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University of Utah

Semi Soluble Salts

Apatite Ca5(PO4)3(F,Cl,OH)
Fluorite CaF2
Calcite CaCO3
Cerussite PbCO3
Malachite CuCO3Cu(OH)2

Department of Metallurgical Engineering


University of Utah
Introduction
There are two types of deposits namely
igneous and sedimentary deposits.
Apatite(Ca10(PO4)6X2, X=F-, OH- ,Cl- ,CO3-) is
one of the most common phosphate minerals
and the major phosphate mineral in igneous
deposits
Francolite, a carbonate fluorapatite (Ca10-a-
bNa2a Mgb(PO4)6x(CO3)xFx+2) is a major
phosphate mineral in sedimentary deposits

Department of Metallurgical Engineering


University of Utah
Phosphate Production(~140,000kmt)

Western Russia
Europe 11,000
Tunisia 7,800
Morocco China
US 41,500 20,000
24,000 Middle East
10,100

Brazil 4,500
South Africa 3,000 Australia

Department of Metallurgical Engineering


University of Utah
The significance of phosphate
production

" We may be able to substitute nuclear


power for coal power; and plastic for wood;
and yeast for meat; and friendship for
isolation - but for phosphorus there is
neither substitute nor replacement."

Isaac Asimov

Department of Metallurgical Engineering


University of Utah

Department of Metallurgical Engineering


University of Utah

Department of Metallurgical Engineering


University of Utah
Phosphate Consumption
Animal
other
Feeds
3%
5%
Detergents
12%

Fertilizers
80%

Department of Metallurgical Engineering


University of Utah
Phosphate Processing Technology
1. Flotation is the most important separation
technology.
2. Scrubbing & washing, heavy medium separation,
air classification, and calcination are also used.
3. Although much research has been carried out to
develop more efficient flotation technology, many
problems regarding the separation/cost-efficiency
still remain unsolved.

Department of Metallurgical Engineering


University
The of Phosphate
Utah Plant Flowsheet in Florida
Phosphate Rock
Run of Mine Ore

Classification
Pebble(+16 mesh) Slimes(-150 mesh)
(final product) Coarse Fine (to tailings pond)
(16x35 mesh) (35x150 mesh)
High Solid(>70%) High Solid(>70%)
Conditioning Conditioning

Coarse Fine
Fatty Acid Flotation Fatty Acid Flotation

Acid Scrub Acid Scrub

Coarse Fine
Amine Flotation Amine Flotation

Coarse Concentrate Tailing Fine Concentrate


(final product) (to tailings pond) (final product)

Department of Metallurgical Engineering


University of Utah
Double Flotation Process

Fatty Acid 1.4 ~ 2.1 lb/t


Fuel Oil 0.6 ~ 0.9 lb/t
Sodium Carbonate 0.8 ~ 1.4 lb/t
Amine 1.5 lb/t
Sulfuric Acid 2.0 lb/t

Overall Average Recovery ~ 80%

Department of Metallurgical Engineering


University of Utah
Soluble Collectors
Solution Chemistry Surface
Surface Reactions Spectroscopy
Collector Adsorption Electrokinetic
Micro-Flotation Surface Tension
Contact Angle

These studies have generally been limited to the study of soluble


collectors, particularly fatty acids, with many interesting findings.

Department of Metallurgical Engineering


18 - Carbon Fatty Acids

Stearic Elaidic Oleic Linoleic Linolenic


Adsorption Density vs. Surface Pressure
for LB Monolayer of Stearic Acid
Determined from the p-A Isotherm and by FTIR/IRS Adsorption Density
Equation After Transfer of the LB Film to the Surface of a CaF2 IRE
Oleate Adsorption Isotherms
(pH ~ 9.5, 20-25 oC)
Comparison of the measured heats of adsorption of oleate at
the fluorite/water interface with isosteric heats of adsorption
for different levels of surface coverage (Miller et al. 1989)

Heat of Adsorption of Oleate (kcal mol-1)


Measured by Calculated from
Microcalorimetry Adsorption Isothern
Data
Chemisorption
(monolayer coverage) 2.36 2.77
Surface Precipitation
(above monolayer coverage) -5.31* -6.60
* At oleate surface coverage q2 = 0.59 (I.e., q = 1.59)
Comparison of the Chemisorption Region for
Fluorite, Calcite, and Apatite
At surface coverage below a monolayer the adsorption densities correlate
with the surface site density of calcium : fluorite > calcite > apatite

Surface Surface Site Adsorption


Density of Density from
Calcium 1x10-5 M Oleate
(mole/m2) Solution
(mole/m2)
Fluorite (111) 12.9 6.5-6.7
Calcite (1011) 8.24 2.5-3.2
Apatite (0001) 6.57 1.5-2.0
Comparison of the Surface Precipitation
Region for Fluorite, Calcite, and Apatite
At surface coverage above a monolayer the maximum adsorption
densities correlate with the solubility and the dissolution rate of the
minerals : calcite > fluorite > apatite

Mineral Maximum Calcium Solubility


Adsorption (M)
Density Calculated Measured
(mole/m2)
-5 -4
Calcite 300 6.76x10 1.5x10
-4 -4
Fluorite 100 2.70x10 1.3x10
-8 -5
Apatite 11 2.13x10 2.5x10
Bridging Coordination Believed to Define the
Nature of Carboxylate Chemisorption at the
Fluorite Surface
Comparison of the Chemisorption Region for
Fluorite, Calcite, and Apatite
At surface coverage below a monolayer the adsorption densities correlate
with the surface site density of calcium : fluorite > calcite > apatite

Surface Surface Site Adsorption


Density of Density from
Calcium 1x10-5 M Oleate
(mole/m2) Solution
(mole/m2)
Fluorite (111) 12.9 6.5-6.7
Calcite (1011) 8.24 2.5-3.2
Apatite (0001) 6.57 1.5-2.0
Comparison of Transferred LB Monolayer
with a Self Assembled (SA) Monolayer of
Stearate at a Fluorite Surface
Monolayer Adsorption Orientation Contact Contact
Type Density from Angle Angle
mole/m2 Surface Advancing Receding
Normal
LB 8.1 10o-14o 111o 100o
SA 7.6 20o-24o 112o 81o
Advancing and Receding Contact Angles for a
Transferred LB Monolayer of Stearic Acid at
Fluorite and Calcite Surfaces
(water drop of varying size, pH 5.8)
University of Utah
Comparison of Oleate Adsorption Isotherms at
Apatite, Fluorite, and Calcite Surfaces
(pH 9.5 and a temperature of 20C to 25C)

Department of Metallurgical Engineering


University of Utah
Significance of Calcium Surface Site
Density in Oleate Adsorption

Surface Calcium Surface Site Adsorption Density from Contact Angle


Density (umole/m2) 1x10-5 M Oleate Solution (1x10-5 M Oleate)
(umole/m2)
Fluorite 12.9 6.5-6.7 750
(111)
Calcite 8.24 2.5-3.2 NC
(1111)
Apatite 6.57 1.5-2.0
(0001)

Department of Metallurgical Engineering


University of Utah
Comparison of Adsorption Density, Contact Angle, and
Flotation Recovery for Apatite Minerals with Oleate as
Collector at 5x10-4 M and pH 10

Adsorption Surface Contact Flotation


Apatite Mineral
Density, Coverage Angle Recovery %
mg/m2
Fluorapatite 1.08 0.49 55 88.7

Carbonatapatite 0.86 0.39 43 71.3

Hydroxylapatite 0.52 0.24 38 62.5

Chlorapatite 0.34 0.20 No 53.2


Attachment

Department of Metallurgical Engineering


University of Utah
Bridging Coordination Believed to Define the
Nature of Carboxylate Chemisorption at the
Fluorite Surface

R (Hydrocarbon Chain)

O O

Ca Ca

Bridging

Department of Metallurgical Engineering


University of Utah
Predominance Diagram for Oleate Species
with 1x10-6 M Calcium

Department of Metallurgical Engineering


University of Utah
Fundamental Issues for Insoluble
Liquid Collectors (Coal, Phosphate,
Potash)
Dispersion
Attachment
Wettability, Spreading
Bubble Filming
Aerofloc Structure and Stability

Department of Metallurgical Engineering


University of Utah
High Solids Conditioning
Single Stage Flotation Response as a Function of Percent Solids during
Conditioning with 1000 g/t AERO 6493 for Coarse Feed from the Cargill Plant.
100

Grade(P 2O5%) and Flotation Recovery % Grade


80
Recovery

60

40

20

0
20 30 40 50 60 70 80 90

Percent Solids for Conditioning

Department of Metallurgical Engineering


University of Utah
Selective Wetting During High
Solids Conditioning

Department of Metallurgical Engineering


University of Utah
Selective Wetting
High speed video photography showing transfer of a
drop of the alcoholic solution of hydroxamic acid from a
quartz surface to an apatite surface

Quartz

Apatite

Department of Metallurgical Engineering


University of Utah
High speed video photography showing the
flotation of coarse phosphate feed

Flotation with AERO 6493 Collector Flotation with FA/FO Collector


Department of Metallurgical Engineering
University of Utah
Section of a 3D X-Ray Micro CT Image of
Dense Aerofloc Structure of a Phosphate
Concentrate

Department of Metallurgical Engineering


University of Utah
Relaxation of hydroxamic acid
collector drop contact angle
180
AERO 6493 Drop Contact
160
140
Angle (Degrees)

120 Quartz(No Attachment)


Dolomite
100 Apatite

80
60
40
20
0
0 100 200 300 400
Equilibration Time (Sec)

Department of Metallurgical Engineering


University of Utah
High speed video photography showing air bubble at apatite
and quartz surfaces after conditioning with the new collector

Apatite Quartz

Air bubble attachment Air bubble contact


at apatite surface at quartz surface

Department of Metallurgical Engineering


University of Utah
Spreading of Alcohol Hydroxamic Acid Drop
at Apatite Surface

Water

Solid Surface
Department of Metallurgical Engineering
University of Utah
Florida Phosphate Mining Start from
1900s

dragline

Mining by hand

Department of Metallurgical Engineering


University of Utah
Florida Phosphate Industry

Flotation

Mining

Wash Plant

Department of Metallurgical Engineering


University of Utah

Phosphorous and Phosphogypsum

Department of Metallurgical Engineering


University of Utah
Problems Associated with
Industry Practice
Particle Size
1. Fine particle flotation
2. Coarse particle flotation

Separation from Carbonates


1. Liberation
2. Chemistry-selective collector, reagents

Department of Metallurgical Engineering


University of Utah
Coarse Phosphate Flotation
Moudgil, 1992

100

Cumulative Recovery of P2O5 (%)

80

60

40

Fine Fraction(-35 mesh)


20
Coarse Fraction(+35 mesh)

0
0 1 2 3 4 5
Cell Number

Department of Metallurgical Engineering


University of Utah
Comparison of Grade/Recovery Curves
Obtained for FA/FO Collector with New Collector
(Coarse Flotation Feed (16x35 mesh, 5.65% P2O5) from Florida)
35

30
Grade % P 2O5

25

20 New Collector
FA/FO
15

10
75 80 85 90 95 100
Phosphate Recovery %

Department of Metallurgical Engineering


University of Utah
Important Features from Bench Scale
Flotation Experiments With Hydroxamic Acid
Collector
Long chain branched alcohols give a
higher flotation recovery
High solids conditioning is required to
achieve efficient separation
Flotation at natural pH
Improved coarse phosphate recovery
Single stage and single reagent
Department of Metallurgical Engineering
University of Utah
Pilot Plant Testing at Central Florida

Department of Metallurgical Engineering


University of Utah
Flotation Results from single stage pilot plant
for feed material from the Cargill SFM plant
using the new hydroxamic acid collector
Feed Condition Product Wt % P2O5 % Recovery %

Dosage 850 g/t Concentrate 27.96 29.6 85.94

Fine Conditioning Solids Tailing 72.04 1.88 14.06


Feed
74 % Feed 100.00 9.63 100.00

Dosage 1200 g/t Concentrate 38.80 31.55 94.88

Coarse Conditioning Solids Tailing 61.20 1.08 5.12

Feed 71% Feed 100.00 12.9 100.00

Department of Metallurgical Engineering


University of Utah
Summary

It seems that a single stage phosphate recovery of


90-95 % is possible with a concentrate grade of 30%
~33% P2O5 for coarse phosphate feed of siliceous
sedimentary phosphate ores.
High solids conditioning is of importance to insure
good dispersion and wetting of phosphate particles
by the insoluble alcoholic solution of hydroxamic acid,
AERO 6493.

Department of Metallurgical Engineering


University of Utah
Improved Recovery of Coarse Particle Flotation Due
to Improved Dispersion of Insoluble Collector

100

90
Grade (% P 2O5) and Phosphate Recovery (%)

80

70
Recovery (with p3815)
60 Recovery (with PEO-1)
Grade (with p3815)
50
Grade (with PEO-1)

40 Grade (without polymer)


Recovery (without polymer)
30

20

10

0
150 300 450 600 750 900 1050 1200 1350
Total Reagent Addition (g/t)

Department of Metallurgical Engineering


University of Utah
Dispersion Effect of PEO at pH 9.0

a b

(a) PEO/Fatty Acid/Fuel Oil (b)Fatty Acid/Fuel Oil

Department of Metallurgical Engineering


University of Utah
Effect of PEO on phosphate grade and recovery
(Coarse feed, total reagent 500g/t, fatty acid/fuel oil 7:3 pH 9)

90
Grade(%P2O5) and Phosphate Recovery(%)
80

70

60 Grade
Recovery
50

40

30

20

10

0
0 5 10 15 20 25 30 35
PEO-1, Weight Percent of Total Reagent Addition

Department of Metallurgical Engineering


University of Utah
Summary
During coarse phosphate flotation with fatty
acid/fuel oil, the total reagent consumption can
be reduced by addition of PEO
Improved flotation efficiency with PEO are due to:
1. Improved dispersion of fatty acid/fuel oil
2. Increased contact angle
3. Enhanced froth stability
For a plant processing 4 million short tons per
year , the annual savings would be $284, 400

Department of Metallurgical Engineering