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MICROCOPY RESOLUTION TEST CHART
NATIONAL QUREAU OF STANDARDS -1963

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17
ORNU-P-1602
Cont-650918 6
1965
MASTER
OCT 6
PRIMARY AMINE EXTRACTION OF BERYLLIUM FROM SULFATE LIQUORS
D. J. Crouse
K. B. Brown
F. G. Seeley
Oak Ridge National Laboratory
Oak Ridge, Tennessee
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To be presented at the
INTERNATIONAL CONFERENCE ON THE CHEMISTRY OF THE
SOLVENT EXTRACTION OF METALS
on September 27-29, 1965; Harwe11, England
REI.EASED FOR ABOUNCEMENT
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IN NUCLLAR SCIENCE ABSTRACTS
.
Research sponsored by the U. S. Atomic Energy Commission
under contract with the Union Carbide Corporation.
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PRIMARY AMINE EXTRACTION OF BERYLLIUM FROM SULFATE LIQUORS*
D. J. Crouse
K. B. Brown
F. G. Seeley
Oak Ridge National Laboratory
Oak Ridge, Tennessee
ABSTRACT
Certain amines are potentially useful extractants for recovering
beryllium from sulfuric acid digests of low-grade beryllium ores. Of
a variety of amines tested, only the primary amines extracted signifi-
cant amounts of beryllium and, of these, 1-(3-ethylpentyl)-4-ethyloctyi-
amine is the most effective. Beryllium distribution coefficients in-
crease with decreasing acidity and are high enough for practical use in
the pH range of 2 to 3. The distribution coefficients increase with
increase in sulfate concentration and are proportional to about the
0.7 power of the amine concentration. Aluminum is extracted, but good
separation from beryllium can be obtained by sa tura ting the pregnant
solvent with beryllium and scrubbing with 0.01M H2SO4•' Fluoride inter-
feres with beryllium extractions from pure sulfate solutions, but aids
extractions from process liquors because it complexes aluminum and re-
duces the one on team of competition : by aluminum for the extractant. Beryl-
lium is readily backwa shed from the solvent with 0.5-1% H2S04 or with
dilute ammonium fluoride solutions.
Research sponsored by the U. S. Atomic Energy Commission
under contract with the Union Carbide Corporation.
LA
PRIMARY AMINE EXTRACTION OF BERYLLIUM FROM SULFATE LIQUORS
D. J. Crouse
K. B. Brown
F. G. Seeley
Oak Ridge National Laboratory
Oak Ridge, Tennessee
INTRODUCTION
The increasing demand for beryllium (for high temperature alloys,
atomic reactor use, etc.) and the scarcity of high-grade beryllium ores
has stimulated interest in the processing of low-grade ores. The ex-
traction of beryllium with di(2-ethylhexyl) phosphoric acid and other
and processes using di(2-ethylhexyl) phosphoric acid have been devel-
oped 9-5 for recovering beryllium from ore sulfate leach liquors. A
characteristic of the phosphoric acid extractant 18 its low beryllium
extraction rate, necessitating long contact times.
de Bruin?, et al., studied the extraction of anionic beryllium com-
plexes from organic salt solutions (oxä late, salicylate, etc.) with tri-
180-octylamine. Unfortunately this amine, as well as other tertiary,
secondary, and quaternary amines tested, will not extract beryllium
from sulfate solutions, e.g., sulfuric acid leach liquors. However,
in recent studies at Oak Ridge National Laboratory it has been shown
that long cha in primary amines can extract beryllium rapidly from sul-
fate liquors and certain of these show promise as practicable beryllium
extractants.
*
Research sponsored by the U. S. Atomic Energy Commission
under contract with the Union Carbide Corporation.
EXPERIMENTAL MATERIALS AND TECHNIQUES
Information concerning the structure, purity, and source of supply
of the amines used in these studies is given in previous publications.
To prevent significant pH change during the extraction tests, the
amines were converted to the sulfate salt form prior to their use. In
most cases, 7Be tracer was added as an analytical aid.. The organic and
aqueous phases were contacted in separatory funnels mounted in a Burrell
wrist-action shaker.
EXTRACTIONS FROM PURE SOLUTIONS
As shown in Tables 1 and 2, the primary amines are the only amine
class with beryllium extraction power adequate for process use, and
extraction performance within this class is strongly dependent on the
alkyl structure. Extractions are most effective with a primary amine
of a secondary alkyl having two relatively long branches. Examples of
amines in this category are l-heptyloctylamine, l-nonyldecylamine, and
1-(3-ethylpentyl)-4-ethyloctylamine (abbreviated HDA for heptadecylamine).
The last 18 the most effective amine found thus far. · (See also Fig. 3).
Armeen L-15, which is of similar structure but with only one long chain
and a methyl group attached to the secondary carbon, gives inferior re-
sults as does Primene JM which is a primary amine of a tertiary alkyl
.
with one long branch and two methyl branches. Attempts to test straight-
cha in primary amines were unsuccessful because of emulsion formation.
Extraction properties of the amines vary greatly depending on the
choice of diluent. Of several diluents tested with HDA, carbon
TABLE 1. EFFECT OF AMINE TYPE ON BERYLLIUM EXTRACTION
Organic phase: 0.1m amine (sulfate salt form) in
diethylbenzene
Aqueous phase: O. IM Na280_0.01M BeSO4, pH 1.5
or 2.5
Contact: 10 min at 1/1 phase ratio
:
nase ratio
Amine
Type
Beryllium
Distribution
coefficient (D)
Amine
pH
Primene JM
Primary
1.5
0.08
0.24
2.5
1-(3-ethylpentyl)-4-ethyloctyl(HDA )*
Primary
2.5
3.4
Amberlite LA-1
Secondary
1.5
0.02
0.03
0.005
0.12
Secondary
2.5
· Di(tridecyl)
N-benzyl-1-(3-ethylpentyl)- :
4-ethyloctyl
Alamine 336
,
Secondary
Tertiary
0.03
0.04
1.5
2.5
1.5
2.5
Aliquat 336
Quaternary
0.02
. 0.06
"In previous reports this amine was identified as Amine 21781
TABLE 2. EFFECT OF PRIMARY AMINE STRUCTURE AN. DILUENT
CHOICE ON BERYLLIUM EXTRACTION
Organic phase: 0.3M amine (sulfate salt form) in indicated
diluent.
Aqueous phase: 0.02M Be, 7Be tracer, 1.8M SO , PH 2.5.
Contact:
10 min at phase ratio of 1/1.
· Berylliun
Distribution
Coefficient
Amine
Diluent
2.7
3.0
1-heptyloctylamine
l-nonyldecylamine
Primene ja
l-methyloctadecylamine (Armeen L-15)
HDA
***
.
0.096
..--
.jome
Solvesso 1008
Solvesso 100
Solvesso 100
Solvesso 100
Solve880 100
95% Solve880 100-5% TDAC
95% Solve88o 100-59 TBP
Benzene
Amsco 125-82
Kerosene
Carbon Tetrachloride
Hexone
4.7
6.5
,
9.8
7.4
8.6
21
0.3
High flash point aromatic petroleum product
0.15M amine
CTDA - tridecano1
(High flash poiat aviation naphtha
tetrachloride gave the highest berylllum distribution coefficients (Table
2). Also, coefficients were slightly higher and phase separation more
rapid with aromatic diluents, such as benzene and Solvesso 100, then with :
aliphatic diluents. Modifying the diluent with tridecanol or TBP depressed
the extraction power but usually speeded phase separation.
Effect of pH and Contact Time
The beryllium extraction efficiency increases rapidly with decrease
in acidity of the aqueous phase. In extractions with 0.3M HIDA In Sol-
vesso 100 from 1.8m sulfate solution, the beryllium distribution coeffi-
cient Increased from 0.3 at pH 1 to 3.5 at på 2 and 17 at pH 4 (Fig. 1).
Beryllium extraction was rapid. At a pH of 2 or below, equilibrium was
reached within one minute (Fig 1). At higher pH's more than 90% of the
attainable extraction occurred within about one minute, but there was
a slow increase in the magnitude of the distribution coefficient up to
contact times of one hour.
Beryllium Loading
Isotherms for extraction of beryllium into 0.3M HDA in Solvesso 100
from 1M sulfate solution leveled off at about 0.5 g/ beryllium loading,
equivalent to 1 mole of beryllium per 5-6 moles of amine (Fig 2). The
initial portions of the extraction isotherms show a slight curva ture
with the distribution coefficient decreasing with decreasing beryllium
concentration in the aqueous phase. However, this is of little apparent
process importance since it occurs in the very dilute region (< 0.02 8
Bel1 in the equilibrium aqueous phase) and therefore imposes no significant
limit on attainable recoveries.
1
Effect of Sulfate and Amine Concentration
Increasing the sulfate concentration from 0.1 to 2%, at a constant
på of 2.5, approximately doubled the beryllium distribution coefficient.
This is shown in Figure 3 for tests with FDA and Primene JM.
The beryllium distribution coefficient is proportional to about
the 0.7 power of the FDA concentration in the range 0.01 to 0.34 (119
4). Consequently, with a given amount of anine, the extraction effi.
ciency is incrused by decreasing the anine concentration. This is
done, however, at the expense of decreasing the bery1111 backwashing
efficiency, if the sulfuric acid backwashing method is used. Distri-
bution coefficients for alusinun, which is an important contaminant
in beryllium ore process liquors, have approximately the same power
dependence on smine concentration as do those for beryllium (11& 4).
The ability to separate beryllium from aluminum, therefore, is not
changed by changing the extractant concentration. Use of relatively
high amine concentrations is desirable since, even at 0.39 concentra-
tion, beryllium loadings on a weight basis are relatively low. From
these considerations, 0.32 anine concentration has been tentatively
chosen as optimum for process tests.
Interference from Fluoride and Aluminum ,
Fluoride interferes severely with beryllium extractions from sul-
fate solutions by complexing beryllium in the aqueous phase. In exa
tractions with 0.1M HDA in diethylbenzene from 0.5% sulfate solution
at 2.5, adding one mole of fluoride per mole of beryllium decrused
beryllium distribution coefficients by a factor of 15 (Table 3).

TABIL 3. ZTICI O FLUORIDE ON BERYLLIUM EXTRACTIONS
Organic phase: 0.17 HDA in diethylbenzene
Aqueous phase: 0.571 sulfate solutions con-
talning 0.012 Be and Owne 0.04
1, PH 2.5
Phase ratio:
Aqueous fluoride
Concentration (1)
Beryllium Distribution
Coefficient (0)
0.0
3.7
0.01
0.25
0.11.
0.02
0.06
0.10
Aluminum interferes with beryllium extraction by competing for
the amine extractant. Although the a luminum distribution coefficients
are low (Fig. 4), its concentration in beryllium ore leach liquors is
usually high enough to interfere significantly with beryllium extraction.
For example, adding 0.37 moles of aluminum per liter to a 0.01M beryl-
lium sulfate solution decreased the beryllium distribution coefficient
for 0.3M HDA from 6.7 to 0.42 (Table !). As described above, fluoride
interferes with beryllium extraction from pure solutions, but its pre-
sence in solutions containing aluminum is desirable since it complexes
the aluminum in the aqueous phase and thereby reduces a luminum competi-
tion for the amine extractant. Beryllium extractions improved on addi-
tion of fluoride up to amounts approximately equivalent to the aluminum
and then decreased with further fluoride addition (Table 4).
EXTRACTIONS FROM LEACH LIQUORS
Since primary amines extract ferric iron strongly, the iron in ore
leach liquors must be reduced to the ferrous state prior to extraction.
The increase in beryllium extraction efficiency with decrease in the
aqueous acidity 18 less pronounced in extractions from leach liquors
compared to extractions from beryllium sulfate solutions. This may mean
that the aluminum distribution coefficients increase more rapidly than
the beryllium coefficients with increasing pH but this has not been veri-
fied experimentally. In.extractions with 0.3M HDA from a synthetic leach
liquor containing 0.5 g of Be, 5 8 of A1, and 2.5 8 of F* per liter, the
beryllium distribution coefficient increased from 0.7 at pH 105 to 142 at
TABLE 4. EFFECT OF ALUMINUM AND FLUORIDE ON BERYLLIUM EXTRACTION
Organic phase: 0.3M HDA in Solve880 100
Aqueous phase: 0.01M Be, 7Be tracer, 1.4M 8042, Al and F" as shown
Contact:
10 min at 1/1 phase ratio
Initial Aqueous
Analysis (M)
Fluoride Aluminum
Mole Ratio
Beryllium
Distribution
Coefficient
Α1
0.0
6.7
0.37
0.0
.
0.0
0.428
0.37
0.05
0.15
O.
0.47
0.55
0.37
0.37
0.10
0.20
0.6
0.71
0.37
1.1
1.8
w
0.37
2.2
a
0.07
The organic phase .contained 0.88 g of Al per liter
10
PH 2.0 and to 1.5 at pH 2.5 (F18 5). Somewhat lower distribution coef-
ficients, i.e., 0:8 at pH 2.0 and 1.0 at pH 2.5, were obtained in ex-
tractions from an actual ore leach liquor (see analysis below). These
coefficients, although low, are high enough for process use. Isotherms
for extraction of beryllium from the synthetic leach liquor at pH 2.5
and 25°C show a maximum beryllium loading of about 0.33 grams per liter
(Fig. 6). Extractions are lower at 50°C which is opposite to the temp-
erature effect observed in extractions from pure solutions (results not
shown).
Control of Aluminum Contamination
.
Since beryllium is extracted more strongly than aluminum, aluminum
contamination of the beryllium extract can be controlled by saturating
-
.
-
-
-
-
-
-
-
the solvent with beryllium. In a countercurrent extraction system, the
-
-
-
relatively large amounts of aluminum extracted in the lower stages are
displaced from the solvent with beryllium in the upper stages. Typical
stage data (Fig. 7) from a batch countercurrent run in which beryllium
was recovered from a synthetic leach liquor with 0.3M HDA in Solve880
100 show the A1/Be weight ratio in the organic phase decreasing from
2.7 to 0.046 with increase in beryllium concentration in the solvent
phase from 0.11 to 0.44 grams per liter. Further separation from a lumi-
num may be obtained, if desired, by scrubbing the extract with dilute sul-
furic acid (0.002-0.01M) prior to backwashing. Ethylenediaminetetraacetic,
acid and dilute fluoride solutions are also effective for scrubbing but
are more costly.
BACKWASHING BERYLLIUM
Beryllium 18 backwashed readily from the amine extract with 0.5-IM
sulfuric acid, chloride solutions, or alkaline solutions (Table 5). Ni-
.
trate solutions were not tested but should be even more efficient than
chloride solutions. Backwashing with dilute fluoride solutions coupled
with subsequent dilute sulfuric acid backwashing has also shown promise.
This method and the sulfuric acid backwashing method are preferred over
the other methods because of lower chemical reagent costs.
In backwa shing with sulfuric acid, most of the acid is fed to the
second stage of a four stage system and water or very dilute sulfuric
acid is fed to the last stage. With this arrangement, acid is scrubbed
from the solvent (the amine is converted from the bisulfate to the sul-
fate form) in the last two stages and the efficiency of acid utilization
is increased. Since the barren solvent contains little amine bisulfate,
it can be recycled directly without causing a large pH drop in the ex-
traction system. Typical distribution data (Table 6) show more than 99%
recovery of beryllium from the extract in four stages using 17 pounds of
sulfuric acid per pound of beryllium oxide. This amount of acid could
have been decreased since the backwa shing in this test was essentially
complete in two stages.
Sulfuric acid oz chloride backwa shing is accomplished primarily
by providing anions which compete with the beryllium sulfate complex
for the amine extractant. In contrast, backwashing with fluoride occurs
primarily through formation of strong beryllium complexes in the aqueous
phase. Fluoride requirements, in this case, therefore, depend much more
on the amount of beryllium rather than the amount of amine in the system.
.
.
"
12
TABLE 5. BACKWA SHING BERYLLIUM FROM AMINES
Organic phase: 0.3M HDA in Solvesso 100 loaded
with about 0.2 g of Be per liter
Contact time: 10 min
Stripping Solution
Phase
Ratio (o/a)
Amount Distribution
Backwashed (%) Coefficient (D)
4/1
1.1
0.1M H2SO4
0.2M H2SO4
4/1
4.3
0.077
0.5M H2S04
0.20
10/1
10/1
10/1
10/1
IM H2S04
3M NaCl-0. IM H2SO4
0.5M Oxalic acid
1.5M NaOH"
0.043
0.0067
2.5/1
V.
b
.
V
3/1
2/1
0.75M Na2CO3
3/1
24
..
.
"Initial organic phase contained 0.38 g of Be per liter
About 90% of the backwashed beryllium dissolved in the strip solution
about 35% of the backwashed beryllium d188olved in the strip solution
,
.
TABLE 6. BATCH COUNTERCURRENT BACKWASHING OF BERYLLIUM
WITH SULFURIC ACID
Organic phase:
Backwash solution:
0.3M FDA in Solvesso 100 loaded with 0.28 &
of Be per liter
0.01M H2S04 (fed to the fourth stage); 6M
H2SO4 (fed to the second stage)
organic/0.01M H2SO4/6M H2SO4 = 8/1/0.18
Flow ratics :
Stage
Beryllium
Distribution
Coefficient (D)
PH
.
Be Conc. (alliter).
Organic. Aqueous
1
0.5
0.051
2.1
0.024
2
0.46
0.1
0.6
1.2
0.0043
0.0035
0.00218
0.0095
0.071
0.05
0.01
0.20
"Barren organic phase contained 0.19 sulfate
-
-
-
-.
--.-.
-
-
-
...
- -
- -
- -
-
-
-
-
-
-
-
-
--
-
--
-
-
-
-
-
-
-
--
----
-
-
-
-
-
--.
-.
--.-
-
-
-
-
14
Results have been best with about one equivalent of fluoride per equiva-
lent of beryllium in the extract. With larger amounts of fluoride, less
beryllium 18 backwashed, presumably due to the formation of some extract-'
able beryllium fluoride complexes. The total amount of beryllium back-
washed in batch tests increased from 75% with a fluoride/beryllium mole
ratio of 1.1/1 to 96% with a ratio of 2.3/1 and then decreased to 80%
with a ratio of 4.6/1 (F1g 8). In these tests the extract was contacted
first with an ammonium fluoride-ammonium sulfate solution and then with
four successive volume 8 of 0.01M H2S04. Each contact was at an organic/
aqueous phase ratio of 6/1. Sma 11 amounts of fluoride, extracted in the
initial contact, greatly enhance the efficiency. In subsequent backwashing
with 0.01M H2S04. In a batch countercurrent demonstration of this back-
washing method, about 95% of the beryllium was recovered from 0.3M HDA
in Solvesso 100 in 5 stages (Table 7). In one promising flowsheet, the
backwa sh solution is neutralized with ammonia to precipitate beryllium
and is then filtered. Some of the filtrate (which contains fluoride)
18 recycled to the first backwashing stage to decrease requiredients for
make-up fluoride.
The products obtained by precipitating beryllium from the backwash
solutions with ammonia usually contain a few percent of aluminum and
may also conta in other contaminants (see below). Most of the aluminum
can be selectively redissolved from the precipitate by reslurrying it
in dilute caustic (pH ~12.5) but this provides no decontamination from
most of the other metal contaminants. Complete redissolution of the
beryllium precipitate in excess caustic followed by filtration to re-
move undissolved contaminants and dilution and heating to hydrolyze and
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TABLE 7. BATCH COUNTERCURRENT BACKWASHING OF BERYLLIUM
WITH FLUORIDE SOLUTIONS
..:: -
.;.,.'-,'m...-... rat.
Organic phase: 0.3M HDA in Solvesso 100 loaded to 0.27 g
of Be per liter from a leach liquor
Backwash solution: 0.4M NH_F_0.15M (NH4)2S04 solution fed
to first stage; 0.01M H2S04 fed to fifth
stage
Flow ration: organic/0.4M NH4F-0.15M (NH4)2S04/0.01M2
H2SO4
.' .".
.
Stage
- Be Conc. (8/liter)
Organic
Aqueous
0.093
..19
0.071
..
0.047
0.029
0.015*
----
-
5. ... ... :
0.09
-
-
--
-
Barren organic phase contained 0.007M F"
-

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precipitates the beryllium 18 an alternative treatment method that
should give purer products.
PROCESS DEMONSTRATIONS
A process based on the information outlined above has not been
tested in continuous equipment but batch countercurrent extraction runs.
have been made with 0.3M HDA in Solvesso 100.
In treating a synthetic
leach liquor (pH 2.9, analysis in Fig. 5), 92% of the beryllium was re-
covered in six stages of extraction and four stages of scrubbing with
0.01H2SO4. The organic aqueous feed/scrub ratios were 10/7.6/2.5.
Beryllium distribution coefficients ranged from 0.9 in the feed stage
to 1.6 in the last extraction stage. Beryllium was backwa shed from the
scrubbed extract with IM H2S04, precipitated with NH2OH, and the preci-
pitate was reslurried with dilute caustic to increase the separation
from aluminum.
The product contained about 0.3% Al based on the beryl-
lium content.
Another demonstration run was made with an actual leach liquor
supplied through the courtesy of the Salt Lake City Station at the U.
11
S. Bureau of Mines. The liquor was prepared by sulfuric acid leaching
of ore from Spor Mountain, Utah, and contained (in grams per liter):
0.65 Be, 4.0 A1, 2.3 Fe, 8 F, and 110 804. As mentioned above, coeffl-
cients for extraction of beryllium from this liquor were appreciably
lower than from the synthetic liquor but beryllium was recovered effec-
tively by operating at a higher organic/aqueous flow ratio. The recove
ery was about 96% complete in six extraction and two scrub stages with
17
backwashing with sulfuric acid, precipitating with ammonia, and reslur-
rying the precipitate in caustic contained 1.1% Al based on the beryl-
method described above will give products of higher purity.
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REFERENCES
1. Hardy, C. J., Greenfield, B. F., and Scargill, D., J. Chem. Soc.,
G. B. 6961) 1. 174.
2. Cattral, R. W., Austral. J. Chem., 14, 163. (1961).
3. Crocker, L., Dannenberg, R. O., Bridges, D. W., Rosenbaum, J. B.,
Recovery of Beryllium from Spor Mountain, Utah, Ore by Solvent
Extraction and Caustic Stripping, U. S. Bureau of Mines Report
RI-6173 (1963).
4. Dannenberg, R. O., Crocker, L., and Bridges, D. W., Expanded In-
vestigation of Beryllium Solvent Extraction of Spor Mountain, Utah, .
Ore, U. S. Bureau of 'Mines Report of Investigation 6469 (1963).
5. Wells, R. A., Everest, D. A., and North, A. A., Nucl. Sci. Eng., 11,
259 (1963).
6. Moore, J. D. and Lash, L. D., Mining Congress Journal, 1, 44 (1963).
7. de Bruin, H. J., Kairaitis, D., and Temple, R. B., Austral. J. Chem.,
15, 457 (1962).
8. V. S. Atomic Energy Commission Reports, ORNL-1734 (1954), ORNL-1922
(1955), ORNL-3030 (1960).
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Organic phase: 0.3M HDA in Solvesso 100, Aqueous phase: Syn-
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......
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Organic phase: 0.3M HDA in Solvesso 100. Aqueous phase: syn-
thetic leach liquor (analysis in Fig. 5), PH 2.5.
..-
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ALUMINUM/BERYLLUM WEIGHT RATIO IN ORGANIC PHASE
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----
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---
Fig. 7. Control of Aluminum Contamination by Loading with Beryllium (stage
data from batch countercurrent test). Organic phase: 0.3M HDA in
Solvesso 100. Aqueous phase: synthetic leach liquor (analysis in
Fig. 5), pH 2.
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Fig. 8. Backwashing Beryllium with Fluoride Solutions. Organic phase: 0.3M
HDA in Solvesso 100 (loaded to 0.29 g Be/1). Procedure: organic
phase contacted with 0.1M (NH4)2SO4 solutions containing 0.23
0.93M NH4F and then with four successive volumes of 0.01M
ive volumes of 0.01M H2504
(all contacts at an organic/aqueous phase ratio of 6/1).
.
END


DATE FILMED
10/ 27/65
15
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