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BUREAU OF MINES
Robert C. Horton; Director
Library of Congress Cataloging in Publication Data:
ILLUSTRATIONS
Illustrations--Continued
10. Effect of oleic acid addition on BeO recovery and grade in beryl rougher
concentrate ••••••••••••••••••••••••••••••••••••••••••••••• ~ •••••• ~ ••••• 9
I~\
11. Effect of oleic acid conditioning time on flotation of fluorite-mica
! sample· ••••••••••••••••••• ., ••••••• ,. ...................................... . 11
ABSTRACT
Minerals engineer.
2Group supervisor.
3Research supervisor.
Sal t Lake Ci ty Research Cen ter, Bureau of Mines, Salt Lake Ci ty I UT.
I.
IfI'
---;~-;:~ .
.,
i
INTRODUCTION
Fluorspar is the commercial name for an highest price. Major uses include the
aggregate of rock and mineral matter con- manufacture of fluorine chemicals, syn-
taining a sufficient amount of the min- thetic cryolite (essential for aluminum
eral fluorite (CaF 2 ) to qualify as a production), preservatives, insecticides,
marketable commodity. Pure fluorite is aerosols, and metal coatings.
calcium fluoride, which contains 51.3 pct Domestic shipments of finished fluorite
Ca and 48.7 pct F. Fluorite is the prin- declined for the third consecutive year
cipal source of fluorine, an element for in 1984. Fluorite output failed to ex-
which no adequate substitute has been ceed 100,000 st for only the fourth time
found. Fluorite is used principally as since 1938. Mexico remained the major
a fluorine source in the making of supplier of metallurgical- and acid-grade
(1) hydrofluoric acid (HF), (2) a flux in fluorite (54 pct), with the Republic of
metallurgy, and (3) a raw material in the South Africa the second largest supplier
manufacture of glass and enamels. (28 pct). Minor amounts were received
Fluorite is marketed in three grades from China, Italy, Spain, and Kenya (2).
that have different physical and chemical A long-term downward effect on the-de-
specifications (1):4 mand for fluorite and fluorine compounds
continues, as steelmakers consume less
Metallurgical grade.--This is also fluorite per unit of output and primary
known as "metspar" or "lump spar and aluminum smelters adopt and refine tech-
is sold on the basis of effective CaF 2 nology that recovers and recycles more
content rather than the actual CaF2 fluorine. New and expanded uses for flu-
content. The effective CaF2 content is orine chemicals will offset these de-
derived by subtracting 2.5 times the creases in long-term demand. From a 1985
percentage of the silica (Si0 2 ) content base, consumption of fluorite equivalent
from the percentage of CaF 2 content. is . expecte(r~to-increase at an annual
"Metspar" users require 60 to 70 pct average rate of 2.7 pct through 1990 (2).
effective CaF 2 , limit Si0 2 to 5 or The long-term U.S. fluorite requirements,
6 pct, limit sulfides to under 0.50 pct, of which 91 pct is imported, will have to
and limit lead to under 0.25 pct. Metal- be derived from secondary sources, sub-
lurgical-grade fluorite is used as a flux marginal domestic ores, or multicomponent
in steel, as an electrolyte in aluminum ores (2).
smelting, and in metal welding, porcelain Most- domestic fluorite is produced
enameling, and glazing. in the Midwest. Production in Illinois
Ceramic grade.--This is also known as accounts for over 90 pct of all U.S.
"glass" and "enamel" grade and must con- shipments. In the West, production was
tain a minimum of 95 pct CaF 2 , with a reported from small mines in Nevada and
maximum of 2.5 pct Si0 2 • It must be fine Texas. Small, unreported amounts of flu-
grained for use in the manufacture of orite were produced in Utah, Idaho, and
opaque and flint glass, as an ingredi- New Mexico (3). Approximately 90 Nevada
ent in welding and coatings, in making deposits containing 5 to 50 pct CaF 2 ,
white- and buff-colored clay bricks, and with byproducts of barite, beryllium,
in vitreous enamels for coating metal ar- scheelite, zinc, gold, and silver, were
ticles and appliances. reported (4-5). Byproduct recovery is
Acid grade.--This is used in the man- necessary to-enable economic processing
ufacture of HF and should contain a mini- of submarginal domestic reserves.
mum of 97 pct CaF2 and not over 1.1 pct Traditional methods of concentrating
Si0 2 , 1.25 pct CaC0 3 , and 0.03 pct S. fluorite use gravity separation, followed
Acid-grade fluorite is the highest qual- by flotation. A flotation procedure us-
ity marketed and therefore commands the ing oleic acid as a fluorite collector
was patented (l) and used to recover
4Underlined numbers in parentheses re- acid-grade fluorite from an Illinois
fer to items in the list of references at jig tailings that contained 44 pct
the end of this report. CaF 2 • Another procedure, which depressed
3
barite with lignin sulfonate and floated beneficiation methods to recover fluo-
fluorite with oleic acid, was used to rite, muscovite, and beryllium values
beneficiate a Yuma County, AZ, fluorspar from the Fish Creek deposit in Nevada.
ore (7). The Bureau of Mines charac- This report summarizes the results of
terized and devlsed new flotation that investigation.
EXPERIMENTAL MATERIALS
Two samples were obtained 'from the Fish Petrographic analyses of the fluorite-
Creek fluorspar deposit near Eureka, NV. mica sample indicated that it contained
One sample was known to contain beryllium major amounts of fluorite, quartz, chert
values. The samples were crushed and (microcrystalline quartz), muscovite, bi-
screened through 10 mesh and thoroughly otite (black mica [(K,H)2(Mg,Fe)2(Al,Fe)2
blended, after which representative por- (8i0 4 )3])' and phlogopite (magnesium mica
tions were submitted for chemical and [(K,H)3Mg3Al(Si04)3])' Minor amounts of
petrographic analysis. The chemical an- pyrite (FeS2), hematite, limonite, potas-
alyses are shown in table 1. sium-feldspar, cal.cite, serpentine [Mg3
Petrographic analysis of the fluorite- (Si0 5 )(OH)4]' apatite. (CaFP 30 ,2 ), schee-
beryllium sample indicated that it con- l,ite (CaW04), sphalerite, smithsonite
tained major amounts of quartz (8i0 2 ), (ZnC0 3 ), Willemite (Zn2Si04)' franklinite
fluorite (CaF 2 ), and muscovite (light- [(Fe,Mn,Zn)(FeOZ)2], an unidentifiable
colored mica [KAl 38i 30 I0 (OH)2])' Minor zinc-iron mineral, chlorite, and kaolin- Ii
amounts of hematite (Fe203)' limonite ite (Al 203 '2Si0 2 '2Hz O) were observed.
(hydrous iron oxides), sphalerite (ZnS), Liberation size was 35 mesh.
iI- potassium-feldspar
(Be3Al2Si6018)'
(KAl8i 308 ),
calcite
beryl
(CaC0 3 ), and
Minus 35-mesh material was prepared for
bench-scale testing by stage crushing
:1
5Re ferences to specific products does 6This was lower than the preferred do-
not imply endorsement by the Bureau of sage of 3 lb/st for NaZSi03, which had
Mines. not ye t been de termined.
5
Sodium Carbonate
100
Sodium carbonate (Na2C03) was used as a
90 water cqnditioner and to aid in gangue
depression. Based on tests varying do-
80 sage levels from 0.5 to 4 Ib/st, a pre-
ferred dosage of 3 lb/st was determined.
~ 70 In these tests, flotation pH was held
w at 9.0, CT for all reagents was 3 min,
u
a:: and dosage levels were 2 lb/st for both
~ 60
Na zSi0 3 and oleic acid. As shown in
figure 3, recovery was nearly constant,
50 while maximum grade of 73.2 pct CaF2
was at 3 lb/st Na2C03' above which level
40 gangue flotation caused a dropoff in
grade.
30 Based on tests varying Na zC03 condi-
7.0· 8.0 9.0 10.0 11.0 tioning time from 3 to 30 min, a prefer-
pH
red time of 15 min was determined. In
FIGURE 2~ - Effect of pH variation on fluorite grade these tests, CT was held at 3 min each
and recovery, fluorite-beryl Iium sample. for Na zSi0 3 and oleic acid, and dosage
levels were held at 3 lb/st for Naz C03
Flotation pH Variation and 2 lb/st for both Naz Si0 3 and oleic
aCid;8 flotation pH was 9.0. Recovery
Prior investigators (8-9) reported held near constant at 97 pet, while grade
that the point-of-zero-charge for fluo- had slight fluctuation from 78.5 pct CaF2
rite was at pH 10.0; therefore, the pH at 3 min CT to 82.5 pet CaF z at CTr s of
for fluorite flotation using an anionic 15 min and longer.
collector should theoretically be below
pH 10, owing to the positive charge 7See footnote 6.
on the fluorite surface. Based on tests 8See footnote 6.
6
90
Recovery
j sant. Based on tests
levels from ° varying dosage
to 4 lb/st, a preferred
dosage of 3 lb/st was determined. In
Grade
70 these tests, flotation pH was 9.0, CT for
I-
z all reagents was 3 min, and dosage levels
w
o were 3 lb/st for Na2C03 and 2 lb/st
ffi 60
0... for oleic acid. As shown in figure 4,
recovery dipped slightly between dos-
50 age levels of 1.5 and 2.5 lb/st Na2Si03'
then increased toward 100 pct above
that level. Grade, on the other hand,
1.0 1.5 2.0 2.5 3.0 3.5 4.0 showed sharp increases up to addition
SODIIJM CARBONATE ADDITION, Ibis!
levels of 3 lb/st Na2Si03' then dropped
FIGURE 3.· Effect of Na2COa addition on fluorite off because of increased gangue
grade and recovery, fluorite-beryllium sample. flotation;
Based on tests varying Na2Si03 con-
ditioning time from 3 to 30 min, a pre-
ferred time of 15 min was determined.
In these tests, CT was held at 3 min
10°F===~==r---~--~--~~1 each for Na2C03 and oleic acid, and do-
sage levels were held at 3 lb/st for
Recovery Na2C03 and 2 lb/st for both Na2Si03 and
90 oleic acid;9 flotation pH was 9.0. Re-
covery held constant at approximately
80 95 pct, while grade increased from
65.5 pct CaF 2 at 3 min CT to 80.4 pct at
15 min CT, then df-opped to 72 pct at
I- 70 30 min CT because of increased gangue
z
w flotation.
U
0::
~ 60 Flotation Under Preferred Conditions
8.~
70 .7 Collector Addition
~
«0:: Based on tests varying collector (tal-
.6 (!)
1.5 2.0 2.5 3.0 3.5 4.0 low amine acetate) dosage from 0.3 to
SULFURIC ACID ADDITION, Ib/st 1 lb/st, a preferred dosage of 0.7 lb/st
was determined. In these tests, CT was
FIGURE 6 •• Effect of H 2SO .. addition on BeO
held at 3 min for both reagents, and
recove.ry and grade in muscovite rougher tail ings.
H2 S04 dosage was held at 2 lb/st; pHwas
held at 3. As shown in figure 7, over-
all beryl recovery fell slightly with
increasing collector dosage, while the
beryl grade of the muscovite tailings was
t; 90 ~-----RD:e;;;c~ov:;;;e:;'ry:;-------J highest at 0.7 lb/st collector; at that
Q.
>-"
dosage also the maximum weight was re-
ffi 80 0.8 ~ moved from the muscovite concentrate.
8 Grade
In
t;
~ 70 .7
0-
W- Silicate Removal
o
« Direct flotation of beryl produced con-
60 J,........_ _---L-_ _--L_ _ _ _l....-_ _~_ __ L_ ____1_ ______' .6 ffi
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 centra·tes with~grades less than 2 pct
TALLOW AMINE ACETATE ADDITION, Ib/st BeO; therefore, silicate flotation was
FIGURE 7. - Effect of tallow amine acetate addi-
used to depress the free Si0 2 and improve
tion on BeOrecovery and grade in muscovite rougher
the grade prior to beryl flotation. Flo-
tation testwork was performed on the sil-
tail ings.
icate flotation circuit to determine the
effects of (1) HF addition and (2) col-
lector (tallow amine acetate) addition on
the flotation of the silicate (beryl and
feldspar) minerals.
70
Hydrofluoric Acid Addition
t; 60
Cl. Hydrofluoric acid '(HF) was used as an
>-" 50 activator for the beryl, as a quartz de-
0::
W pressant, and as a pH modifier. Based
~ 40
o on tests varying HF dosage from 0 to
~ 30 10 lb/st, a preferred dosage of 5 lb/st
ui was determined. In these tests, the pulp
20 2 0
was first conditioned with HF for 3 min,
~
10 r{!) then with 1 lb/st collector for 3 min,
after which the silicates were floated.
0'----""-----'----'------'------' 0 . As shown in figure 8, both recovery an9
2.0 4.0 6.0 8.0 10.0 grade increased with increased HF addi-
HYDROFLUORIC ACID ADDITION, Ib/st
tion up to about 5 lb/st, then fell
FIGURE 8. - Effect of HF addition on BeOrecov- sharply with further HF additions; gangue
ery and grade in s i Iicate rougher concentrate. flotation caused the ,fall in grade, while
·1
: i
9
reagent bui~dup on the beryl' surface depress gangue flotation in the beryl
lowered the recovery. At 5 lb/st HF ad- circuit, which would lower the beryl
. dition, concentrate grade was 4.80 pct grade. To accomplish this, the pulp was
BeO with a recovery of 89 pct; pulp pH washed for 5 min with 2 lb/st NaOCI, then
was 2.75 at this preferred dosage. allowed to settle for another 5 min.
The excess liquid was decanted and
Collector Addition the solids repulped with fresh water.
! Then the pulp was conditioned for 5 min
I
,~ The- collector, tallow amine acetate in and allowed to settle for another 5 min
a 5-pct solution, was used to separate before the excess fresh water' was
the silicate minerals from the free 8i0 2 • decanted.
Based on tests varying collector dosage
from 0 to 5 lb/st, a preferred dosage Beryl Flotation
of 0.5 lb/st was determined: In these
tests, the pulp was conditioned with Testwork had indicated that beryl
the collector ,following conditioning selectivity could be improved by using
for 3 min with 5 lb/st HF. As shown in aflotat!on pH of 11.0. Flotation test-
figure 9, grade decreased steadily with work was thus performed to determine
increasing amounts of tallow amine ace- the optimum (preferred) amount of collec-
tate, whereas recovery jumped sharply tor needed for beryl flotation at this
with as little as 0.5 lb/st collector, pH.
then continued to increase gradually
before falling off slightly at dosage Collector Addition
levels above 3 lb/st. At 0.5 lb/st col-
lector, concentrate grade was 4.55 pct Food-grade oleic acid was used as the
BeO with a recovery of 81 pct. collector for the beryl. Based on tests
varying dosage from 0.3 to 1 lb/st, a
Collector Removal preferred dosage of 1 Ib/st was deter-
mined. In these tests, pH was held con-
Sodium hypochlorite (NaOCloSH2 0) was stant at 11, and conditioning time at
used to remove the collector from the 3 min. As shown in figure 10, the beryl
mineral surfaces in order to gain selec-
tivity in the beryl circuit. Removal of 70 ,..------r---...,....,...-----,---;
residual collector was necessary to
90
60
80 8 +- 50 5
(.)
70 7
Q.
Grade
U >-"40 4 0
a. 60 60 a::: (j)
t Pamak 4A ••••
Aero 830., •••
lb/st pct CaF2
2.0
2.0
56.0
56.4
pct
97.9
93.6
both reagents, and dosage was 2 lb/st for
Na2Si03 and 1.5 lb/st for oleic acid. As
shown in figure 12, recovery decreased
1I Oleic acid •• 1.5 77 .2 92.2 very gradually until the pH reached 10,
then fell very sharply, while grade con-
Determination of Preferred Conditions tinued to increase with increasing pH
level. At pH 9, grade was 75 pct CaF2
Oleic Acid Conditioning Time with a recovery of over 90 pet.
80
~ 60
w
U
~
0:: t5
a::
70
~ 50 w
0..
60
40
50
30~--~--~----~--~----~--~
o 5 10 15 20 25 30 8.0 9.0 11.0
CONDITIONING TIME, min pH
FIGURE 11..- Effect of oleic acid conditioning time FIGURE 12. - Effect of pH variation on fluorite
on flotation of fluorite-mica sample. grade and recovery, fluorite-mica sample.
12
100~------r-------'-------,
Mica Flotation
CONCLUSIONS
REFERENCES