubbing and subsequent neutralization
has been required in certain cases to prevent
atmospheric and stream pollution. The fluoride,
however, represents a potentially valuable
recoverable material. The basis of design and
operation of a small process is described for
the economical recovery of a substantial part
of the evolved fluoride in the form of a commercial
15% strength hydrofluosilicic acid. This material
is finding increasing acceptance overseas as a
fluoridating agent for public water supplies and
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the major part of the production from this plant
is utilized for this purpose.
CONTROL OF GASEOUS FLUORIDE EMISSIONS. A.J. Teller.
Chem. Eng. Progr., Vol. 63, No. 3, 1967, pp. 75-
9.
Methods for removal of NH^, SiF^, and HF from
waste gases from various nrocesses are compare:].
Design problems are evaluated in terms of economic
considerations. Plugging of scrubbing system
with particulate matter from gas streams is a
major problem and can be reduced by concurrent
or cross current flow of liquid with respect to
gas. The no. of transfer units for removal of
gaseous F compds. ranges from 4 to 3. Recovery
efficiencies of over 99% are necessary. A primary
section of integral transfer devices followed
by a secondary section of differential transfer
devices is effective and of low cost. Blending
of various waste streans may be desirable.
RECOVEPY OF FLUOPINE IN THE FERTILIZER INDUSTRY.
Francois Moritz. Ind. ch im. Beige , Spec. No. 32,
Pt. 2, 1967. pp. 394-6.
An efficient scrubber for the recovery of F from
the gases generated during the production of Ca
superphosphate is described. In this multichamber
scrubber, SiP4 in air reacts with water to produce
l^SiFg and cryst. SiO^. The gas and liq. are
brought into contact in each chamber by liq.-
circulating sprayers. Solids which form in the
scrubber are collected by scrapers that pass slowly
across the bottom of the scrubber. These solids
are easily filtered.
RECOVERY OF HYDROFLUORIC ACID FROM WASTE
FLUOROSILICIC ACID. PRELIMINARY STUDIES. P.C. Good
and J.E. Tress. U.S. Bur. Mines, RI 7213, 1968.
Fluosilicic acid is generated by plants processing
phosphate rock in the manufacture of fertilizers.
Most phosphate rock contains 3-5% F in the form
of the mineral fluoroapatite. When the F-bearing
material is treated by either acid or thermal
processes, much of the F is volatilized as SiF
a presenting a serious air pollution problem.
Tests show that direct hydrolysis of H2SiF6 to
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SiC>2 anHF at elevated temperatures was subject
to mechanical difficulties and that corrosion
was a serious problem. Elimination of SiO? from
the HF product is poor. An alternative orocedure,
hydrolysis of lime-neutralized H2SiF5 by steam
at 950-1100 C. yielded a product "containing SiO
2 <1.8% of the fluoride content. Condensates
containing<300 g/liter HF were orepared.
RECOVERY OF FLUORIDES FROM GASEOUS RY-PPODUCTS IN
THE PRODUCTION OF PHOSPHORIC ACID OR PHOSPHATES.
Albert H. Cooler. U.S. Patent 3 ,245 ,756(CI. 23-88)
April 12 , 19 66. AppI June 22, 1954. 2 pp.
The gases liberated in the production of phosphates
or H3PO4 from F-contg. materials are freed of
solid dust particles and treated with anhyd. NH
3 or a mixt. of and H2O vapor to yield SiF
4 and HF as a concd. fluoride in solid form.
The mixt. is slurried with water and treated with
anhyd. NII3 or NH^OH, at pH 8 to obtain a soln.
of NH*F and SiO?. Fine sized, high purity SiO
2 is filtered off and dried. The NH^F soln. is
further processed to obtain the desired fluoride
products. Thus, on treatment with NaOH or Na2
CO3 and Na aluminate and heating to 75-85°, Na
3AlFc was pntd. , filtered, dried, and calcined
at 500-700° to obtain a granulated product. Other
fluorides may be obtained by appropriate treatment.
FLUORINE RECOVERY FROM PHOSPHATIC FERTILIZER
MANUFACTURE. . English. Chem. Process Eng., Vol.
48, No. 12, 1967. pp. 43-7.
The present demand for fluorine is expanding so
rapidly that the traditional sources-natural
cryolite and fluorspar-may soon be exhausted.
An alternative source is fluorapatite, containing
3-5% fluorine, used principally for the production
of superphosphate and phosphoric acid for
fertilizers by the 'wet' process. This article
describes how the by-product from the process,
fluorosilicic acid, which is generally discarded,
could be used in the commercial production of
fluorosilicates, cryolites and fluorides.
FLUORIDE RECOVERY FROM PHOSPHORUS PRODUCTION. J.C.
Rarber and T.D. Farr. Chemical Engineering Progress
Vol. 66, No. 11, 1970. pp. 56-62.
85
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Commercial fluorine compounds (cryolite and
aluminum fluoride) can be recovered from phospnorus
plant fluorine wastes. Several processes have
been described in which fluorine compounds are
recovered pure enough to meet stringent
specifications required in the production of
aluminum. In the recovery processes, waste gases
are scrubbed with ammonia solution to form ammonium
fluoride and ammonium fluosilicate. Then the
scrubber solutions are ammoniated further to
precipitate silicon and iron compounds, and these
impurities are removed by filtration. The
subsequent steps used to recover specification-
grade products from the purified solution depend
upon its P9O5 content. Alternate steps are
described for using ammonium fluoride solution
with high P2O5 content.
Costs for fluoride disposal are increasing because
stringent pollution abatement standards are being
put into effect. Double liming of waste water
is required at some places because the fluoride
concentration of the waste.water must be reduced
to low values. The increases in disposal costs
also make valuable product recovery more
attractive.
ECONOMIC AVAILABILITY OF BYPRODUCT FLUORINE IN THE
UNITED "STATES. 1. UTILIZATION OF BYPRODUCT
FLUOSILICIC ACID IN THE MANUFACTURE OF ALUMINUM
FLUORIDE. 11. UTILIZATION OF BYPRODUCT FLUOSILICIC
ACID IN THE MANUFACTURE OF CALCIUM FLUORIDE. R.C.
Johnson, J.W. Sweeny, and W.C. Lorenz. U.S. Bureau
of Mines IC 8566, 1973. 97 pp.
The availability of domestic byproduct F in H2
SiFg at various price levels of AlFo was
determined. The supply of byproduct H2SiFg is
restricted in amount to certain geographic regions
where plants processing phosphate rock are located
and the byproduct can be collected. The maximum
possible U.S. annual supply, based on plant
capacities, is 373,400 tons of H2siF6 containing
295,400 tons of F. Estimated cost studies are
made for five different size plants producing
acid-grade CaFj from waste H2SiFg recovered from
wet-process phosphoric acid and superphosphate
fertilizer manufacture.
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UTILIZATION OF WASTE FLUOROSILICIC ACID. 1.
LABORATORY INVESTIGATIONS. 2. COST EVALUATION.
H.E. Blake et al U.S. Bur. Mines, RI-7502, 1971.
60 pp.
Two processes are described for utilizing byproduct
H2SiF6 from phosphate fertilizer manufacture.
One process involves conversion of H2siFg to acid-
grade CaF2 by precipitating the Si02 with NH3,
filtering, and treating the NH4f filtrate with
Ca(OH)2. Over 95% of the fluoride is converted
to CaF2. The other process involves neutralizing
the H2SiFg with Ca(OH), and Si02, filtering, and
volatilizing HF from trie dry precipitate by
hydrolytic decomposition at 1050°. The HF-H20
vapors are condensed and the fluoride is
precipitated as NaF HF by adding NaF to saturation.
Anhydrous HF is recovered from the NaF HF by
pyrolysis at 400°. Over 80% of the F in H2siF
g is recovered as anhydrous HF. Metallurgical
grade AIF3 was prepared by reacting the offgases
with activated Al203 in preliminary tests.
CLOSED POND SYSTEM FOR WET-PROCESS PHOSPHATE PLANTS.
R.G. Hartig. U.S. Patent 3,720,757, Mar. 13, 1973,
Appl. Aug. 3, 19 70. 6 pp.
Fluorine values are removed from liquid effluents
of wet-process phosphate plant complexes and the
purified effluents are returned to the process
for reuse. Silicon tetrafluoride in the effluents,
by the addition of NaF, is converted to Na^SiF
g, which is separated from the effluent ana
calcined to form NaF and SiF^. The NaF is returned
to the effluent stream and the SiF^ is recovered
as H2SiFg by H20 scrubbing. Addition of Si02
converts HF in the effluents to Na2SiFg. Any
H3PO4 in the effluents reacts with NaF and SiO
2 to form NaH^PO^ which is separated from the
Na2SiFg as a liquid effluent stream. The NaH2
PO4. is then treated with part of the SiF^ formed
in the calcination step to form H3PO4. Since
no H2o folutions are discarded from the process,
contamination of surface and ground H20 is
eliminated.
RECOVERY OF HYDROGEN FLUORIDE FROM AQUEOUS
FLUOSILICIC ACID. R.G. Hartig. U.S. Patent
87
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3,711,596, Jan. 16, 1973, Appl, Mar. 4, 1965. 9
pp.
At least 95% of the F in aqueous H^SiFg is
recovered as anhydrous liquid HF in a multi-step
process. Aqueous H2SiFg is stripped with steam
to produce a first gas stream composed of HF,
H2O vapor and SiF^, which is then contacted by
a flame to produce a second gas stream containing
HF, H2O vapor, and solid SiO? in suspension.
After removal of the Si02, this second gas stream
is passed upward through a first fluidized bed
of NaF to produce finely-divided NaHF,, which
is transferred to a second fluidized Bed at
elevated temperature. There a stream of HF is
circulated upward through the bed of NaHF2 to
drive off HF and recover NaF for recycling to
the first fluidized bed. A portion of the
circulating HF is withdrawn, cooled and condensed
as anhydrous liquid HF product.
FLUOSILICIC ACID RECOVERY FROM DILUTE PHOSPHORIC
ACID WASH SOLUTIONS. Laurence W. Bierman, Jr.,
Jerry L. May(Simplot, J.R., Co.). U.S.Patent
3,615,195(C1 23/165, C 01b), Oct. 26, 1971, Appl.
Dec. 11, 1968. 9 pp.
CaSO^, from the reaction of H2SO4 with phosphate
ores contg. fluoride in the wet process of manufg.
H3P04' *s washed with an aq. washing liquor to
remove adhering H3PO4, and this wash soln. is
returned to the reactor-digestor system after
a F-recovery process. The defluorination process
consists of: adding strong H2SO^ and acid-sol.
SiO, to the wash soln. £0 provide a H2S04 concn.
of 29-4 5 wt. % and to convert HF to SiF4 and H
2SiFg; passing a gas, such as air or steam, through
the acidified wash soln. at 130-240°F to strip
volatile F compounds from the mixt.; and absorbing
the fluorides in a medium, such as aq. 25wt.%
H2SiF66 soln.
CALCIUM FLUORIDE FROM FLUOSILICATES AND BYPRODUCT
GYPSUM. G.E. Kidde. African 74 02,881, Mar. 25,
1975, Appl. US June 11, 1973, CA 84,61960. 24pp.
Byproduct H2SiFg solution from the manufacture
of H2PO4 is reacted with NH3 to bring the pH to
8.8-9.2, precipitating the Si02. The mixture
88
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is filtered and the filtrate is heated to remove
NH^and leave a solution of NH4F HF. The NH4F
HF solution is reacted with beneficiated byproduct
CaSO* 2H20 to form CaF2 and (NH4)2S04. The
reaction mixture at pH 0.3-1.0, is filtered to
separate commercial-grade CaF2.
RECOVERY OF FLUORINE, URANIUM, AND RARE EARTH METAL
VALUES FROM PHOSPHORIC ACID BY-PRODUCT BRINE
RAFFINATE. C.A. Wamser and C.P. Bruen (to Allied
Chemical Corp.). U.S. Patent 3,937,783, Feb. 10,
1976, Appl Feb. 21, 1974. 8pp.
A process is described for the simultaneous
recovery of F,U, and rare earth metal values from
apatite. The apatite is digeted with HC1 at <
110 to form an H3PO4 solution containing CaCl
2, F,Uf and the rare earth metal values together
with an incoluble residue which is separated.
An Al compound selected from AICI3, ^-(0^)3, Al
2(SO)3 and mixtures thereof may be admixed with
the H3PO4 solution and the solution may be treated
to reduce the U5+ to U4+. The H3PO4 solution
is then contacted with an organic solvent capable
of dissolving HoP04 but having limited miscibility
with H20 free of H3PO4 to produce an organic phase
containing the H3PO4 and an aqueous phase
containing CaCl2, F, U, and the rare earth metal
values. After separating the organic phase, the
aqueous phase is neutralized to pH 9-11 with a
base selected from alkali hydroxides, alkaline
earth hydroxides, alkali carbonates, alkaline
earth carbonates, NH4OH, alkaline earth silicates,
alkaline earth oxides, and mixtures thereof.
The resulting basic solution Of CaCl2 is separated
from the precipitated solids which contain the
F, U, and rare earth values.
ALUMINUM FLUORIDE MADE FROM FLUOFOSILICIC ACID.
Chemical and Process Engineering, Vol. 53, No. 11,
June 1972.
The whole of the world demand for fluorine
compounds in the aluminium industry could be met
by making full use of the fluorine present in
phosphoric acid plant waste gases. This was the
conclusion of P.M.R. Versteegh and T.J. Thoonen,
in a paper recently presented to the Fertiliser
Society, London, when they described a process
89
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for making aluminium fluoride from fluorosilicic
acid.
The process uses Gibbsite (Al203.3H20) as the
source of aluminium, and ammonia in a
carrier/recycle system.
RECOVERY OF FLUORINE AND PHOSPHATES FROM WASTE
WATERS. R.J. Hirko and H.E. Mills(to Occidental
Petroleum Corp.). 3elg. 327,305, July 16, 1975,
Appl. US Apr. 3, 1974, CA 84, 184604. 27pp.
Waste H20 from phosphoric acid manufacture is
mixed with CaCOo to 0.3-0.8 equivalent of
Ca/equivalent of F and mixed; then excess CaCO
3 is added and CaFo precipitates. Thus 3834 g
of waste H2O containing F 0.94, P2O5 1.70, SO3
0.41, Si02 0.59% and other soluble metallic
compounds'is mixed with 34.4 g of industrial CaCO
3 at 43°; the mixture is agitated 5 min and the
pIJ increases from 1.39 to 1.85. There is no
precipitation of a fluoride compound. A second
addition of CaC03 (10.69g) increases the pH to
3.0 and CaF2 precipitates after mixing for 37
min. The precipitate is separated by filtration
and dried to yield 1.41 g of solid CaF2.
PRODUCTIOH OF SYNTHETIC FLUORSPAR FROM WASTE
FLUOSILICIC ACID. Karl-Heinz Fellberg Siegfried
Schneider, and Friedrich Wolstein. Phosphorus
Potassium, No. 85, Sept.-Oct. 1975. pp. 39-40 .
The title orocess, characterized by the equation
H2SiFc + 3CaC03 3CaF2 + Si02 + 3C02 +1^0, was
jointly developed by Bayer A.G. and Kali-Chemie
A.G.; a production plant is now being designed
jointly with Friedrich Uhde G.m.b.fl. An aqueous
suspension of ground limestone and the I^SiF^
are continuously fed to a system of series-
connected reactors. By proper control of the
reaction, C02 is released and Si02 remains in
solutions as 'a metastable sol. After a short
retention time, auxiliary materials are added
to improve filtration and the solids are separated
from the sol. The CaF2 sludge, which contains
30% H20, is dried to produce a finished product
containing > 90% CaF^ together with 2.5-3.5% SiO
2, CaC03, and other impurities; the F yield is
> 99%. Only a few ppm of dissolved F remain in
90
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the SiC>2 sol, which is treated with quicklime
for flocculation, thereby further reducing the
content of dissolved F. The CaF2 is suitable
for the production of HF and can be compacted
for use in the production of steel. Fluosilicic
acid solutions of concentration as low as 10%
have been used successfully.
RECOVERY OF FLUORIDES AS BY-PRODUCTS. M.D. Sanders.
In: Phosphoric Acid by A.V. Slack, New York: Marcel
Dekker, 1968 . pp. 765-777.
Most of the commercially important phosphate ores
contain 3 to 4% fluorine after beneficaition.
Fluorine compounds in phosphate rock react with
sulfuric acid during the attack on the rock; the
fluorine appears in the vapors as hydrofluoric
acid (HF) and silicon tetrafluoride (SiF*) and
fluosilicate salts. Acid from rock low in silica
may also contain hydrofluosilicic acid (HF).
There are three possible sources of by-product
fluorides in wet-process phosphoric acid
manufacture. Vapors from the reactor slurry may
be scrubbed with water to recover fluosilicic
acid, sodium salts may be added to the filter
acid to precipitate sodium fluosilicate, and the
concentrator vapors may be scrubbed to recover
fluosilicic acid.
A substantial fraction of the fluoride input to
wet-process phosphoric acid plants can be
economically recovered as fluosilicic acid or
fluosilicate salts. The acid is usually the most
desirable primary by-product in fertilizer
phosphoric acid plants. It has large end uses
as such and silicofluorides of high purity can
be produced from it. Fluosilicic acid is a low-
cost intermediate material for other fluorides.
The growing demand for fluosilicic acid and
fluosilicates as such, and the uses of these
chemicals as intermediates in the production of
other fluorides, would seem to make recovery of
by-product fluorides an economically attractive
adjunct to wet-process phosphoric acid production.
RECOVERING URANIUM FROM WET-PROCESS PHOSPHORIC ACID.
91
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F.J. Hurst, W.D. Arnold, and A.D. Ryon. Chem. Eng.
, Vol. 84, No. 1, Jan. 3, 1977. pp. 56-7.
One successfully-piloted solvent-extraction orocess
and another solvent extraction process under
investigation perform a twofold function to recover
U from wet-process H3PO4 and thereby remove the
radioactive contaminant from subsequently-prepared
phosphate fertilizers. The successfully-piloted
DEPA-TOPO, or reductive stripping, process uses
the synergistic combination of di(2-ethylhexyl)
phsoohoric acid (DEPA) and trioctyl phosphine
oxide (TOPO) to extract the oxidized U as U+b,
while the OPAP, or Oxidative stripping, process
utilizes a mixture of mono and di-octylphenyl
phosphoric acid (OPAP) to extract the U as rj+4
, the prevailing oxidative state in fresh H^PO
4. Both processes are very similar and can be
operated in identical equipment^ The concentration
cycle involves three unit ooerations; (1)
pretreatment of the ^PO^ to remove organic natter,
to adjust the valence of the U, and to adjust
the temperature of the acid to 40-50°; (2) solvent
extraction and stripping of the U to increase
its concentration by a factor of 50; and (3)
post-treatment of the HjPO^ to remove extractant
contamination. The n purification cycle consists
of extraction, scrubbing and stripping steps.
URANIUM RECOVERY FR0?1 PHOSPHATE ROCK. Chem. Eng.
News, Vol. 55, No. 1, Jan. 3, 1977. p.7.
Freeport Mineral will recover uranium as an oxide
from processing phosphate rock in making ^oPO*
for fertilizers. Facilities using technology
developed by Freeport are scheduled to begin
operations late in 1978 in the company's plant
at Uncle Sam, on the Mississippi River above Mew
Orleans. Capacity will be 690,000 lb/yr of uranium
oxide, known as yellow cake, or about 3% of U.S.
uranium oxide production in 1975. Half of the
facility's capacity has been sold under a long-
term contract, which includes $10 million in
advance payment from an undisclosed buyer.
SEPARATION OF URANIUM FROM AN AQUEOUS LIQUID
CONTAINING_UPANYL IONS AND CONTAMINATING CATIONS.
Leonard Elikan, Ward L. Lyon, and Parameshwaran
S. Sundar(Westinghouse Electric Corp.). Ger. Offen.
92
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2,451,595 (CI. CO1G), May 7, 1975, US Appl 411,886,
Nov. 1, 1973. 21 pp.
An improved process is described for recovering
U oxides from the wet-process HoP04 or H?S04 soln.
contg. FeJ+ 7-15 and U (as UO^ ) 0.1-0.2 g/1.
The H3P04 or H2S04 soln. is mixed with a FIjO-insol.
org solvent (kerosine) contg. a complexing"agent
such as bis(2-ethylhexyl) H phosphate and tri-
n-octylphosphino oxide synergisic agent. The
resulting ©eg. phase eontg. tj is rtduetd with
an aeidie Fe §Qln. t© obtain U4+ in the ag, phage
(Fe 25-40, U 5-15 gle). Then, the is oxidized
to U02 and mixed with (NH4)2C03 to increase
the U concn. The mixt. is treated with the
complexing agent mixt. to ext. the U022+ and with
(MH4)2C03 or NH4IPC03 to ppt. U02(0H)2S.5(NH4)2co
30.5H2O(I). The I is calcined at 350-900° to
remove NH3 and C02 and obtain U02 or U3Og denending
on the atm. The potd. I containes U 4.45 and
Fe 0.0040%.
MANUFACTURE OF PHOSPHATIC FEPTILIZERS AND RECOVERY
OF BYPRODUCT URANIUM-A REVIEW. R.J. Ring(Aust.
At. Energy Comm. Pes. Establ., Lucas Heights,
Australia). Report AAEC-E-355, 1975. 99 pd.
The processes used in the production of phosphatic
fertilizers are reviewed and those in which U
can be extracted as a byproduct are described
in detail. Recovery from wet-process H3P04 by
solvent extraction is the most promising approach.
URANIUM RECOVERY FROM PHOSPHORIC ACID NEAPS REALITY
AS A COMMERCIAL URANIUM SOURCE. R.C. ROSS .
Engineering/Mining .Journal, Vol. 17 6, No. 12, 1975.
pp. 80-5.
Marine phosphorites contain 50-200 ppm of U, which
is extracted by wet-process H3P04 plants. The
U can be extracted in the reduced (U4+) state
from the acid solution, containing 30% of
, with H3P04 or H4P?07, or in the oxidized (UO
2^+) state with a mixture of bis(2-
ethylhexyl)phosphoric acid and trioctylphosphine
oxide. The potential recovery from all U.S. wet
process plants is established at 5.5-6 rnillion
93
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lobs of annually.
RECOVERY OF URANIUM FROM PHOSPHATE ROCK. Mac C.
Metziger, Alfred Long, and Emil M. Stoltz, Jr. (to
the United States of America, as represented by
the Atomic Energy Commission). 1U.S. Patent
2,743,156, Apr. 24, 1956.
Ground phosphate rock was leached with 25% H^SO
4, and the resulting crude H3P04 contg. small
amts. of U was oxidized with CI to convert U to
the U02++ state. Na2C03 was until a pH
of 3.5-4.5 was obtained. After two successive
filtrations to remove CaS04 and other residue,
the clarified NaH2P04 soln. contained 46.2 mg./l.
of U. At 60 , 0.4 g./l. Na2S204 and 0.5 g./l.
diatomaceous earth filter aid were added to form
a ppt. contg. 6.69% 0303, which represented a
91.8% recovery of U. An upgrading step was
introduced in which the soln. obtained on
dissolving the ppt. in warm H2S04 was oxidized
with NaC103 or other suitable oxidizing agents.
A U phosphate ppt. then was formed by neutralizing
with NH^OH. The resulting ppt. contained 63.7%
U308, which indicated a recovery of 98.6% U in
the upgrading step. This step can be repeated
several times.
URANIUM RECOVERY FROM WET-PROCESS PHOSPHORIC ACID.
Bruce F. Greek, Otis W. Allen, and Donald E. Tynan
Ind. Eng. Chem., Vol. 49, 1957. pp. 628-38.
Recent developments in U extn. from low grade
ores are discussed. U in phosphate rock could
not be recovered economically except as a by-
product of phosphoric acid manuf. I.M.C.'s rock
consists mainly of complex Ca phosphate-fluoride
compds. This is digested with H2S04 under
controlled conditions. The soln. is 1st allowed
to come in contact with Fe to reduce U(VI) to
U(IV) then with an alkyl pyrophosphate, forming
a complex. The org. complex in a diluent (kerosine)
is sepd. from the H3PO4 soln. and the U recovered
by reaction with HF. A detailed description of
the plant equipment with flow-sheets and
photographs is given.
RECOVERY OF URANIUM FROM WET-PROCESS PHOSPHORUS
ACID BY EXTRACTION WITH OCTYLPHENYLPHOSPHORIC ACID.
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F.J. Hunt, D.J. Crouse(Oak Ridge Antl. Lab., Oak
Ridge, Tenn.) Ind. Egn. Chem., Process Pes. Develop.
Vol. 13, No. 3, 1974. pp. 286-96.
Com. wet-process HoPO^ produced from Florida
phosphate rock contains 0.1-0.2 g of U/l. A
process for recovering the U by extraction with
a mixt. of mono and dioctylphenyl phosphate in
an aliph. diluent was developed and demonstrated
successfully in bench-scale mixer-settler tests.
The U is recovered from the solvent by contacting
it with IONH3PO4 contg. NaClO^; the chlorate
oxidizes the U to the less-extractable hexavalent
state and effects its transfer to the aq. phase.
The strip soln. can be loaded with U to 15-20
g/1, a factor of" >100 richer in U than the
original acid. These soln. are highly amenable
to processing in a 2nd cycle with the synergistic
extractant combination of bis (2-ethylhexyl)
phosphate plus trioctylphosphine oxide. The U
is stripped from the solvent with (HFI^) 2CO3 soln.
and recovered as a high-grad- (>98% U^O^) product.
RECOVERY OF URANIUM FROM ORGANIC SOLVENTS. French
T. Hagemann, Leonard I. Katzin, and Nison N.
Hellman(to the United States of America, as
representd by the Atomic Energy Commission). U.S.
Patent 2,743,157, Apr. 2 4, 1956.
The vol. of U-contq. org. solvent solns. is
substantially reduced, and a method is provided
for recovering substantially U-free solvent
suitable for reuse. The efficiency of the reextn.
processes for recovery of U from org. solns. contg.
U(VI) is improved markedly by use of a reagent
which forms a preferably aq. sol. complex compd.
with U. For example, an ethereal uranyl nitrate
soln., obtained by extg. a HNO3 soln. of irradiated
Th0C03 v/ith diethyl ether, was reextd.
countercurrently with aq. 3N (NH^^SO^ soln.
The recovery of U was 99.5%. Instead of sulfate,
the ag. stripping solns. can contain, as a
complexing agent, phosphate, oxalate, or fluoride.
RECOVERY OF URANIUM FROM INDUSTRIAL PHOSPHORIC ACIDS
BY SOLVENT EXTRACTION. I. SUMMARY STATUS REPORT.
II. INDEX OF MONTHLY PROGRESS REPORTS. D.A. Ellis
U.S. Atomic Energy Comm. DOVJ-81, 1952. 81pp.
95
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The solvent extn. process described consists of
the following steps: (a) Bring the acid into
contact with a soln. of alkyl phosphoric acid
in a suitable diluent; (b) sepn. of the phases;
(c) removal of the extd. U from the org. phase
by pptn. with HF or other reagents, or by re-
extraction into other solns. Studies have been
made of the effects of oxidation potential of
the acid, of treatment with silicious materials,
of temp, of the acid, and of phosphate concn.
of the acid. A number of alkyl phosphoric and
pyrophosphoric acids have been tested. The methods
of manuf., the effects of structure on the extn.,
and the use of various diluents have been
investigated. A multistage countercurrent mixer-
settler has been constructed and operated under
various conditions. This has made possible the
production of considerable quantities of U-contg.
ext. An extensive study was made of the pptn.
of U from org. exts. with HF. A few pptns. were
made with NFU. Extn. of U from the org. soln.
with concd. H3PO4 and with HC1 solns. was also
studies. An investigation was made of the
breakdown of the extractants under various
conditions, and of methods of rejuvenation that
would enable the extractants to be recycled.
Various modifications in analytical procedures
were developed, both for 0 analysis and detn.
of the compn. of the extractants.
EXTRACTION OF URANIUM FROM IMC(INTERNATIONAL MINERALS
PHOSPHORIC ACID WITH VARIOUS DIALKYLPYROPHOSPHORIC
ACIDS. James E. Magner U.S. At. Energy Comm.
DOW-160, 1957. 16 pp.
Various dialkylpyrophosphoric acids were tested
as extractants for U from IMC HjPO^. Included
in the testing program were didecyl esters prepd.
at IMC (fresh plant ester and recycle plant ester)
and esters prepd. in this lab. (didecyl and
dicapryl derivs.). From Nucl. Sci. Abstr. 14,
Abstr. No. 11683(1960).
OCIDATIVE STRIPPING PROCESS FOR THE RECOVERY OF
URANIUM FROM WET-PROCESS PHOSPHORIC ACID. Fred.
J. Hurst, David J. Crouse(United States Atomic Energy
Commission). 1U.S. Patent 3,835,214 (CI 423/10;
B Old, C Olg) , Sept 10, 1974, Appl 280,922, Aug.
15, 1972. 4 pp.
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In a process for recovering U as a by-product
of wet-process H3PO4 manuf., the aq. H3P04 soln.
is 1st treated to convert all the U to the
tetravalent form. The H0PO4 soln. is then
contacted with a mixt. or mono- and bis[p-(l,1,3,3,-
tetramethylbutyl)phenyl] phosphates dissolved
in kerosine. The U enters the org. phase from
which it is subsequently stripped by contact with
aq. 8-12M H3PO4 contg. an oxidizing agent, e.g.
2-10 g NaClOj/I. The U(IV) is thereby oxidized
to U(VI) which enters the aq. phase. The U-loaded
stripping soln. is then dild. with H20 to 5.5-
6.5M H3P04, followed by a 2nd extn. with an org.
phase contg. bis(2-ethylhexyl) H phosphate and
trioctylphosphine, oxide in an inert org. solvent.
The U-loaded 2nd org. phase is then contaced with
aq. 0.5M ()5CO3 soln. to form a slurry of 2(NH
4)2*^03 U02C03 2H2O. The solids are sepd., washed,
ana calcined to produce high-purity U oxide.
EXTRACTION OF URANIUM FROM PHOSPHATE SOLUTIONS.
H.R. Baxman. 1U.S. At. Energy Coram. AECD-3746,
1956.
A process for the extn. and depoisoning of U in
strong H3PO4 with Bu-jPO^ (TBP) is described.
The'formation of a complex between uranyl and
phosphate ions necessitates the use of a salting
agent which is capable of destroying this complex
and releasing the uranyl ion into an org.
extractable species. Of various salting agents
tried, Fe(N03)3 was the most successful. It not
only provides nitrate ion for the fomration of
U02(NO3)2 f but also forms a very stable ferric-
phosphate complex, thus completely tying up the
phosphate ion when added in eguimolar quantities.
Stripping of the enriched solvent is accomplished
with U3PO4. From INuclear Sci. Abstr. 13, Abstr.
No. 2054(1959).
RECOVERY OF URANIUM FROM PHOSPHATE BY ION EXCHANGE.
Summary Status Report No. 3. R.H. Bailes. Dec.
7, 1949. Decl. Sent. 29, 1955. 20 pp. Contract AT-
30-1-GEN-2 36.
A process which will produce UF4 of 95% purity
from commercial 30% H3PO4 has been developed.
This process will recover 98% of the uranium in
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the feed acid. Based on a currently available
feed stream of 500 tons of 30% H3PO4 per day,
the manufacturing cost is estimated at %5.17/lb
U^Og in an ion-exchange plant costing $213,000.
In addition to the U, this acid also contains
a substantial amount of V. With the same ion-
exchange plant, 91% of the V can be recovered
as a 50% concentrate of V2O5 in the amount of
25 pounds VoOc/lb. U3Og at an additional cost
of only $0.ll/lb V9O5. The V recovery process
now operating on this acid stream extracts only
about 80% of the V present. Thus, the value of
the additional 3 pounds of V20cj/lb U^Og made
available by the ion-exchange process could
properly be credited to the ^363 raw material
cost. With V2OC at $1.00/lb the net cost of U
30g would then Be only $2.50/lb. It should be
stated that these cost calculations have been
based on an assumed resin life of only 500 cycles.
If the resin life is of the order of 1000 or more
cycles as currently available laboratory data
indicates may be possible, the cost of UgOg could
be reduced from $2.50 to about $2.00/lb., and
the V2O5 cost from $0.11 to $0.09/lb.
REDUCTIVE STRIPPING PROCESS FOP THE RECOVERY OF
URANIUM FROM WET-PROCESS PHOSPHORIC ACID. Fred
James Hurst, David Jones Crouse(U.S. Atomic Energy
Commission). S. African 71 03,457 , Dec. 6, 1971,
US Appl 53,058, Jul 3, 1970. 11 np.
Phosphate rock contg. U^Og is treatgd with H?SO
4, producing a H3PO4 soln. contg. U and a CuSO
4 ppt. The soln. is treated with a reducing agent,
changing the U5+ to U4+ form. The soln. is then
stripped with a (^4)2003 soln. to give NH4 uranyl
tricarbonate, which forms a thick slurry. This
is readily filtered, washed, and calcined to give
PHOSPHATE ROCK PROCESSING URANIUM WILL BE ROCOVERED
IN FLORIDA PLANT. F.J. Hurts, et al. , llnd. Eng.
Chem. Process Design Develop. , Vol. 11, No. 1, 1972.
Davy Poweraas Inc., of Lakeland, Fla., is to design
a uranium separation plant which will be installed
at the phosphoric acid plant of W.R. Grace & Co.
at Bartow, Fla., under a contract recently
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negotiated between Grace and Uranium Recovery,
of Rockville, Md. Hitherto, the uranium content
of Florida rock (0.012-0.024% U3Og) has been
considered too low for economic recovery. Details
of the process to be used have not been disclosed,
but an organic solvent will be used to extract
the uranium values which will be transported to
a central processing plant for refining. The
company is currently negotiating for a second
installation at another (unnamed) fertilizer
producer's plant. The combined capacity of the
two plants, if both are built, will be 500 s.
tons p.a. of uranium concentrates.
Research work on-the recovery of uranium from
wet-process phosphoric acid manufactured from
Florida rock has been carried out at the Oak Ridge
National Laboratory, Oak Ridge, Tenn. A solvent
comprising di(2-ethylhexyl)-phosphoric acid and
trioctylphosphine oxide in a high-boiling aliphatic
diluent is used to extract the uranium values
from the phosphoric acid; the solution is then
contacted with phosphoric acid containing ferrous
ions to reduce the uranium to the tetravalenr
state, in which it is less soluble in the organic
solvent and therefore returns to the aqueous pnase.
The phosphoric acid used in this stage is pace
of the raffinate from the extraction stage, The
tetravalent uranium is then oxidized back to tne
hexavalent state by bubbling in air or by addition
of sodium chlorate, and is then extracted a second
time with the same organic solvent. It is finally
recovered from the organic solution at an overall
yield of about 95% of stripping with an aqueous
ammonium carbonate solution. Ammonium uranyl
tricarbonate is precipitated and, after filtration,
is calcined to UjOg.
RECOVERY OF URANIUM FROM WET-PROCESS PHOSPHORIC
ACID. Fred J.' Hurst, David J. Crouse, and Keith
B. Brown(Oak Ridge Natl. Lab., Oak Ridge, Tenn.;,
Ind. Eng. Chem., Process Pes. Develop, 1972, Vol.
11, No. 1. pp. 122-8.
A 2-cycle process for recovering U by extn. with
bis(2-ethylhexyl) H phosphate plus
trioctylphosphine oxide in an aliphatic diluent
was developed and demonstrated successfully in
bench-scale mixer-settler tests. The U ic,
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recovered from the solvent and concd. by reducing
it to the less extractable tetravalent form with
Fe++ contained in reduced process raffinate.
This soln. is oxidized and processed in a 2nd
cycle with the same extractantv In the second
cycle the U is stripped from the solvent with
ammonium carbonate soln. and recovered as a high-
grade (>97% U3O0) product. Overall recovery of
U is 95%. In the bench-scale tests, losses of
the relatively expensive solvent to the aq.
raffinate were satisfactorily low (<0.1 ml/1.).
A NEW PROCESS TO RECOVER URANIUM FROM WET PROCESS
PHOSPHORIC ACID. Engineering/Mining Journal. Vol.
17 5, No. 5, 1974. p. 9.
A new process to recover uranium from wet process
phosphoric acid, developed by Gulf Research &
Development Co., was being demonstrated early
in April at the Agrico Chemical Co., Pierce, Fla.
The new technology makes it economically feasible
to extract uranium from phosphate rock as the
rock is being processed and made into phosphoric
acid, Gulf said. The unique oilot plant being
used to demonstrate the process is mounted on
two enclosed truck trailers-provideing the mobility
for transfer to various phosphoric.acid production
facilities. When transferred to a new location,
the pilot unit is tied into the orocess stream
of the acid plant and operated by Gulf long enough
to demonstrate the process. The process is
basically a modification of a system developed
by the Atomic Energy Commission at its Oak Ridge
National Laboratory. Total recovery of all of
the uranium in phosphate rock processed in central
Florida would amount to between 5% and 10% of
total uranium production in 1980, Gulf said.
The process is an environmentally clean, closed
system.
URANIUM RECOVERY FROM PHOSPHORIC ACID WEARS REALITY
AS A COMMERCIAL URANIUM SOURCE. Richard C. Ross.
Engineering/Mining Journal, Vol. 176, No. 12, pp.
80-5.
Marine phosphorites contain 50-200 ppm U, which
is extd. by wet process H3PO4 plants. The U can
be extd. from the 30% P?Oe ac^ soln. in the
reduced (U^+) state with H3PO4 or H4P20-J, or in
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the oxidized (U022 ) state with a mixt. of bis(2-
ethylhexyl) phosphoric acid and trioctylphosphine
oxide. Potential recovery from all U.S. wet-
process plants is estd. at 5.5-6 million lbs.
U^Og annually. Three actual recovery processes
are described, including the AEC Uranium extraction
process of the 1950s, the Oak Ridge National
Laboratory Process, and the Uranium Recovery
Process.
PHOSPHORIC ACID - THE NEW NUCLEAR FUEL. Richard
J. Guimond. EPA Draft, April, 1976.
This article discusses the technological aspects
of recovering uranium fuel as a by-product of
phosphoric acid manufacturing. The socio-economic
significance of phosphoric acid as a source of
uranium fuel in the past, present, and future
is examined. It evaluates the potential impact
of this source on usable uranium reserves and
discusses new technical discoveries in this area.
SOLVENT EXTRACTION OF URANIUM FROM WET-PROCESS
PHOSPHORIC ACID. Fred J. Hurst, D.J. Crouse, Keith
Blanchard Brown U.S. At Energy Comm. 1969, ORNL-
TM-2522, 49 pp.
A large number of reagents were screened, in
laboratory tests, for possible use as extractants
for recovering uranium from commercial wet-process
phopshoric acid. Results indicated that the
synergistic extraction combination of di(2—
ethylhexyl) phosphoric acid plus trioctylphosphine
oxide in a kerosene type of diluent was
sufficiently promising to merit further evaluation.
Although the uranium extraction coefficients, for
this combination are not high, they are adequate
for effective process application.
Based on the results of batch tests, a tentative
flowsheet has been outlined that appears to have
several advantages over the process previously
used for the recovery of uranium from wet-process
acid. For example, (1) the synergistic extractant
is stable and can be recycled extensively, (2)
the uranium is extracted in its hexavalent state,
which avoids the expensive reduction step with
iron metal, (3) the uranium is easily stripped
from the solvent with solutions of ammonium
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carbonate, and (4) the product obtained is
relatively high-grade and is easy to handle in
subsequent purification processes.
The chief disadvantage of the new process is the
relatively high cost of the extractant. In process
applications:, it would be necessary, therefore,
to operate with a comparatively low loss of the
extracting solvent. Engineering studies will
be required to evaluate this and other operational
variables.
IV. Marketing Practices and Economics
A. Economics and Pricing
FERTILIZER SITUATION. Econ. Res. Serv., USDA, Rpt.
F5-7, Jan. 1977. 26pp.
U.S. fertilizer manufacturers' inventories during
the fall of 1976, although below year-earlier levels,
were generally abundant. Large increases are scheduled
in U.S. anhydrous Mfli capacity during 1977, and wet-
process H3PO4 capacity will increase slightly. If
production holds steady, supplies will be adequate
for 1-976-77 and prices paid by farmers should be steady
to lower. Mid-April 1976 prices for fertilizers were
as much as 30% below year-earlier levels. Fertilizer
use increased 15% to a record-high 49 million tons
in 1975-76. The opening of several new plants during
1977 should increase capacity by close to 3 million
tons by January 1, 1978. Domestic capacity to produce
wet-process acid fell by 300,000 tons during 1976
to about 8.7 million tons. Two new facilities are
scheduled to begin operation in 1977, bringing annual
U.S. production capacity close to 9.2 million tons.
The import-export picture was mixed during 1975-76,
as the world market for fertilizers softened. The
declared value of U.S. fertilizer exports declined
from over $1.6 billion in 1974-75 to slightly more
than $1.3 billion in 1975-76. International fertilizer
prices fell by as much as two-thirds between the third
quarter of 1974-75 and the end of the 1975-76
fertilizer year. The U.S. Agency for International
Development financed the export of 451,000 tons of
fertilizer in 1975-76, representing 8% of total U.S.
exports. World use of P2°5 fertilizers rose 4% to
an estimated 26.2 million tons in 1975-76. A further
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modest gain is expected in 1976-77. World production
capacity is expanding, and 1976-77 supply is estimated
at 33 million tons. World prices for phosphate
fertilizers are expected to be steady to lower in
1976-77.
FERTILIZER SUPPLY, EXPORTS TO BE MONITORED. Chem. Mkt.
Rep., Vol. 204, No. 22, Nov. 26, 1973. pp. 3, 19.
Department of Commerce last week announced
establishment of a system of monitoring exports,
domestic supply, and pricing of certain fertilizers.
The fertilizer monitoring system will provide timely
data on each company's production, inventories,
imports, shipments, foreign orders, and pricing for
ten basic classes of fertilizer materials. The
department said that the information is needed by
the department itself, as well as by the Cost of Living
Council, the Council of Economic Advisors, and other
interested agencies to determine whether there will
be an adeauate supply of fertilizer to meet the needs
of domestic commerce. Under the monitoring orogram,
producers and importers will submit reports monthly
and exporters will submit semimonthly. Initial reports
are to be compiled as of November 30, and submitted
within eight business days to Department of Commerce,
Office of Export Administration Renorting forms will
be available from the deoartment and its 43 district
offices.
CONGRESS THREATENS FERTILIZER EMBARGO. Fram Chemicals
, Vol. 137, No. 4, April 15, 1974.
Sometime this month the fertilizer industry will be
called before the House Committee on Banking and
Finance to explain why the U.S. should not impose
a ban on fertilizer exports. Five identical bills
(H.R. 13079-13082) have been introduced in the House
to "prohibit the exportation of fertilizer from the
United States until the Secretary of Agriculture
determines that an adequate domestic suonly of
fertilizer exists." Over 120 members of the House
are listed as sponsors, some of them from key
agricultural states.
The cries for embargo are the outgrowth of the greatest
demand for fertilizer in history. With farm prices
at all-time highs and some 50 million additional acres
brought back into production in the last two years,
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demand has far outstripped supply. USDA has pegged
the fertilizer shortfall for this crop season at an
optimistic 2 to 5%; most industry observers predict
it will be much closer to 10 to 15% despite the fact
that the industry is operating at peak capacity.
Through the first six months of the fertilizer year
(July-December), fertilizer output was up 7% over
the previous year, but disappearance into U.S. market
channels was up 14%.
Industry leaders are united in the belief that an
embargo would be destructive to U.S. interests, would
discourage further U.S. production expansion, and
would create chaos in U.S. and international markets.
ECONOMIC FACT SHEET 1976. Florida Phosphate Council,
Lakeland, Fla.
The direct and indirect econoinic effects of the Florida
phosphate industry for 1976 are summarized.
ENERGY USE AND ECONOMICS IN THE MANUFACTURE OF
FERTILIZER. J.L. Sherff. In Energy, _Agriculture and
Waste Management. Ann Arbor Sci. Publishers, 1975.
pp. 433-41.
The ^energy content of fertilizers, effects of energy
shortages on fertilizer availability and cost, and
alternatives are discussed. Anmonia requires the
most energy, because of its N component which is the
basis for almost all N fertilizers. Dependim on
the product, N fertilizers require 49-62 million
Btu/ton of N in their manufacture. Phosphate
fertilizers require 12-19 million ^tu/ton of PoOc
including the energy required to product the pnosohate
rock and S raw materials. Potash fertilizers require
about 6 million Ftu/ton of Fuels and electric
power constitute roughly 12% of the cost of fertilizer
manufacture. The manufacture of fertilizers in
1973 required the expenditure of $172 million for
fuels, largely natural gas, and $12 million for
electric power. The manufacture of phosphate
fertilizers required $63 million for fuels, and $25
million for electric power. The total use of fossil
fuels was 574 trillion Btu in 1973. The fertilizer
industry consumes 0.3% of the nation's electric power,
0.1% of the distillate and residual oil, and 2.4%
of the natural gas supply. Problems encountered in
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the processing of major fertilizer raw materials are
escalations in the price of gas and the cyclical nature
of the industry. With the exception of NH-,, the switch
to alternate fuels is inexpensive but manufacturers
will convert only by necessity.
FERTILIZER SHIPMENTS UP, PRICES FIRMING. Chem. Week
, Vol. 119, No. 11, Sept. 15, 1976. p. 33.
Fertilizer markets are strong, with fertilizer movement
up sharply from a yr ago and prices firming.
Producers' shipments in July were 32% higher than
a yr earlier. Shipments of nitrogen products rose
17%, phosphate shipments jumped 22% and potash
shipments soared 284%. The main reason: dealers are
rushing to replace their inventories, depleted by
extra-heavy demand last spring. Farm purchases are
somewhat less vigorous but still strong, with the
exception of some winter wheat areas that have been
hurt by dry weather. Producers' inventories, as a
result of the heavy shipments and a mere 2% increase
in output, were 13% below the levels of a yr ago.
Phosphate inventories at the end of July were 30%
below a yr earlier, and nitrogen product inventories
were down 11%. Potash inventories, which had been
very heavy, were trimmed to 1% above last year's
levels, as a temporary $0.10/unit cut in prices got
strong response from buyers. Potash prices moved
back up to $0.65/unit of standard material, f.o.b.
Saskatchewan, as of September 1. With that increase,
fertilizer prices are now firm across the board.
ECONOMIC SIGNIFICANCE OF THE FLORIDA PHOSPHATE INDUSTRY.
King Lee Wang, B.W. Klein, and A.F. Powell(Office
Economic Analysis, Mineral Supply, Washington, D.C.).
U.S. Bur. Mines I.C. 8653? 1974. 51 pp.
This Bureau of Mines study illustrates the economic
significance of the Florida phosphate industry to
the State and to the Nation. Environmental
considerations related to phosphate industry activity
are discussed briefly. Based on forecasts of Florida
phosphate production in 1975, and using 1972 dollars,
regional and national output value, income, and
employment created by the phosphate industry were
estimated for 1975. State and Federal government
tax revenues generated by the phosphate industry,
are also measured. Further, the concentrated impact
of the phosphate industry on certain Florida areas
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and on regional industries is examined. Finally,
the phosphate industry's importance to the U.S. balance
of payments, U.S. agricultural production, and the
Frasch sulfur industry is considered, in addition
to byproduct fluorine, and potential byproduct uranium
from fertilizer manufacturing.
ECONOMICS OF PHOSPHORIC ACID PROCESSES. J.G, Kronseder
Chem. Eng. Progress, Vol. 64, No. 9, Sept. 1968.
pp. 97-102.
Cost comparisons are given for five general processes
for the manufacture of wet-process H3PO4: the
dihydrate, anhydrite, semihydrate, 2-stage gypsum,
and semihydrate gypsum process. The capital costs
of each process for a battery limits 600 tons/day
p2°5 Plant producing 40% P2Or acid are : ($ million)
5.098, 4.85, 4.976, 5.2 and 5.83 respectively. The
H2S04 plant common to all the. processes would cost
$4.5 million. Production costs, assuming P205
recoveries of 89, 91, 93, 95, and 97% respectively
for each of the processes and S cost of $40/short
ton are: $91.78, $90.69, $88 .94, $87."38, and
$87,18/ton P0O5. For S cost of $50/short ton the
production costs are: $101.53, $100.23, $98.28,
%97.32, and $96.12/ton P205 respectively. The raw
material costs for each process are the same at
identical recoveries; for S at $40/short ton and 93%
recovery there are: rock ($10/ton) $34.40, H2S04
$45.04/ton, and defoamer ($0.15/lb) $0.75/ton. it
is concluded that the differences in capital costs
for other than the semihydrate gypsum process are
not great. Only the semihydrate gypsum process offers
any opportunity for significant improvements in
production costs and investment capital compared with
the dihydrate process.
WORLD PHOSPHATES ALLIANCE. Wall St. J. (East Edition)
, Vol. 188, No. 97, Nov. 16, 1976. p. 19. ~
Six countries that are large producers of phosphates
decided to set up a joint organization in a bid to
increase their control over fluctuations of the world
market. Plans for the organization were approved
by delegates from Morocco, Algeria, Tunisia, Togo,
Senegal, and Jordan. The organization would control
the production and marketing of the mineral and its
derivatives, such as phosphoric acid and
superphosphates. The conference was called to study
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joint steps to combat the current slump in the world
market for phosphates, a basic raw material used in
making fertilizers. Another major reason was the
U.S. decision to step up its exports of phosphates,
chiefly to Europe. The six nations control 60% of
the world's phosphate reserves. Morocco alone, with
its control of the former Spanash Sahara, which Morocco
acquired a yr ago, controls 70% of world deposits.
PHOSPHATE ROCK PRODUCER C*N'T AFFORD TO CUT PRICES.
Eur. Chem. Mews, Vol. 27, Mo. 715, Dec. 19-26, 1975.
p. 16 .
It is not economically feasible for the fertilizer
industry to expect the raw material producers to lower
their prices to help the industry through this
difficult period, according to the executive vice-
president of International Minerals & Chemicals (IMC).
The costs of producing phosphate, potash, and ammonia
will increase drastically over the next 4 years, and
if the raw material producer is to grow and expand
then even present prices and profits are inadequate
to justify additional investment. According to IMC
calculations, at the end of the crop yr 1974-75, world
buyers of phosphate rock had 12 million ton of
excessive inventory. Normal inventory, to operate
manufacturing Plants, is about 25 million tons, while
total rock inventory in buyers' warehouses was around
37 million ton, about 5 months' supply. However,
since June, buyers have been disposing of 1.5 million
ton/month more rock than they have been buying. At
this rate, inventories will be reduced to'minimum
levels in another 3 months, at which time normal buying
rates should be resumed.
MOROCCO SLASHES PHOSPHATE PRICE. Eur. Chem. News, Vol.
28, Mo. 720, Jan. 23, 1976. p. 4.
Morocco has finally succumbed to the pleas of the
depressed world fertilizer industry and made
substantial cuts in the price of its phosphate rock.
Effective January 1, 1976, prices have been slashed
29% dropping the list price of 75-77% "PL rock from
$68 to 543-50/ton fas Casablanca. Market prices
earlier stood at $58-60/ton after last quarter
discounting. The move means that Morocco's Office
Cherifien des Phosphates is now in open competition
with US rock producers. This position has now been
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completely reversed and OCP's prices fob Morocco are
$5/ton cheaper averaged across the grades than US
export prices ex-Tampa. OCP's competitive edge,
however, will be blunted by higher freight charges.
The point has nonetheless been taken and Phosrock
has wisely abandoned a 10% increase previously
scheduled for the beginning of this yr and is
maintaining a $55/ton price tag on its 74-75% BPL
material. Even Morocco's new official quotations
don't tell the full story and market prices have in
fact plunged lower. Official OCP list prices are
70-72% BPL rock $43/ton fas Safi, $46/ton fas
Casablanca, 75-77% BPL $48-50/ton fas Casablanca.
zQl other rock producers are understood to be following
the OCP price lead.
PHOSPHATE ROCK PRICING BY MOROCCO. Eur. Chem. News,
Vol. 27, No. 709, Oct. 31, 1975. p. 12.
Doubts are being expressed in Western Europe on the
firmness of Morocco's stance on phosphate rock prices.
Officially Morocco maintains that it will not move
from its $68/ton list price but there are reports
of individual discounts being negotiated by phosphate
rock consumers on the basis of increased rock off-
take. Discounts are said to be typically in the region
of $7-10/ton. Western European phosphate rock
requirements this yr are down by something like 30%
on estimates made at the end of last yr and discounts
are therefore being offered as an incentive for
consumers to take additional quantities of rock to
bring them nearer to original estimates. The discounts
however are not being generally offered.
AN ECONOMIC ASSESSMENT OF THE WORLD'S PHOSPHATE INDUSTRY,
WITH PARTICULAR EMPHASIS ON THE SOUTH AFRICAN INDUSTRY.
B.G. Russell. Johannesburg, South Africa:Dep.
Mines,Minerals Bureau, Republic South Africa, Rept.
No. 2, 1976. 79pp.
Important aspects of the phosphate industry in the
major producing and consuming countries are presented
and the South African industry is reviewed in detail.
The phosphate processing industry is largely
concentrated in countries that do not produce the
raw materials; this situation is expected to change
progressively, with the raw and processed commodities
coming increasingly from the same source. South
Africa's phosphate industry is expected to expand
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very substantially over the next 5 yr, when it will
become an important exporter of both raw and processed
phosphates. Phosphoric acid, which will be produced
in large amounts after 1977, is expected to meet stiff
competition on world markets; long term prospects
are favorable.
FLORIDA PHOSPHATE POCK PRICING. Chem. Week, Vol. 118.
No. 4, Jan. 23, 1976. p. 19.
The Phosphate Rock Export Assn. (PhGsrock) has trimmed
prices of phosphate rock, effective immediately. The
reductions are $6-7/mt, f.o.b. Tampa and Jacksonville,
Florida, or about: 14%. The new prices are firm for
at least 12 months, with freight equalization offered
where required by competition. Rock with 66% bone
phosphate of lime (BPL) content is cut to $30/mt,
68% material to $33, 70% to $37, 72% to $41, 75% to
$47. The move brings Phosrock prices into line with
competitive actions by African producers. Morocco
has offered discounts on customer-by-customer basis.
WORLD PHOSPHATE ROCK PRICING. Jpn. Chem. Week, Vol.
16, No. 812, Nov. 20, 1975. p. 1.
The phosphate rocks demand and supply position has
become dull and Morocco, a leading phosphate rocks
supplying country vying with Florida (US) in exports
of- phosphate rocks, intends to reduce the export price
to japan from next yr, while Florida phosphate rocks
suppliers have notified Japan of their decision to
raise the export price to Japan by an average 7.4%
beginning January 1976. Japan's compound fertilizer
industry has formally expressed its intention of
opposing the price hike, and has decided to carry
out a campaign against the mark-up in cooperation
with related trading firms in the industry.
DIAMMOHIUM PHOSPHATE PRICING. Chem. Mark. Rep., Vol,
2, No. 5, Feb. 2, 1976. p. 24.
Throughout recent months, a weak agricultural market
•has served to debilitate the price structure of
dianmonium phosphate (DAP). Industy sources report
that inventories for both feed and fertilizier grades
are higher than usual for this time of yr, and although
projections for 1976 look good little is happening
at present to alleviate current shaky market
conditions.
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UNITED STATES PHOSPHATE PRICES FIRM. Pert. Int.y No.
87, Sept. 1976. p.3.
The market for phosphate fertilizers firmed noticeably
in July with both domestic and exporting suppliers
issuing new price lists. The prices are slightly
higher than the latest Phoschem prices which quote
the same figures per ton, f.o.b. vessel, for delivery
through September. Phoschem's prices in the final
quarter of the yr are $105 per mt f.o.b. for granular
triple superphosphate and $140 per mt for diammonium
phosphate. Nominal phosphate capacity is well in excess
of current demand forecasts but the many closures
and reduced operating levels in the United States
have contributed towards a much lower production level,
with the result that prices have firmed. High hopes
of a good autumn season in the United States have
encouraged optimism over prices in the final quarter
of 1976, although this would anpear to be dependent
upon at least part of the idle caoacity regaining
inactive.
PRODUCTION OF PHOSPHORIC ACID VERSUS PRODUCTION OF
PHOSPHATE POCK CONCENTRATE FOP EXPORT. A.7*. Phillips.
Phosphorus and Potassium, Vol. 78, July-August 1975.
pp. 22-28.
The number of countries exploiting phosphate reserves
for exnort has increased during the last decade and
should continue to grow in the future. It is only
natural that a country that is or nlans to be in a
position to export phosphate rock should qive
consideration to upgrading this resource by nrocessing
the phosphate further to provide fertilizer or
fertilizer intermediates for export, since there are
many well-established reasons for creating such an
industry. The ouroose of this article is to discuss
by way of example, the Major factors to be considered
in studying the oossibility of producing wet-process
phosphoric acid for exnort.
Estimates made recently at TVA indicate that by 1980
world demand for phosphate fertilizers will nrobably
be about 31.2 million tons P2^5' with a range of 28.3-
34.1 million tons. Assuming that industrial uses
increase proportionately, demand increase between
1974 and 1980 will probably be about 31 million tons
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phosphate rock, possibly as much as 45 million tons.
Subtracting consumption growth in the United States-
which is unlikely to become a net importer-leaves
the expected increase of world trade in all forms
of phosphate equivalent to about 25 million tons of
phosphate rock, with a maximum of 35 million tons,
by 1980.
When investigating supply both the basic supply of
rock and the potential supply of phosphoric acid must
be considered. Adequate supplies of phosphate rock
for the world by 1980 seem assured. In fact,
projections indicate a supply increase by 1978 of
over 40 million tons relative to the 1974 level, with
75% of this increase arising in North Africa and the
United States. In addition, if the current high price
of phosphate -rock is maintained, a further expansion
of supply in those nations already exporting rock
and in many others where economics have heretofore
been unfavourable, can be expected by 1980.
A recent TVA study cites the estimated 1978 production
costs of a phosphoric acid plant is a developing
country as follows:
Phosphoric Acid: 600 t.p.d.P205 capacity
operating at 90% capacity
Total plant investment: $40,874,000
Working capital: $15,020,000
Raw materials Unit/tonne $/unit Cost,
product $/ton
Unground rock, ton 3.31 35 115.85
Sulphuric acid, ton 2.75 35 96.25
Sub-total 212.10
Fixed and variable costs
Cooling water, M gals 5.5 0.02 0.11
Electricity ,kVJh 3.30 0.015 4.95
Labour,man-hrs 0.51 5.62 2.87
Maintenance(5% TPI) 11.47
Taxes and insurance(2%TPI) 4.49
Depreciation15yrs) 15.30
Interest(10% of 1/2 TPI) 6.12
Overhead(100% of labour) 2.87
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Sub-total
Production cost Jyi* zZ
Interest on working capital 60.37
(10% of 1/2)
Total production cost at 0% return on equity 264 87
B. U.S. Supply and Demand
TRENDS IN UNITED STATES FERTILIZER CONSUMPTION.,
Phosphorus Potassium, No. 81, Jan.-Feb. 1976. np
34.
The United States is the world's largest producer
of both phosphate rock and phosphate fertilizer.
It was the second largest consumer (after the farmin
industry of the U.S.S.R.) in 1974-75. Since 1945 ^
there have been very few years in which the use of
phosphate fertilizers declined. The growth rate fv
1945 to 1974 averaged almost 4.5%/yr. United Stat m
farmers have recently adopted a more business-like63
attitude to the cost: price ratio. There are
independent variables that influence the demand fo
agricultural products. Fertilizer price movement *
will tend to follow those for farm outputs Some
of the variables are weather, pests, and governmenf
policy. Trends in consumption of ohosphates in th
United States by regions (nine regions) are analyzed
UNITED STATES FERTILIZE CONSUMPTION. Chem-. Mark. Rep.
, Vol. 210, No. 20, Nov. 15, 1976. p.4.
Record fertilizer use by U.S. farmers in 1975-76 was
influenced largely by both a return to adequate
supplies and lower cost. Fertilizer consumption jumped
15% to resume its annual upward trend. The rapid
increase in fertilizer use is a further indication
that farmers are aware of the relationship of good
soil fertility to maximum, profitable crop yields.
Even at today's lower grain prices, fertilizer use
remains an essential and profitable practice given
the current favorable grain-to-fertilizer price ratio.
Total nutrient content of fertilizers is now reported
at 42.2%, an increase from the yr-earlier level of
40.6%.
COMMERCIAL FERTILIZERS-CONSUMPTION IN THE UNITED STATES
YEAR ENDED JUNE 30/ 1976 (PRELIMINARY REPORT). U.S.D.A.
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Statistical Rep. Service, Crop Rep. Board, Washington
D.C., Nov. 1, 1976. 12 pp.
Consumption in the United States and Puerto Rico during
the yr ended June 30, 1976 was a record 48.9 million
tons, up 15% from the 42.5 million tons consumed during
the 1974-1975 fertilizer yr. This is 4% above the
previous record of 47.1 million tons consumed in fiscal
yr 1974. The five leading states in order of total
consumption and the change in consumption from the
previous yr were: California, up 7%; Illinois, up
16%; Iowa, up 22%; Texas, up 19%; and Indiana, up
26%. Primary nutrient content (N,P205, and K20) was
20.8 million tons, up 18% from a yr earlier. Nitrogen
consumption increased 20% to 10.3 million tons;
phosphate usage increased 16% to 5.2 million tons;
and potash, also "at 5.2 million tons was up 17%.
Consumption of mixed fertilizer containing two or
more primary plant nutrients was 22.9 million tons
during the 1976 fertilizer yr, up 11% from 1975.
The average analysis for mixed fertilizer was 10.53%
N, 19.27% phosphate, and 12.49% potash. The analysis
for the preceding yr was 10.17-18.00-12.49. The total
analysis of plant nutrients in mixed fertilizer
increased from 40.66% a yr earlier to 42.29 in 1976.
Secondary nutrients and micronutrients materials
increased from 1.9 million tons in 1975 to 2.2 million
tons in 1976.
UNITED STATES FERTILIZER SUPPLY-DEMAND. Chem. Hark.
Rep., Vol. 210, No. 25, Dec. 20, 1976. pp. 4,24.
Total US farm consumption of fertilizer will fall
to 20.4 million nutrient tons next yr., a 1.9% decline
from record levels set in 1976, according to Chase
Econometric Associates, Inc. Total tonnage in 1978
will increase to 21.3 million tons. Nitrogen demand
will decline 2.6% in 1977, while phosphate and potash
move down 1.6% and 0.9%, respectively. Demand in
1978 should pick up over the previous yr by 5.8% for
nitrogen, 3.3% for phosphates, and 5.5% in potash.
In spite of a decrease in demand, nitrogen prices
are expected to recover to 6-8% next spring, over
spring 1976, and then fall by 4-5% in 1978. Phosphates
and potash are-expected to move up 3-4% by next spring.
Exports of all fertilizers are now expected to climb
5-7% in both 1977 and 1978 as the world's economic
climate improves and major fertilizer importing
countries continue to expand their food production.
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Nitrogen will continue to be tight internationally,
while phosphate and potash world balances will remain
pretty much where they were in 1976. With nitrogen
pipelines empty, shipments will greatly increase in
1977 as producer stocks decline by 5%. Nitrogen
producers should be running at 82-84% of capacity
and imports will climb 4.5%. Phosphate producers
may be able to rid themselves of one-fifth of their
inventory next yr, and 46% by the end of 1978.
Production will increase to only 85-86% of capacity
over the same time. Capacity will increase 5% over
the next 2 yr. but it will not be absorbed by the
market. Although some outmoded plants will be closed
in 1977. Potash shipments from producers are expected
to start slowing in the spring as farm sales drop
below 1976 levels. US production is expected to run
at 85-86% of capacity over the next 2 yr, while Canada
averages 70-72%.
PHOSPHORIC ACID PRODUCTION IN THE UNITED STATES.
Engineering/Mining Journal, Vol. 17 6, No. 12, Dec. 19 75.
pp. 81-2.
A cluster of 12 wet process phosphoric acid plants
is located in central Florida, and another seven are
on the Gulf Coast in Texas, Louisiana, and Mississippi.
The Gulf Coast plants all use central Florida rock,
which is transported in the sane vessels used to shin
S to the Florida plants. In addition, there are a
number of plants in the West (which use western rock),
a few up the Mississippi River (which use central
Florida rock), and one plant each in northern Florida
and North Carolina. Total wet process nhosohoric
acid production capacity of the US is 9,1.60,000 tons
P2O5. Because of growing demand for fertilizers,
two new plants and a number of Plant expansions are
under construction. By 1976 total wet nrocess acid
capacity is projected to increase by more than 35%.
DEMAND FOR PHOSPHATES LAGS OTHFT? FE.RTILIZEPS. Chem.
Week, Vol. 120, No. 2, Jan. 12, 1977. ra.24. ~
November shipments of phosphate products in the U.S.,
excluding phosphate rock, were 16% lower than for
the same month of 1975, says the Fertilizer institute.
November potash shipments, on the other hand, rose
10% and nitrogen product shipments were un 3%. Total
shipments of all products except phosnhats rock were
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down 1%. Cumulative data for the first five months
of the 1976-77 year show nitrogen products up 8%,
phosphate up 2%, potash up 45%, and all products except
phosphate rock up 11%. Product inventories were
generally down 10% at the end of November. Phosphate
rock inventories, however, were still 42% higher than
a year earlier.
THE NONFARM MARKET. Lyn Prestwich and Marilyn Messerly.
Farm Chem., Vol. 139, No. 11, Nov. 1976. pp. 78-9,
82-3, 86-7, 90.
The nonfarm fertilizer market is a 2.4 + million ton
market worth $550 million at the manufacturer's level.
Home lawns and golf courses account for about 70%
of total nonfarft use. Other significant markets are
office parks, neighborhood payks, churches, high
schools, shopping centers, apartment complexes,
government buildings and grounds, universities,
memorial gardens, and highway rights of way. The
maVket is expected to grow at about 4% per yr. The
traditional channel of distribution-manufacturer to
distributor to consumer will yield to more direct
methods. Mass chain merchandisers will get more of
the do-it-yourself market, which in itself will yield
to the lawn service companies, particularly where
commercial buildings are concerned.
C. World Supply & Demand
WORLD FERTILIZER POSITION FORECAST. Chem. Mark. Rep.
, Vol. 209, No. 29, June 14, 1976. pp. 5,37.
Manufacturers of fertilizer materials will find at
the end of the current fertilizer yr that they will
have experienced the second-best marketing yr in
history. Sales will have measured out to between
44 million and 45 million tons, exceeded only by the
47 million tons s.old in 1973-74, according to the
president of the Fertilizer Institute. The nitrogen
fertilizer movement should be 10%, perhaps 15% higher
than last yr. Phosphate movement will be 5-7% higher
and potash use at least will hold its own with 1974-
75, or perhaps increase slightly. Another good year
should lie ahead because fertilizer continues to be
a vitally needed product in food and fiber production.
Nitrogen fettilizer inventories at year's end will
be low, customer demand should be strong with predicted
favorable grain prices and US and world economics
appear to be on the upswing.
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PHOSPHATE SUPPLY FORECAST. Eur. Chem. Hews, Vol. 29,
No. 7 65, Oct. 1, 19 76. p. 16.
Total North American phosphate consumption will
increase from its present level from around 5.5 million
ton/yr of P2°5' of phosphoric acid, to around
7 million ton by 1980, leaving the U.S. with a large
surplus of phosphates for export well into the 1980s,
according to the president of International Commodities
Export Company (ICEC). While there will continue
to be excess capacity and a surplus of P2O5 over fche
next 5 yr, ICEC does not expect this surplus to
continue into the 1980s, when there could actually
be some small localized shortages.
PHOSPHATE FERTILIZER SHORTAGE WORLDWIDE. Chem. Eng.
Hews, Vol. 52, No. 25, June 24, 1974. pp. 10-11.
The chairman of the Phosphate Rock Export Association
predicted a shortage for the next 2-3 vr with improved
supplies by 1977. European countries as well as most
of the developing countries are now dependent on the
U.S. for a source of phosphate. The communist
countries are fairly well supplied with Russia
producing approximately 21% of the world's supply
of nhosohate rock. Production of phosphate rock is
scheduled to increase approximately 50% on a world
wide basis between 1974 and 1978. Prices will" increase
because of the increased cost of production.
FERTILIZER SURPLUSES LIKELY BY 1980. Chem. Week, Vol.
119, No. 10, Sent. 8, 1976. p. 17.
New foreign capacity will almost certainly depress
exports of U.S. fertilizers to less-developed
countries, a British agricultural economist predicts.
The British Sulphur Ltd. (London) presented a forecast
of world ammonia capacity to top 100 million m.t./vr
by 1980, with significant surpluses in Eastern Europe
and the developing nations. Urea surpluses could
be especially troublesome because planned capacity
by 1980 in less-developed countries will be 19.2
million tons (N equivalent), while developed nations
will have 17.2 million-tons capacity. Finished
phosphate fertilizers are potentially even more
troublesome. Arab states will become formidable
phosphate suppliers. Last yr they exported 402,000
m.t. of phosphates (as P2°5» "forms). 3v 1980,
Arab states will have an exportable surplus of 1.7
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million m.t. In South Africa, the phosphoric acid
surplus could pass 300,000 m.t. while U.S. ohosphate
makers will generate 1.8 million-ton surplus.
DANGER IN LOWERING OF PHOSPHATE FERTILIZER USE. Chem.
Age(London), Vol. 113, Sept. 17, 1976. p.2.
A stern warning on the risks associated with the
current trend of cutting back in the consumption of
phosphate fertilizers in response to higher prices,
has come from Agricultural Sector chairman of Albright
& Wilson. He said that the effect of the increase
in the price of ohosnhate rock has been truly alarming.
This caused a serious cut-back in many countries.
For example, France reduced her consumption by 21.5%,
Ireland by 40%, United Kingdom by 25%, U.S. by 1?%,
and in many other countries the problem was also very
serious. This should serve to remind us how important
it is that we should take full advantage of the
supplies of phosphorus that are available to us.
FERTILISER EXPORT PLANT PLANNED. FeedstuffS, Vol. 45,
Mo. 34, Aug. 23, 19 76. P. 42.
The Jacksonville Port Authority has approved plans
to issue up to $50 million in tax-free bonds to build
a olant that would ship huge amounts of super
con'centrate fertilizer to the Soviet Union and to
import ammonia from the USSR. Hooker Chemical Co.,
a subsidiary of Occidental Petroleum of Los Angeles,
is to select a site for loading facilities that would
handle 90,000 tons of superphosphoric acid and 40,000
tons of dry fertilizer. The facility also will be
capable of receiving and storing 30,000 tons of
ammonia.
FERTILIZER EXPORT PLANT PLANNED. Feedstuffs, Vol. 48,
No. 34, Agu. 23, 19 76. p.42.
The Jacksonville Port Authority has approved plans
to issue up to $50 million in tax-free bonds to build
a'plant that would ship huge amounts of super
concentrate fertilizer to the Soviet Union and to
import ammonia from the USSR. Hooker Chemical Co.,
a subsidiary of Occidental Petroleum of Los Angeles,
is to select a site for loading facilities that would
handle 90,000 tons of superphosphoric acid and 40,000
tons of dry fertilizer. The facility also will be
capable of receiving and storing 30,000 tons of
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ammonia.
PHOSPHATE ROCK CAPACITY. Phosphorus Potassium No. 62
Nov.-Dec. 1972. pp. 3-5.
World phosphate rock production capacity in 1972
totalled 103 million tons/yr in terms of saleable
products. The actual level of output in 1972 is
expected to correspond to an overall level of capacity
utilization of 90%; however, there remain considerable
variations in the degree of employment of capacity
in individual producing countries. The effect of
the sharp increase in demand for phosphate rock in
1972 has been to force the largest and best established
producers to operate full out to cover the new level
of market requirements. Even the Florida phosphate
mining industry claims to have no surplus capacity
available with which to supply additional material
to export markets. According to the Fertilizer
Institute index, the average rate of capacity
employment in the United States phosphate mining
industry rose to 89% in first haif of 1972, compared
with 72% in the same period twelve months before.
Tbe additions to world phosphate mining capacity
totalled 4.9 million mt in 1972, with a further 5.2
million mt following in 1973. Most of these increases
are represented by developments in North Africa, such
as Morocco and Spanish Sahara, and in the U.S.S.R.
There have only been marginal changes in capacity
levels in the United States, while the growing interest
in the construction of new mines in Florida is unlikely
to result in effective capacity before 1975.
PHOSPHATE TRADE WITH RUSSIA MAY COMMENCE IN 1975. Fla.
J. Comm., Vol. 15, No. 6, June 1973. p. 18.
Occidental Petroleum Corporation plans still further
expansion of its Suwannee River mine complex in North
Florida to fulfill the requirements of its recently-
signed $8 billion chemical fertilizer agreement with
Russia. If no hitches develop, the trade will commence
no later than 1978, possibly as early as 1975.
Occidental Chairman has disclosed that negotiations
have been underway for Russia to take delivery of
about 100,000 tons of phosphates in 1975, about 400,000
tons in 1976, and about 600,000 tons in 1977 to get
the program started early. Plans are underway for
the expansion of a Florida chemical complex to increase
production of high-analysis fertilizers and
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Occidental's concentrated superphosphoric acid.
Shipment of super phosphoric acid produced at the
Suwannee River chemical complex will be made through
Jacksonville Bulk Terminals, another Occidental
subsidiary which now handles approximately 1,200,000
tons of cargo annually in domestic and international
trade. The agreement with Russia also provides that
Occidental and Bechtel Corporation of San Francisco
build four ammonia and urea plants in Russia and
receive a percentage of production as payment.
PHOSPHATE PRODUCTION DOWN IN NORTH AFRICA. J. Flour
Anim. Feed Milling, Vol. 157, No. 11, Nov. 1975 . p.21.
The market position in phosphate rock from Morocco
has been deteriorating steadily throughout 1975.
Moroccan production in the first half reached 8,044,000
mt, with deliveries slightly lower at 7,897,000 mt.
Overall, deliveries in the first half were down by
14% over the same period 1974, but in the second
quarter, deliveries were down by 27%. This position
is mirrored in the situations of other phosphate rock
producers, with the exception of the US, where the
market, although not flourishing, seems considerably
healthier. Tunisian production in the first half
was down by 6%, while deliveries were down by no less
than 34%. Production in Toga was down by 34% while
deliveries were down by 42%.
MORE UNITED STATES ROCK FOR FOREIGN MARKETS. Chem.
Week, Vol. 119, No. 23, Dec. 8, 1976. pp. 15-16.
Looking beyond the relatively steady growth of demand
in their domestic markets, U.S. producers of phosphate
rock see enough promise in overseas markets to justify
new mining and beneficiation projects that within
the 1975-1985 decade will enable them to increase
their combined output 75%, to 81 million tons. The
wave of expansions, which could easily soak up more
than $1 billion in new capital investments, is already
well advanced. Global competition is clearly on the
rise. Morocco, whose known phosphate rock reserves
exceed those of all other nations in toto, by 1980
is expected to boost its production capacity to 30
million tons/yr, up from its 1974 rating by 43%. At
the moment, phosphate rock and its various derivatives
are generally plentiful. The longer-term outlook
is another matter. It's dominated, say some market
analysts, by an inexorable rise in global demand,
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generated by a growing world population's unrelenting
quest for ever-greater quantities of higher-quality
food and fiber products from olant and animal crops
that cannot be grown without adequate amounts of
phosphorus. Foreign consumers of phos rock are keenly
interested in U.S. reserves, even though North African
mines represent a much closer source of supply. At
least five companies are in line to become new entrants
in phosphate mining.
FLORIDA PHOSPHATE ROCK PRODUCTION. Fla. J. Comm., Vol.
15, No. 1, Jan. 19 73. p. 1.
Occidental Chemical Company's phosphate mine near
Jasper, Florida will increase capacity of the mine
to approximately 3,000,000 tons of rock annually.
The move is related to negotiations with Soviet Russia
looking toward export of about .1 ,000,000 tons of
phosphate annually from Jacksonville to Russia. The
firm has disclosed plans for a barter arrangement
with Russia, taking urea and ammonia in payment for
the rock.
PHOSPHATE FERTILIZER DEMAND *7ILL STRENTHEN. Chem. Mark.
Rep. , Vol. 208 , No. 26, Dec. 29 , 1975. o. 19.
Producers are now gearini up for what is expected
to be a better-than-average yr for ohosphate fertilizer
movement both here and abroad- Although dealers are
still offering discounts on the list prices of various
producers materials in order to reduce excess
inventory, manufacturers claim that the price
undercutting will end soon. Analysts say that the
heart of this bright projection lies in the assumption
that farmers throughout the world will be willing
to pay the higher prices for phosphate fertilizer
materials because they have now realized that
phosphates are necessary if increased crop yields
are to be achieved. During the better part of 1975,
agricultural phosphate producers saw their product
inventories steadily rise because farmers refused
to buy any materials at the higher prices that
manufacturers had instituted around the first quarter
of the yr. Dealers reoort that stocks are moving
at a more rapid pace than last yr. Further, oroducers
claim that they are seeing an increased amount of
orders for phosphate fertilizer materials this season
as opposed to the preceding one. On world markets,
producers are equaily hor>eful. In the latter part
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of 1975, a rash of product orders coming from Eastern
Europe in particular has become evident. People in
the industry feel that before the end of the first
quarter of the yr, other markets will have increased
activity. Recently, the Phosphate Chemicals Export
Association, which handles fertilizer exports for
its eight member companies, reported a price increase
on its products that would become effective March
1, 1976.
PHOSPHATE ROCK PRODUCTION IN U.S.S.R. Mining Eng.,
Vol. 24, No. 12, Dec. 1972. pp. 54-6.
Three of the world's largest phosphate deposits are
located in the U.S.S.R. These have an estimated
reserve of 2600 million short tons of elemental P.
The phosphate operations are centered about the two
cities of Apatity and Kirovsk. Mining operations
center around Kirovsk with four mines, Korov, Yuksnor,
Tsentralny (Central), and Rasvumchorr, located within
four to six miles of town. Both open pit and
underground mining are practiced at most of the mines.
Traditionally, the Kola Peninsula has been the
U.S.S.R.'s major source of phosphate rock (apatite)
and indeed is one of the world's major phosphate
operations. Present production levels will increase
significantly as the U.S.S.R.'s demand for phosphate
grows over the next few yr. It is estimated that
by 1975, mining operations in the Korovsk region will
increase to provide 30 million tons of ore and 16
million tons of apatite concentrate. In addition
to shinning apatite concentrates, part of the mine
output is marketed unconcentrated and ground for direct
agricultural use. The concentrate is an important
export item for the U.S.S.R. economy and is shipped
through the port of Murmansk to Germany, Holland,
Belgium, and the United Kingdom.
PHOSPHATE-POTASH Miri'TI IM BRAZIL. Chem. Meek, Vol.
120, No. 7, Feb. 16, 1977. p. 31.
Look for Brazil's phosphate and potash imports to
drop sharply during the next 5 yr as two new mining
projects are developed by state oil and petrochemicals
company Petrobras. After a 3-yr struggle over
ownership of a 450-nillion-mt phosphate reserve in
Minas Serais state, the National Economic Development
Council has authorized Petrobras Fertilizantes to
take 40% of a $150-million mining venture there.
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Output of the new projeci by 1980 is estimated at
2 million tons/yr of phosphate concentrate. The
council also has given Petrobras the go-ahead to form
a mining subsidiary that will own 50% of a $30-million
potash mining project in Sergipe state. Government
mining officials say the ventures will eliminate
imports of both products and leave some potash
available for export.
PRODUCTION OF PHOSPHORIC ACID VERSUS PRODUCTION OF
PHOSPHATE ROCK CONCENTRATE FOR EXPORT. Phosphorus
Potassium, No. 78, July-Aug. 1975. pp. 22-8.
The number of countries exploiting phosphate reserves
for export has increased during the last decade and
should continue to grow in the future. It is only
natural that a country that is, or plans to be, in
a position to export phosphate rock should give
consideration to upgrading this resource by processing
the phosphate further to provide fertilizer or
fertilizer intermediates for export since there are
many well-established reasons for creating such an
industry. The major factors to be considered in
studying the possibility of producing wet-process
phosphoric acid for export are discussed. These
include the selection of the process, the suitability
of the phosphate rock, the source of the H2SO4, the
capital requirements, and the production costs.
Factors contributing to the world market potential
for the acid are also discussed. The status of supply
and demand, economic considerations, and national
political trends are considered.
WORLD NITROGEN FERTILIZER MARKET OUTLOOK. TVA Circular
Z-50, August 1974.
From the standpoint of the present and future worldwide
nitrogen market, the following conclusions can be
drawn.
1. Presently, there is a worldwide nitrogen shortage
caused by a lack of investment in plant facilities
during the recent period of oversupply. This shortage
will continue for the next 3 years, its severity
depending in part on feedstock availability, olant
operating rates, and the effect on demand of fertilizer
prices in relation to farm outnut price levels.
2. The industry is responding to the crisis by
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planning and constructing new production facilities.
Over 18 million tons of additional capacity has been
announced since the first cf the year; and additional
20 million tons are in preliminary planning stages;
and other plans are under consideration. Great
progress is being raade by the industry in its attempts
to meet the growing demand for nitrogen fertilizers.
3. While there will be a move toward a balanced market
by the late 1970's, the growth in demand for nitrogen
should continue to pressure supplies and more
production capacity may be needed by 1980 and beyond.
But, capacity additions are now getting close to the
point where oversupply could result once again if
the rate of new announcements should continue for
any length of time at the pace of the last few monts.
4. Plans are being made and alternative feedstock
sources investigated, indicating that the world
nitrogen fertilizer industry is willing to invest
in the growth potential of the nitrogen market and
will make every effort to meet the world's nitrogen
demands to ensure adequate food supplies for all.
NITROGEN, PHOSPHORUS, AND POTASSIUM SUPPLY-DEMAND.
Ceres, Vol. 9, No. 3, May-June 1976. p.11.
The total supply of fertilizers produced and available
in the world in 1974-75 amounted to 86.8 million tons,
an increase of 3.2% over the previous yr. The rate
of increase was much lower than the 1973-74 rate
increase (8.6%) and was unequally distributed.
Nitrogen had an increase of 4.3% and phosphate and
potash increased respectively 2.2 and 2.4% in 1974-
75. Consumption fell by 2.5% in relation to that
1973-74, which amounted to more than 86 million
tons. Nitrogen consumption showed a slight increase
(110,000 tons) with phosphate decreasing 1.2 million
tons and potash 923,000 tons. Consumption decreased
in the industrialized countries (North and Central
America, Europe, and Oceania), while the three
developing continents increased theirs. A table of
consumption-production of nitrogen, phosphorus,
potassium for 1974-75 by continents is given. The
highest utilization rate was by far in Europe, with
192 kg/ha as compared with 65 in North and Central
America. The volume of world trade in all fertilizers
amounted to 25.5 million tons representing
approximately 31.3% of world consumption.
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INTERNATIONAL TRADE IN PHOSPHATE ROCK. PRESENT AND
PROJECTED TO 1985. B.F. Buie, G.L. Daugherty, and Allen
T. Cole. U.S. Bureau of Mines OFR 67-76, Dec. 1975.
127p.
World demand for P2O5 is projected to 1985 on the
assumption that demand will increase at the same rate
as the gross domestic product. The anticipated growth
rate is 6% per annum. The forecast of world demand
for P2O5 *-n 1985 is 66.59 million tons. The three
major producing countries in the past five years have
been the U.S., U.S.S.R., and Morocco, in that order.
The same countries,in the same order, are expected
to be the leading producers in 1985, and to be
producing more than 70% of the world supply. The
indicated world reserves of phosphate rock are more
than adequate to support the forecast production to
beyond 1985. Discovery of additional reserves is
expected to result from additional exploration and
development. A section on demand for fertilizer P
2O5 is included.
V. Laws and Regulations
FINAL GUIDELINE DOCUMENT; CONTROL OF FLUORIDE EMISSIONS
FROM EXISTING PHOSPHATE FERTILIZER PLANTS. U.S.
Environmental Protection Agency, Report No. EPA 450/2-
77-005, March 1977.
This guideline document provides a brief description
of the phosphate fertilizer industry, the five
manufacturing categories for which fluoride emission
guidelines are established, and the nature and source
of fluoride emissions. Also, information is provided
regarding the effects of airborne fluorides on health,
crops, and animals.
Emphasis has been placed on the technical and economic
evaluation of control techniques that are effective
in reducing particulate and gaseous fluoride emissions,
with particular emphasis on retrofitting existing
plants. The cost basis for adoption of State standards
based on the emission guidelines is developed by
engineering cost estimates on a hypothetical phosphate
fertilizer plant complex where assumed mediocre
controls are replaced with controls based on the
emission guidelines.
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The emission guidelines and the control equipment
on which they are based are discussed. The
environmental assessment of the emission guidelines
is presented and discussed.
Fluoride emissions from phosphate fertilizer plants
have been determined to be welfare-related [i.e. no
demonstrated impact upon public health for purposes
of section 111(d)]. Fluorides do, however, cause
damage to livestock and vegetation in the immediate
vicinity of fertilizer plants. Ingestion of fluorides
by livestock from hay and forage causes bone lesions,
lameness and impairment of appetite that can result
in decreased weight gain or diminished milk yield.
It can also affect developing teeth in young animals,
causing more or less severe abnormalities in permanent
teeth. Exposure of plants to atmospheric fluorides
can result in accumulation, foliar lesions, and
alteration in plant development, growth, and yield.
Good control of fluoride emissions from phosphate
fertilizer manufacturing operations is achievable
by water scrubbers which are properly designed,
operated, and maintained. The most satisfactory
scrubber for general use is the spray crossflow packed
scrubber. Other scrubbers, such as the venturi and
the cyclonic spray tower can give satisfactory results
when used in series. One design involves a venturi
ahead of, and integral with, the scrubber.
A description of the performance of water scrubbers
in fluoride emission control is given. The industry-
wide range of control is given by a variety of
scrubbers and is discussed.
The scrubber data associated with best control
technology were obtained from EPA sponsored tests
conducted during the development of Standards of
Performance for Mew Stationary Sources. Most of the
scrubbers tested were the spray crossflow packed type,
but a few venturi were tested.
Emission guidelines for existing phosphate fertilizer
manufacturing facilities for control of fluoride
emissions are as follows:
FLUORIDE EMISSION GUIDELINES FOR EXISTING
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PHOSPHATE FERTILIZER MANUFACTURING PLANTS
Process Source
of Fluorides
of P2O5 input
Emission Guidelines
Total Fluorides - Weight per unit
gAg
lbs/ton
Wet-Process Phos-
phoric Acid
Superphosphoric Acid
Diammonium Phosphate
Triple Superphosphate
0.01
0.010
0.03
0.1
0.02
0.01
0.06
0.2
(ROP)
Granular Triple
Superphosphate
0.1
g/hr kilogram
0.2
lbs/hr ton
5 x 10"
Granular Triple
2.5 x 10
^Superphosphate Storage
hese denominator units are in terms of P2O5 stored.
The SPNSS are identical to the above emission
guidelines for existing sources.
PHOSPHATE MANUFACTURING POINT SOURCE CATEGORY:
PROPOSED PERFORMANCE AND PRETRF.ATMENT STANDARDS.
~EPA (401 M St. SW, Wash., DC 20460), FEDERAL
REGISTER, 40(18):4110-4113, Jan. 27, 1975.
Pretreatment standards for existing sources are no
limitation for BODc, total suspended solids (TSS),
and pH; 70 mg/1 total P; and 30 mg/1 fluoride (F~)
for defluorinated PO4""3 rock and defluorinated H^PO
a. The performance standards for new sources are
70 mg/1 total P, 30 mg/1 F~, and 50 mg/1 TSS' and the
pretreatment standards are no limitation for BOD^,
TSS, and pH; 70 mg/1 total P; and 30 mg/1 F~. For
the sodium phosphates subcategory, the pretreatment
standard for existing sources is no limitation for
B0D5, TSS, and pH; 0.80 kg/kkg total P; and 0.30 kg/kkg
"F . The performance and pretreatment standards for
new sources are 0.35 kg/kkg TSS, 0.56 kg/kkg total
P, 0.21 kg/kkg F~, and pH 6-9? and no limitation for
BODg, TSS, and pH, 0.80 kg/kkg total P, and 0.30 kg/kkg
F~, respectively. The regulations aonly to sources
discharging into publicly owned treatment works.
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CONTROL OF FLUORIDE EMISSIONS FROM EXISTING PHOSPHATE
FERTILIZER PLANTS, DRAFT DOCUMENT. U.S. EPA, Research
Triangle Park, North Carolina: Environmental Protection
Agency; Apr. 1976. 239 pp.
The U.S. Environmental Protection Agency is required
under 40 CFR Part 60 to publish a guideline document
for development of State emission standards after
promulgating any standard of performance for a
designated pollutant. Standards of performance
limiting emissions of F from new and modified phosphate
fertilizer plants were promulgated on August 6, 1975.
This draft document includes the following information:
(1) Emission guidelines and times for compliance;
(2) A brief description of the phosphate fertilizer
industry, the five manufacturing categories for which
emission guidelines are established, and the nature
and source of F^emissions; (3) Information regarding
the effects of airborne F on health, crops, and
animals? and (4) Assessments of the environmental,
economic, and energy impacts of the emission
guidelines. The final document will be published
after receipt and consideration of public comments.
UNITED STATES PHOSPHATE INDUSTRY THREATENED. Chem.
Mark. Rep., Vol. 209, No. 11, Mar. 15, 1976. pp. 7,24.
The fertilizer industry is concerned that amendments
to the Clean Air Act now being drafted by the Senate
Public Works Committee may lessen this nation's ability
to meet its phosphate needs from its own reserves
and thereby become more dependent upon foreign sources.
The amendment seeks to preserve the existing air
quality in areas where little or no industry is already
located. It proposes to do this through a complicated
classification system that would trigger curbs being
placed on further expansion of mines or plant sitings
when an arbitrary increment or range of any pollutant
is reached. For certain areas of Florida, North
Carolina, Idaho, and Montana, it could mean that the
phosphate reserves in those areas could never be fully
developed. This amendment could well make American
farmers dependent on foreign sources for phosphate
fertilizer according to the president of the Fertilizer
Institute.
PHOSPHATE FERTILIZER INDUSTRY: PROPOSED PERFORMANCE
STANDARDS FOR NEW STATIONARY SOURCES. FEDERAL REGISTER,
Vol. 39, No. 205:37601-37607, Oct. 22, 1974.
127
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Performance standards are proposed for wet-process
phosphoric acid plants, super-phosphoric acid plants,
diammonium phosphate plants, triple superphosphate
plants, and granular triple superphosphate storage
facilities. The text of the proposed regulations
is provided and covers fluoride standards, monitoring
of operations, test methods and procedures definitions,
and applicability and designation of the affected
facility. The standards will require installation
of high efficiency gas scrubbers.
PHOSPHATE MANUFACTURING POINT SOURCE CATEGORY: PROPOSED
PERFORMANCE AND PRETREATMENT STANDARDS. FEDERAL
REGISTER, Vol. 40, No. 18: 4110-4113, Jan. 27, 1975.
Effluent pretreatment standards for existing sources
and performance and pretreatment standards for new
sources are described for the sub-categories of
defluorinated phosphate (PO^-3) rock, defluorinated
(F~) for defluorinated PO* rock and defluorinated
H3PG4 performance standards for new sources are 70
mg/1 total P, 30 mg/1 F~, and 50 mg/1 TSS and the
pretreatment standards are no limitation for BOD5,
TSS, and pH; 70 mg/1 total P; and 30 mg/1 F~. For
the sodium phosphates subcategory, the pretreatment
standard for existing sources is no limitation for
BOD5, TSS, and pH; 0.80 kg/kkg total P; and 0.30 kg/kkg
F~. The performance and pretreatment standards for
new sources are 0.35 kg/kkg TSS, 0.56 kg/kkg total
P, 0.21 kg/kkg F~, and pH 6-9; and no limitation for
BOD5, TSS and pH, 0.80 kg/kkg total P, and 0.30 kg/kkg
F~, respectively. The regulations apply to sources
discharging into publicly owned treatment works.
MANUFACTURING POINT SOURCE CATEGORY: EFFLUENT GUIDELINES
AND STANDARDS. FEDERAL REGISTER, 40(18): 4101-4109,
Jan. 27, 1975.
Effluent reduction guidelines and controls are
described for the sub-categories of defluorinated
phosphate (P04~3) rock, defluorinated phosphoric acid
(H3PO4) and sodium phosphates. The limitations are
based on control technology currently available and
economically achievable. The analyses of waste
characteristics and sources for each subcategory are
described. Treatment methods and management procedures
are included for the cooling pond system and fluoride
(F~), P04~3, and sulfuric acid contaminants.
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Calculations are presented for determining the
permissable vol of nrocess waste water discharge
according to surface area impoundment and precipitation
containment. The limitations prohibit the discharge
of process waste water pollutants into navigable
waters. The total P,F~, and total suspended solids
(TS5) limitations are 70 mg/1, 30 nq/1, and 50 mg/1,
respectively, for the defluorinated PO^"^ rock and
defiuorinated H3PO4 subcategories. ^or the sodium
phosphates subcategory, the permissible discharges
after application of the technology currently available
are 0.50 kg/kkg TSS, 0.80 kg/kkg total, and 0.30 kg/kk*g
F~. Limitations based on technoloy economically
achievable are 0.35 kg/kkg TS3 0.56 kg/kkg total P,
and 0.21 kg/kkg F~.
BACKGROUND INFORMATION FOR STANDARDS OF PERFORMANCE:
PHOSPHATE FERTILIZER INDUSTRY. Volume 2: Test Data
Summary. Environmental Protection Agency, Office of
air Quality Planning and Standards Rept. No: EPA-450/2-
74-019b, Oct 74. 63pp.
This document provides background information on the
derivation of the Standards of performance for the
phosphate fertilizer industry. Volume 2 presents
summaries of the emission testing data cited in Volume
1. The summaries are concerned principally with tests
for 'fluorides and visible emissions, but also describe
the facilities, characteristics of the exhaust gas
streams, and conditions of operation.
BACKGROUND INFORMATION FOR STANDARDS OF PERFORMANCE:
PHOSPHATE FERTILISER INDUSTRY. VOLUME 1. PROPOSED
STANDARDS. Environmental Protection Agency, Office
of Air Quality Planning and Standards. Rept. No. EPA
450/2-74-019a, Oct. 1974. 140 pp.
This document provides background information on the
derivation of the standards of performance for the
phosphate fertilizer industry. Volume 1 provides
a general description of the facilities for which
standards are proposed and provides the rationale
for the proposed standards of performance. Included
is an analysis of the economic impact of the standards
on the industry. The proposed standards require
control at a level typical of well controlled existing
plants and attainable with existing technology. To
determine these levels, extensive on-site
investigations were conducted, and design factors,
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maintenance practice, available test data, and the
character of emissions were considered.
FERTILIZER MANUFACTURINO POINT SOURCE CATEGORY-EFFLUENT
GUIDELINES AND STANDARDS AND PROPOSED LIMITATIONS.
Federal Register, Vol. 39, No 68, Part III, April 8,
1974, pp. 12832-12844.
The purpose of this notice is to establish final
effluent limitations guidelines for existing sources
and standards of performance and nretreatment standards
for new sources in the fertilizer manufacturing
category of point sources, by amending 40 CFR Chapter
1, Subchapter n, to add a new part 418. Subcategories
regulated include: phosohate, ammonia, urea, ammonium
nitrate, and nitric acid. Limitations guidelines
are established representing the degree of effluent
reduction attainable by the application of the best
practicable control technology currently available
and economically achievable. Additionally, the
rnvironmental Protection Agency simultaneously proposes
a separate provision stating the application of the
limitations and standards to users of publicly-owned
treatment works which are subject to pretreatment
standards under the Federal Water Pollution Control
Act. Notice is given of proposed regulations
concerning the application of effluent limitations
guidelines for existing sources to pretreatment
standards for incompatible pollutants.
FERTILISER MANUFACTURING POINT SOURCE CATEGORY, EFFLUENT
LIMITATIONS AND GUIDELINES FOR EXISTING SOURCES AND
STANDARDS FOR NEW SOURCES FOR THE PHOSPHATE SUE-CATEGORY.
Federal Register, Vol. 40, No. 152, August 5, 1975,
on. 33052-54.
Pursuant to the authority of the Federal Water
Pollution Control Act, notice is given that the
Environmental Protection Agency (EPA) has proposed
to amend Subpart A of the Phosphate Subcategory. After
due consideration of phosphate fertilizer
manufacturers' claims, the EPA believes that the
allowance for discharge from a water impoundment due
to rainfall events can be restated so as to make its
application less cumbersome and more easily understood.
Additionally, the EPA concurs that in some situations
it may be appropriate to allow some discharge from
the facility due to leaks and spills which are
otherwise unavoidable. The agency believes, however,
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that any allowance for such discharge must require
prompt management attention to and correction of the
leaks and spills. The amount of pollutants discharged
by facilities affected by this subpart should not
be substantially altered by this change in regulatory
language, nor is there likelihood of any significant
effect on the energy necessary for pollution control
or any other non-water quality related environemntal
impacts.
FERTILIZER MANUFACTURING POINT SOURCE CATEGORY. EFFLUENT
GUIDELINES AMD STANDARDS. Federal Reqister, Vol. 40,
No. 9, Jan. 14, 1975, pp. 2650-3.
Regulations are promulgated under the Federal Water
Pollution Control Act limiting (as applicable) BOD
c, total suspended solids, pH, NH3, nitrate, and total
P in the effluent from (NH^J^SO^, and mixed and blend
fertilizer prodn. subcategories.
EFFLUENT GUIDELINES AND STANDARDS. FERTILIZER
MANUFACTURING POINT SOURCE CATEGORY. PHOSPHATE, AMMONIA
UREA, AMMONIUM NITRATE, AND NITRIC ACID SUBCATEGORIES.
Federal Reqister, Vol. 39, No. 68, Apr. 8, 1974, pp.
12833-41.
Regulations are promulgated under the Federal Water
Pollution Control Act limiting (as applicable) P,
F, suspended solids, pH, NH3, org. n and nitrate in
the effluent of the title industries.
SPECIFICITY REQUIRED IN MINERAL LEASES GRANTED BY STATE
AGENCIES. Florida Laws, Ch 69-239, 1969 amending Fla
Stat Sec 253.45, pp. 942-943.
The trustees of the Internal Improvement Trust Fund,
and any other administrative ageney having title to
or control over any state owned lands, may sell or
lease any water, phosphate, soils, timber or minerals
in any of the lands other than hard-surfaced beaches
used for recreation and certain areas contiguous
thereto. The state agencies authorized to grant leases
shall specify in each lease the particular minerals
the lessee is permitted to drill or mine and the manner
in which the same may be extracted.
DEVELOPMENT DOCUMENT FOR EFFLUENT LIMITATIONS GUIDELINES
AND NEW SOURCE PERFORMANCE STANDARDS FOR THE BASIC
131
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FERTILIZERS CHEMICALS SEGMENT OF THE FERTILIZER
MANUFACTURING POINT SOURCE CATEGORY. Environmental
Protection Agency, Effluent Guidelines Div., E.E.
Martin.
Findings are presented of an extensive study of the
fertilizer industry for the purpose of developing
effluent limitation guidelines and standards of
performance and pretreatment standards. The fertilizer
industry is divided into five categories for more
meaningful separation and division of waste water
treatment and development of effluent guidelines.
These subcategories are phosphate, ammonia, urea,
ammonium nitrate, and nitric acid products. The
phosphate subcategory includes all ancillary operations
necessary for phosphate production. Effluent
guidelines for best practicable control technology
currently available, best available technology
economically achievable, and new source performance
standards are recommended for each category.
Manufacturing processes, wastes, and waste treatment
methods and their costs are discussed.
LEGAL ASPECTS OF PHOSPHATE MINING IN NORTH CAROLINA.
M.A. Almond. Sea Grant Publication UNC-SG-75-05, Feb.
1975, 29p.
The removal of phosphates from beneath navigable
waters in >!orth Carolina may produce adverse effects
upon marine life adjacent to the operation. On the
other hand, the phosphate is critically needed to
provide fertilizer to increase crop yields in a hungry
world. The pertinent state statutes and legal thinking
likely to be used in the administrative or legal
solution of this problem are analyzed. The on-land
phosohats mining orocess can cause environmental
problems in three areas: air pollution, land
reclamation, and groundwater. Underwater mining could
also cause major problems, such as salt water
intrusion, eutrophication, and irreparable damage
to the state's shrimp industry. Several legal remedies
are explored that might insure that the future
development of phosphate mining is consistent with
the preservation of estuarine resources. These
remedies are governmental regulations, private
remedies, contractual remedies, and the good faith
of the mining industry. Any such solutions must depend
in large part on the presence and spirit of one
corporation, Texasgulf, Inc., mainly because Texasgulf
132
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is at present the only company mining phosphate in
the state.
ECONOMIC ANALYSIS OF PROPOSED EFFLUENT GUIDELINES.
INDUSTRIAL PHOSPHATE INDUSTRY. Arthur D. Little Inc.,
Cambridge, Mass., Environmental Protection Agency,
Washington, D.C., Nov. 19 74.
An initial analysis was made of the economic impact
of proposed water effluent guidelines upon certain
products in the industrial phosphate industry. This
analysis was based on abatement cost data supplied
by the EPA. The products covered included phosphorous,
phosphoric acid produced from phosphorous, and
anhydrous phosphorous derivatives, and certain
derivatives of phosphoric acid but not including
fertilizers. The effluent guideline development
document supplying the abatement costs used in this
analysis indicated that zero discharge was a practical
goal and that the cost of achieving zero discharge
did not exceed 1.6% of the selling price of any of
the products studied. On the basis of these costs,
it was concluded that there would be no significant
economic impact on the products studied.
ECONOMIC ANALYSIS OF EFFLUENT GUIDELINES: NONFERTILIZER
PHOSPHATE MANUFACTURING INDUSTRY. PHASE II. Milton
L. David, C. Clyde Jones, and J.M. Malk. Development
Planning and Research Associates, Inc., Manhattan, Kans.,
Environmental Protection Agency, Washington, D.C., Mar.
1976. 131 pp.
This study of nonfertilizer phosphate manufacturing
industry study, SIC 2819 and 2874, specifically
involved three segments—4 defluorinated phosphate
rock (DFP plants, 11 defluorinated wet phosphoric
acid plants and 1 sodium tripolyphosphate (STPP) plant.
Most of the plants are reasonably profitable. Pricing
of these products is complex in that their demand
is derived, i.e. feed phosphates, liquid fertilizers,
soaps and detergents. Feed phosphates and liquid
fertilizer markets together are expected to grow at
8 to 12 percent per annum. STPP use is declining.
Because of the amount of in-place pollution control
technology, direct pass-on of control costs is not
expected. The 4 DFP plants currently meet control
requirements-and should not be impacted. Three
defluorinated acid plants may close due to pollution
control regulations although one of these may close
133
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under baseline conditions. The STPP plant may close
in face of impending pollution control guidelines.
DEVELOPMENT DOCUMENT FOR EFFLUENT LIMITATIONS GUIDELINES
AND NEW SOURCE PERFORMANCE STANDARDS FOR THE PHOSPHORUS
DERIVED CHEMICALS SEGMENT OF THE PHOSPHATE MANUFACTURING
POINT SOURCE CATEGORY. Elwood E. Martin. Environmental
Protection Agency, Washington, D.C.., Effluent Guidelines
Div., Jan. 1974. EPA Rpt. No. 440/l-74-006a. 158 pp.
A study was made of the phosphate manufacturing point
source category for the purpose of developing effluent
limitations guidelines, Federal standards of
performance, and pretreatment standards for the
industry. For the purpose of this study, the phosphate
manufacturing industry was defined as the manufacture
of the following chemicals: Phosphorus (and by-product
ferrophosphorus), phosphoric acid (dry process only),
phosphorus pentoxide, phosphorus pentasulfide,
phosphorus trichloride, phosphorus oxychloride, sodium
tripolyphosphate and the calcium phosphates. Effluent
limitations guidelines were developed as a result
of this study, defining the degree of effluent
reduction attainable through the application of the
best practicable control technology currently available
and the best available technology economically
achievable. The standards of performance for new
sources were also defined. Processes, wastes, and
costs are also discussed.
General
WORLD GUIDE TO POLLUTION CONTROL IN THE FERTILIZER
INDUSTRY. British Sulphur Corp. Ltd., London, 1975.
125 pp.
A listing by country is given of companies providing
design, engineering, and construction of processes
for treating gaseous and liquid effluents and solid
wastes from fertilizer plants and related facilities.
Included is a listing of fabricators and suppliers
of equipment for these processes. The listed companies
are also indexed by processes on items of equipment
offered. Governmental agencies and consultancy
services associated with pollution control are
included. This guide consists of more than 400 entries
from 24 countries.
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A STUDY ON THE EFFLUENT DISPOSAL OF SUPERPHOSPHATE
FERTILIZER FACTORY. H.C. Arora. Indian Journal of
Environmental Health, Vol 16, No. 2, Aprl 1974. pp.
140-150.
Existing waste water treatment units of a super
phosphate fertilizer factory are described. The
effluent quality is analyzed and modifications are
proposed for improvements in the quality of the final
effluent. Use of the waste containing hydrogen
fluoride for the manufacture of fluosilicic acid (an
insecticide) or for further conversion to sodium or
magnesium silico fluoride (a preservative for portland
cement surfaces) is suggested.
NEW SULFURIC ACID CAPACITY IN FLORIDA-PHOSPHATE
INDUSTRY'S PLANNING PROBLEMS ARE SULFUR INDUSTRY PROBLEMS
TOO. Sulphur , No. 123, Mar.-Apr. 1976. pp. 20-4.
The close relationship between the Florida-North
Carolina phosphate industry and its sulfur suppliers
has facilitated the orderly planning of linked capacity
developments. The ease with which sulfur and rock
can be shipped, either by barge or larger vessel,
between Gulf Frasch sulfur producing areas and Florida-
North Carolina has led in recent years to a
considerable degree of vertical integration. The
development of highly specialized engineering services
has contributed to the efficiency with which capacity
developments have been realized. The producers have
been less successful in matching of related sulfur-
phosphate capacity development to total world market
demand. The status of the various expansion plans
which have been announced since 1972 for sulfur-
phosphate industry is reviewed.
NITROGEN AND PHOSPHORUS: FOOD PRODUCTION, WASTE, AND
THE ENVIRONMENT. K.S. Porter, Editor. Ann Arbor,
Michigan: Ann Arbor Sci. Publ. Inc., 1975. 372pp.
The studies described in this report deal with the
issues of maintaining agricultural efficiency and
protecting the environment. There are eight sections
to the report: (1) N and P in the environment, (2)
the response of lakes to P, (3) the influence of human
activity on the export of N and NO3 from Fall Creek,
(4) flows of N and P on land, (5) economic analysis
of reducing P losses from agricultural production,
(5) animal waste management with nutrient control,
135
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(7) sociological investigations at three watersheds,
and (8) assessment and management of N and P. Each
section is the collaborative result of several authors
in different professional disciplines.
INORGANIC FERTILIZER AND PHOSPHATE MINING INDUSTRIES—
WATER POLLUTION AND CONTROL. EPA-WQO-12020-FPD-09/71,
Sept. 1971. 228pp.
A state-of-the-art survey was made of the water
pollution problems which result form the production
of inorganic fertilizers and phosphate rock.
Information required to complete the study was obtained
through an extensive literature search, questionnaires
sent to the major fertilizer producers, and visits
to selected production plants. Ninety eight plants
representing thirty three different companies were
surveyed. Productic^n figures since 1940 and estimates
of production through 1980 were accumulated for
phosphate rock and the major fertilizer products.
The specific production operations which are the
principal generators of contaminated waste waters
were identified, and the waste water volumes and
compositions for each operation were determined
wherever possible. The capability of current
technology to treat and control the contaminated waste
waters generated by the fertilizer industry was
evaluated. Problem areas where additional research
and development effort is needed to provide adequate
control of waste water discharge were identified.
PREVENTION OF SURFACE WATER CONTAMINATION AND AIR
POLLUTION BY FLUORINE COMPOUNDS FROM PHOSPHATE PLANTS.
Rufus G. Hartig. U.S.Patent 3,642,438 (CI. 23/153;
C 01b), Feb. 15, 1972, Appl. 816,206, Apr. 15, 1969.
5 PP..
Combined waste gas streams from phosphate rock
processing, contg. HF, SiF4, H20 vapor, S02, and
phosphate dusts, are prescrubbed with recirculated
aq. liquor contg. Si02 and "25% HoSiFg. The SiF4
is not absorbed and leaves with tne orfgases. The
HF reacts with the Si02, forming H2SiFg which decomps.
to SiF4 vapor. The gases are then scrubbed with an
aq. slurry contg. excess NaF which reacts with residual
HF to ppt. NaHF2 and with SiF4 to ppt. Na2SiF6. The
scrubber liquor is filtered, and the filter cake is
dried and heated to 600°F which decomps. the NaHF2
to form NaF and gaseous HF which can be removed as
136
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product or recycled to the prescrubber. The solids,
contg. NaF and Na^SiFg, are heated to 1300°F whereby
Na2SiFg is decompa. to form NaF and gaseous SiF*.
The NaF is recycled to the scrubber liquor. The gases
are scrubbed with water to prep, a soln. contg. H2
SiFg and pptd. Si02. The Si02 is filtered off and
a portion is recycled to the prescrubber liquor.
The filtrate consists of a 15-25% H2SiFg soln. which
is removed as product.
FERTILIZER FIRM GETS REQUIRED PERMIT FOR PHOSPHATE ROCK
MINING. Chem. Mark. Rep., Vol. 211, No. 6, Feb. 7,
1977. p. 28.
Beker Industries Corporation says that the Florida
Environmental Regulation Commission has aporoved the
application for a permit to construct an industrial
waste water facility in connection with Beker1s
proposed phosphate rock raining operation in Manatee
County, Florida. This permit is one of the key
requirements to enable ^eker to construct its proposed
phosphate rock mining facility. The company says
it is vigorously pursuing the applications already
made to obtain the other needed permits.
World fertilizer atlas, fifth edition. -The British
Sulphur Corp. Ltd., London, 1976. 108 pp.
Fertlizer plants throughout the world are listed by
country and shown on maps with the capacity, types
of products, and planned expansions supplemented by
statistical data on production, consumption, and trade
in the three major nutrients; information is provided
also on the major crops, total and cultivated land
area, population, and gross national product.
FLORIDA PHOSPHATE LANDS. Federal Register, Vol. 41,
No. 123, June 24, 1976. pp. 26066-8.
/
Interim recommendations are provided for the
minimization of health risk to individuals building
and occupying structures on reclaimed phosphate lands
that may contain elevated concentrations of radon
daughters.
DEVELOPMENT DOCUMENT FOR PROPOSED EFFLUENT LIMITATIONS,
GUIDELINES, AND NEW SOURCE PERFORMANCE STANDARDS FOR
THE FORMULATED FERTILIZER : SEGMENT OF THE FERTILIZER
MANUFACTURING POINT SOURCE CATEGORY. EPA Report No.
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440/1-74/042; Sept. 1974. 66pp.
This document presents the findings of an in depth
technical study (phase II) conducted by Davy Powergas
Inc. on fertilizer processes.
EFFLUENT GUIDELINES AND STANDARDS, PHOSPHATE
MANUFACTURING POINT SOURCE CATEGORY. Federal Register
Vol. 41, (122, Pt. II), June 23, 1976. pp.25974-79.
Final effluent limitations and guidelines for existing
sources and standards of performance for new sources
are established by the Environmental Protection Agency
for defluorinated rock phosphate, defluroinated
phosphoric acid, and Na-phosphate manufacturing
facilities. For both the defluorinated rock and
defluorinated phosphoric acid categories, existing
and new plants are limited to a maximum of 105 mg
of P/l. of effluent for any one day and a 30 day
average of 35 mg of P/l. of effluent. Fluoride is
limited to 75 mg of F/l. of effluent for any one day
and to 25 mg of F/l. of effluent for the 30 day
average. Total suspended solids ar limited to 150
mg/1. of effluent for any one day and 50 mg/1. for
the 30-day average.
LAND USE CONFLICTS AND PHOSPHATE MINING IN FLORIDA.
J.W. Sweeney In: Proc. 7th Forum Geol. Industrial
Minerals: Tallahassee, Fla.: Fla. Dep. Natural Resources;
Bureau Geol., Spec. Publ. No. 17, June 1972. no. 9-
11.
The land-pebble mining industry of central Florida
was examined to identify trends in land use, conflicts
in land use, and the effect of the conflicts on mineral
resources. Many conflicts exist in the study area,
such as with other users of land resources and land
surface; with high revenue land users; for land surface
in urban and suburban areas; and restrictions
concerning utilization. Projections show that lands
in phosphate company ownership are expected to be
made available to help meet the need for future urban
expansion in the study area. Some phosphate resources
have been lost due to land use conflicts; however,
most of the loss has been small. Land use conflicts
and phosphate .mining are reconcilable and considerable
progress toward their maximum and multiple use of
land and mineral resources can be resolved through
planning based on factual data.
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FERTILIZER PRODUCTION AS RELATED TO ENERGY USED. Agric.
Econ. Stat., Vol. 25, No. 2, Feb. 1976. p. 4.
Total world consumption of nitrogen fertilizer in
1972-73 was estimated at 36 million mt. The
consumption in developing countries, however, was
only 6 million tons, or 16.7% of the total. On the
basis of previous trends and of increased fertilizer
production capacity, it is expected that the use of
nitrogen fertilizer will more than double by 1985
to about 85 million tons. With major increases in
consumption in the developing countries by 1985, the
nitrogen fertilizer requirements of these countries
are expected to be more than one quarter of the total.
Nitrogen production has a high energy requirement.
One kg of nitrogen requires approximately 2 kg. of
fossil fuel for its manufacture, packaging, transport,
distribution and .application. Phosphate fertilizer
consumption in 19 72— 73 was estimated at 22 million
mt, with approximately 3 million tons used in
developing countries. By 1985 world demand is expected
to increase to 42.5 million tons, ^y then, the
developing countries are expected to use 20% of the
total. At these rates of consumption, lov/er grade
rock and/or deposits less favorably Placed than those
used at present will then have to be drawn upon.
The production of one kg of Phosphate fertilizer
requires about 0.25 kg of fossil fuel equivalent.
In 1972-73 consumption of potash fertilizer stood
at 18.75 million mt. Of this, about 1.0% was used
in developing countries. By 1985, world demand for
potassium fertilizer is expected to increase to about
38 million tons/yr, with 6.*5 million tons going to
the developing countries. Shortages of raw material
are not foreseen at present. The production of one
kg of potassium fertilizer requires approximately
0.18 kg of fossil fuel enuivaient.
PHOSPHATE INDUS THY AND ENVI RQNMFWTAL CONTROL. r?ruce
Congleton . In: Proc. 7th Forum Geol. Industrial
Minerals; Tallahassee, Fla.: Fla. Dep. Natural Resources;
Bureau Geol., Soec. Publ. T,o. 17, June 1972. pp. 185-
86.
The Florida phosphate industry is a leader in
environmental control, both in terms of dollars spent
and significant achievements. Since 1960 the industry
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has spent over $71 million for air pollution and
control devices, including installation, research
and development, and maintenance. Water pollution
control expenditures also total in the millions, with
over $69 million spent in the same 10-yr period.
The industry also is a leader in water conservation
measures, havinn spent nearly $18 million since 1966
for conservation devices. Since phosphate is rained
by strip mining, land reclamation plays an important
part in the environmental control picture. The
phosphate industry has a voluntary program of
reclamation which accounts for over 20,000 acres of
land useable after mining has taken place. In terms
of progress in environmental control, the industry
has solved the F emission problems and is currently
at work solving 3C>2 and particulate problems. The
industry also has Been extremely successful in limiting
P and TT discharges into area streams. The industry
continues to cooperate with state and local pollution
control officials on matters of environmental control,
and future plans include even closer cooperation and
assistance, as well as increased expenditures.
FLORIDA PHOSPHORIC ACID PLANT STARTUP-EAPLY 1977. Chem.
Week, Vol. 119, No. 22, Dec. 1, 1976. p.9.
Bartow Chemical Products will be bringing a 380,000-
tons/yr (P2O5) Phosphoric acid plant onstream early
in 1977 in Bartow, Florida. The company is a joint
venture of USS Agri-Chemicals Division of U.S. Steel
and vj.F. Grace. Grace earlier has indicated the new
plant would be fully operational in 1973. Output
of the complex will be divided between the partners.
The U.S. Steel division says its share of the
phosphoric acid will be used to increase production
of fertilizers at its Bartow operations.
I. POLLUTION PROBLEMS IN PHOSPHORIC ACID PRODUCTION.
In: Phosphoric Acid by A. v. Slack. New York: Marcel
Dekker, 1963. pp. 727-739.
Production of wet-process phosphoric acid involves
the problem of disposing of several waste products
that are potential environmental pollutants. These
are mainly fluorides and dust, and each may contribute
both to atmospheric and water pollution.
Since a wet-process phosphoric acid plant is often
part of a plant complex that includes rock mining,
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drying, and grinding, acid production, and conversion
of the acid to a fertilizer product, and since wastes
from all these operations become mingled,this
discussion will cover other parts of the complex as
well as the acid plant. Most of the discussion is
on practice in Florida (U.S.), where pollution problems
have been intensified because of the high concentration
of phosphate plants in the Phosphate mining area in
the central part of the state.
The most serious water pollution problem comes from
the fluorides and acidic wastes oroduced in phosphoric
acid manufacture. Raw phosphate rock contains from
3 to 4% fluorides, practically all of which is released
and converted to some other form when the rock is
treated with sulfuric acid. The resulting distribution
of the fluorides with acidulation is approximately
20 to 30% in the. product phosphoric acid, 20 to 40%
in the calcium sulfate dihydrate (gypsum) formed and
30 to 60% in the gyosum pond water. The sources of
fluorides in the pond water are gynsum transfer water,
liquor from fluorine scrubbers, and floor wash water.
A^.r pollution problems encountered in the manufacture
of phosphoric acid are quite different and much more
complex than those involving water oollution. The
primary concern is with the fluorides evolved and
discharged to the atmosphere. Dust and sulfur dioxide
are also of concern.
Potential health hazards as well as solutions to
surface water contamination and air emissions as
practiced by the Florida phosphate industry are
discussed.
INORGANIC FERTILIZER AND PHOSPHATE "IINDUSTRIES—
WATER POLLUTION AND CONTROL. Battelle Memorial Inst.,
Richland, Wash., MQA 12020 FPD 09/71, Sept. 1971. ?29pp.
A state-of-the-art survey was made of the water
pollution problems which result from the production
of inorganic fertilizers and phosphate rock.
Information required to complete the study was -obtained
through an extensive literature search, '.-ruestionna ires
sent to the major fertilizer producers, and visits
to selected production plants. Ninety eight plants
representing thirty three different companies were
surveyed. Production figures since 1940 and estimates
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of production through 1980 were accumulated for
phosphate rock and the major fertilizer products.
The specific production operations which are the
principal generators of contaminated waste waters
were identified, and the waste water volumes and
compositions for each operation were determined
wherever possible. The capability of current
technology to treat and control the contaminated waste
waters generated by the fertilizer industry was
evaluated. Problen areas where additional reserach
and development effort is needed to provide adequate
control of waste water discharge were identified.
ANOTHER KIND OF STRIP TUNING THAT'S STIPRING UP A STORM.
U.S. News and World Report, Vol. 82, No. 20, May 23,
1977. pp. 41-2.
A battle over mining phosphate-a fertilizer critical
to world food production-is pitting neighbor against
neighbor in the Polk County area near the west coast
of Florida.
Plans to expand phosphate digging are putting industry
and environmentalists ar odds over dangers to health,
water and tourism.
Opponents contend the strip mining is ugly and could
drive away tourist business. They claim it threatens
the State's water sunoiy and endangers the lives and
health of those living nearby.
Industry leaders argue that environmental nuestions
are being answered and that mining nrovides needed
jobs.
RADIOLOGICAL DUALITY OF THE ENVIRONMENT. EPA Report
No. EPA-520/1-75-010, May 1976 258 pp.
Special Report: Individual and population doses in
the U.S. resulting from various categories of radiation
sources are summarized, and the data are assessed.
The three major source categories of radiation dose
are^ambient ionizing radiation, the application of
radiopharmaceuticals, and technologically enhanced
natural radiation. Cosmic and terrestrial radiation,
worldwide radioactivity, ore mining and milling,
fallout, uranium fuel cycle, federal facilities,
occupational and industrial radiation, consumer
products, and medical radiation are examined.
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Projected estimates of annual population dose from
transportation; radiation protection guides; and annual
external gamma v.'hole-body doses from natural
terrestrial radioactivity and nonseries primordial
radionuclides are tabulated.
ECONOMIC FEASIBILITY OF A PROCESS FOP REMOVAL OF S02
FROM STACK GASES OF COAL-FIRED POWER PLANTS AND FOR
PRODUCTION OF A FERTILIZES MATERIAL. Illinois Inst,
for Environmental Quality, Chicago, Illinois, Univ.
at Urbana-Champaign. Inst, for Environmental Studies,
June 1975. 100pp.
This study orovides a preliminary estimate of the
cost of an installation for removal of sulfur dioxide
from stack gases of a coal-fired power plant wherebv
a material suitable for fertilizer is produced and
a comparison of this cost with that of an alternative
method of removal of sulfur dioxide from stack gases.
IMPACT OF RISING ENERGY COSTS ON THE DOMESTIC PRODUCTION
OF SELECTED COMMODITIES. Christopher Haycocks. U.S.
Bureau of Mines OFF 88-76, May 1976. 124 pp.
The importance of energy in the future of both the
United States and, indeed, the world's industrial
development cannot be overemphasized. World
consumption of energy has increased rapidly in recent
years, reflecting the explosion in world industrial
capability as well as the increase in standard of
living. The purpose of this study is to determine
what effect the increased power costs might have on
the Production of selected commodities in the United
States. The commodities selected for study are:
Dituminous coal, iron and steel, Phosphate, copper,
and oil shale.
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Center's Oceanographic Station Data File, which
contains data taken primarily by Hansen casts over
a period of more than 50 years, from before 1920 to
1970. Data summaries for 6 ocean areas are depicted
by computer graphic displays—temperature-salinity
composites, tabular vertical array summaries, station
distribution plots, and frequency distribution
histograms.
SULFUR OXIDE REMOVAL FROM POWER PLANT STACK GAS. AMMONIA
SCRUBBING: PRODUCTION OF AMMONIUM SULFATE AND USE AS
AN INTERMEDIATE IN PHOSPHATE FERTILIZER MANUFACTURE.
Tennessee Valley Authority, Muscle Shoals, Ala., APTD-
0615, Sept. 1970. 324 pp.
Ammonia scrubbing and production of phosphate
fertilizer has promise, under certain conditions,
as a method for recovering sulfur oxides from stack
gases. The main economic factors are r>roduct volume
(depending on power plant size and S content of coal),
net sales revenue, and basis of financing. Private
industry participation in. financing and operation
appears unlikely because of the high projected cash
flow necessary to attract canital. There is a net
profit for plants about 500 mw and larger but it is
not large enough to attract investment except perhaps
under special conditions. The situation is improved
if there is supplemental income in the form of a
payment for the service of sulfur oxide control; in
this case the larger product volumes (e.g., 1000 mw
at 3.5% S in coal or 500 mw at 5% S) give a projected
total income adequate for financing. The economics
under power industry financing are more promising.
For plants 500-600 mw and larger in size the recovery
method is favored over limestone - wet scrubbing
because there is loss deficit passed on to the power
consumer after payment to investors of the regulated
return on investment. Only a few recovery
installations of this type can be accommodated by
the fertilizer market.
LEGAL ASPECTS OF PHOSPHATE MINING IN NORTH CAROLINA.
Michael A. Almond. Sea Grant Publication UNC-SG-75-
05, Feb. 1975. 31 pp.
The article presents the ecological dilemma in a
complex setting. The removal of phosphate from beneath
navigable waters of North Carolina may produce adverse
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effects upon marine life adjacent to the operation.
On the other hand, the phosphate is critically needed
to provide fertilizer to increase crop yields in a
hungry world. The ecological resolution of this
scientific, economic, legal, political, and humanistic
problem is not simple. The author sets forth the
pertinent North Carolina statutes and legal thinking
likely to be used in the administrative or legal
solution of this problem. He points out that wide
discretion is vested in state officials and that here
several wortny interests are to be reconciled and
where delicate policy decisions must be made, flexible
regulation may well provide the only viable answers.
TOWARD A NATIONAL POLICY ON ENERGY RESOURCES AND MINERAL
PLANT FOODS. Samuel P. Ellison Jr. Texas Univ., Austin.
Bureau of Economic Geology. Special pub., 1973. 138
PP.
A report is made on the first of the university
conferences concerning what our national nolicy should
be on oil, gas, coal, nuclear, geothermal, solar
sources on energy resources and on all varieties of
mineral plant foods. Directions on what policy should
be taken on educational endeavor are included.
PROPOSED PHOSPHATE LEASING ON THE OSCEOLA NATIONAL FOREST
IN FLORIDA, bureau of Land Management, Silver Spring,
Md. Eastern States Office., DEIS, Dec. 12, 1973. 533
pp.
The action under consideration is the issuance of
41 phosphate preference right leases for 52,000 acres
on the Osceola National Forest, north central Florida.
Issuance of these leases would result in surface mining
approximately 30,000 acres of the forest. This mining
would result in the permanent removal of 120,000,000
tons of phosphate rock over a period of approximately
30 years. Approximately 6 endangered soecies would
have their habitat temporarily or Permanently removed.
Assuming off the forest processing of the mined ore
between 10,000 to 14,000 acres of private land would
be under slime ponds. Approximately 9,000 acres of
the forest would be converted to lakes and ponds.
TrIE FLORIDA PHOSPHATE INDUSTRY: A HISTORY OF THE
DEVELOPMENT AND USE OF A VITAL MINEPAL. A.F. Blakely.
vjerthei.m Committee, Harvard University, 1973.
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This Dook follows the historical development of the
discovery and exploitation of phosphate minerals,
highlighting the technological changes, adaptations
in organizational structure, impact of a flucuating
economy, and increasing concern over conservation
and environmental issues.
Three major stages of development are chronicled:
I. 1880 - end of World War I
The early history of the industry from the commencement
of mining in the late 1880's through the years of
experimentation as the industry struggled to achieve
a stable and profitable operating basis.
II. 1920 - 1941
The development of programs to launch more
efficient mining techniques and technological
innovations as the industry branched out from
strictly mining into chemical production of
phosphate products.
III. 1940 - present
The expansion and growth of the industry in
response to ever-increasing world demand for
phosphate products is coupled with increased
awareness of conservation and environmental
policies.
STANDARDS FOP EFFLUENTS FROM FERTILIZE? INDUSTRY. G.".
Saxena. Indian Journal of Environmental Health, Vol.
15, No. 4, October 1973, Pp. 305-321.
The India water quality standards prescribed for
fertilizer effluents for disposal into inland surface
waters onto land for irrigation, and into public sewers
are discussed, A summary of select fertilizer
industries with reference to characteristics of their
effluents and treatment orocedures adoote? by them
is also presented.
FERTILIZER MANAGEMENT FOR POLLUTION CONTROL.
• lartin, VJ.E. Fenster, and L.D. Hanson. miscellaneous
Publication Paper Mo, 1360 of the University of "innesota
Agricultural Experiment Station, St. Paul, Agricultural
Practices and Water Quality, Iowa State University Press,
Ames, Iowa, 1970,. pp. 142-158.
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Nitrogen and phosphorus, as nutrient elements, are
important to both land and aquatic plants, and normally
reach water supplies via land runoff in the erosion
debris. Fertilizer usages in the midcontinent area
are rapidly increasing to maximize production and
increase efficiency, and further increases are
expected. Fertilizer phosphorus quickly converts
to unavailable forms in mineral soils and the evidence
indicates that one of the ways of reducing the level
of soluble phosphorus in water would be to effect
soil contact such as by filtration through the soil
medium. Nitrogen fertilizer application rates should
approximate crop needs, which for a given soil type
and climatic zone are based on production potential
estimates for the crops to be grown. Management
recommendations refined through the years for
maximizing production are not incompatible with the
objective of reducing nutrient contamination of natural
waters. Further research is needed on nutrient
balances and reactions in soils to maintain supplies
at levels needed for crop production. Water quality
standards as established by the federal and state
water pollution control grouos should be compatible
with the need for maintaining adequate nutrients for
efficient crop production consistent with management
programs designed to minimize losses to adjacent water
supplies.
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