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PTER SEVENTEEN
-
Solvent Extraction
INTRODUCTION
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EXTRACTANTS
Solubility
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Ethers .
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Alcohols .
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Aldehydes
Ketones .
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Oximes .
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Organic acids .
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Phenols .
Esters
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Amines . . . . . . .
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Otherextractants .
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THEORY
Mechanism .
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Extraction
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Stripping
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Extraction isotherms
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THE ORGANIC PHASE .
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Solventloading .
Nature of the extracted species .
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Polymerizationofextractant
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JRoleofdiluents .
Effect of extractant concentration
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Extraction by mixed solvents
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Third-phase formation
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332
ENGINEERTNG ASPECTS
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Percent extraction
Phaseratio . . .
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Separation factor .
Multiple extractions .
Countercurrent extraction
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Equipment .
Economic aspects . .
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375
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369
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373'
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. 382
APPLICATIONS .
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Recovery .
382
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Beryllium
Boron . . . . . . . . . . . . . . . . . 383
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Cesium .
383
Copper . . . . . . . . . . . . . . . . 383
Gold and silver .
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Thorium . . . . . . . . . . . . . . 384
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Tungsten
385
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Uranium
385
Separation . . . . . . . . . . . . . . . 385
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. 359
cobalt-nickel
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Hafnium-zirconium
389
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..
Niobium-tantalum
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Plutonium-uranium-fission products
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. 390
...
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Scandium-uranium
. . . . . . . . . . . 392
Vanadium-uranium
LITERATURE
"
'392
1NTRODUCTION
SOLVENT
EXTRACI ION involves two operations :
1 ) Extraction The metal values in the aqueous phase are extracted by
agitation with a n organic solvent immiscible in that phase . The two phases
are then allowed to separate; the aqueous phase is discarded or recycled. and
the loaded organic phase saved .
So1;ent estractiorz
333
2) Strippirlg Recovery of the metal values from the loaded organic phase
by agitation with a small volume of suitable solution. The stripped solvent
is then recycled. In this way a concentrated solution containing the metal
values in a relatively pure f o ~ mis obtaiped (Fig. 17-1).
Organic
phose
(Loaded)
Leoch
solution
'
J.
Extraction
Stripping
.f
Organic
phose
recycle
(unloaded)
t I
Barren
solution
(roffinate)
Pure metol
solt for reduction
to metol
Strip
solution
Recovery
PPrecipitating
'
Strip
solution
recycle
Ogent
The earliest record known in which an organic solvent was used to extract
metal ions is by PCligot,* who in 1842 observed that uranyl nitrate is
.appreciably soluble in diethyl ether, and used this property for separating
uranium from other constituents of pitchblende. Based on this discovery,
about one hundred. years later. (from 1942 to 1953), the Mallinckrodt
Chemical Works operated a uranium refinery for the U.S. Atomic Energy
Commission (the Manhattan Project).
The first large-scale use of solvent extraction in metallurgy was in connection with preparing uranium containing < 1 ppm of contaminants for the
atomic energy program. This requisite purity was obtained by dissolving
high-grade ore or concentrate in HNO,, selectively extracting the uranyl
nitratc into ether, and stripping the ether with water to give.a conzentrated
solution of pure uranyl nitrate. In 1953 the National Lead Company used
tributylphosphate as the extractant, and subsequently the Mallinckrodt plant
also converted to the use of this reagent.
In 1951 the U.S. Bureau of Mines in cooperation with the U.S. Atomic
334
Prir~ciples'of e.~tractivemetallurgy
So/tient extraction
EXTRACTANTS
An ideal extractant should fulfill the following requirements:
1) Selectivity
3) Easily stripped
4) Separates easily from water, i.e.,
a) Density is appreciably different
b) Low viscosity
c) High surface tension
5) Safe to handle, i.e.,
a) Nontoxic
bj ~ o n f l a h a b l e
c) Nonvolatile
* Very few cases are known in which a diluent can extract metal ions from solutionsee p. 348.
76.1
45
153.82
76.14
61.2
119.38
Non flammable.
Chlorofornl
Carbon
tetrachloride
Carbon
disulfide
Substituted
hydrocarbons
81
84.16
Benzene
Toluene
o-Xylene
m-Xylenc
p-Xylene
Aromatic
hydrocarbons
"C
Boiling
point,
Hydroaromatics Cyclohexane
11-Hexanc
Kerosene
Naphtha
Compound
Aliphatic
hydrocarbons
Group
Molecular
weight
1.2628
1.5942
1.4916
0.779 1
Density
at 20C
0.37
0.969
0.58
I .O
CP
Viscosity
at 200C,
270
temp.,
"C
Spontaneous
ignition
1.02
esu
Dipole
moment,
IO ~ s
2.641
2.238
4.806
1.890,
Dielectric
constant
at 20C
;
i
-r
Soluent extraction
337
Ethers
Simple ethers are light, volatile, and highly flammable liquids having the
general formula R.O.Rt. The most commonly used &her is diethyl (Table
17-2), which is simply called ether. Many metal ions are extracted by ether
from HF, HCl, and HNO, solutions, but not from H,SO,. The extracting
power of ethers decreases with increasing molecular weight.
Table 1722. Physical properties of some ethers.
.
Diethyl
B-, B'-dichloro-,
ether
diethyl ether
34.6
- 45.0
7.5
1.3
178.0
75.6
1O
.
0.717
0.23
1.222
2.06
Alcohols
Monohydric alcohol., may be primary, secondary, or tertiary:
R
R-COH
R-CH20H
R
Primary
22 Habashi. Metallurgy 11
Secondary
Tertiary
338
The lower members are soluble in water, and the solubility decreases with
increasing molecular weight. The solubility of n-octyl alcohol (or 1-octanol),
CH3 . (CH,), .OH, is 0.03 g in 100 g water. It is used, for example, in separating cobalt from nickel.
Aldehydes
A commonly used aldehyde is furaldehyde or furfural,
Ketones
A commonly used ketone is methyl-isobutyl ketone, known as hexone
(Table 17-3).
CH3
I
CH3
Hexone
Table 17-3. Physical properties of methyl isobutyl ketone (hexone).
Specific gravity
Boiling point, "C
Vapor pressure at 20C, mm H g
Flash point, "C
Solubility in water, Val%
Solubility of water in hexone, Val%
Viscosity at 20C, centipoise
0.8024
116
15.7
27
-7
2.2
0.585
Solvent extraction
en01 forms, as shown below
C-OH
II
C=O
Keto
C=O
CH3
CH3
En01
Acetyl acetone
rl
~~L!-cH~-c-cF~
+ l
0
I1
11
OH
S / - ~ - ~ ~ = ~ - ~ ~ 3
Keto
En01
Thenoyl trifluoroacetone
Oximes
Oximes, i.e., compounds containing the group =N-OH, have been used.
for many years in analytical chemistry as precipitants for metals. The orhydroxyoximes are well known as specific for precipitating copper, e.g.,.
Salicylaldoxime
2-Hydroxy-5-dodecylbenzophenone oxime and 5,8-diethyl-7-hydroxy-6dodecanone oxime are finding extensive use in extracting copper from leach
solutions, under the trade names LIX-63 and LIX-64, introduced to the
market by the General Mills Corp.
Dioximes, i.e., compounds containing the (=N-OH), group, e.g., dime-.
thy1 glyoxime, have also been known for many years as chelating agents.
for metals. Dimethyl glyoxime is specific for nickel:
H3C
CH3
C-C
I1 II
N N
,
'
HO
\
OH
Dimethyl glyoxime
340
Organic acids
Many organic compounds exhibit acidic properties, but in this section only
those which contain the carboxyl group and are of metallurgical interest are , .
included.
1
a) Fatty acids, R.COOH The low members are soluble in water and the
solubility decreases with increasing molecular weight. Numerous acids have
Table 17-4. Phenols suggested as extractants.
p-Dodecyl phenol
/==\-R
\--/
R
o-Phenyl phenol
OH
I
4-Chloro-2-phenyl phenol
4-sec-Butyl-2(&-methyl)benzyl phenol
-I\
CH,~HCH~CH,
Polyol
I
R - / \ O H
\-- /
I
Soluent extraction
341
b) Naphthenic acids are carboylic derivatives of cycloparaffin hydrocarbons, having a structure as shown:
They are derived from crude petroleum oils and have a variable composition.
The molecular weight varies from 170 to 330.
Table 17-5. Acidic organic phosphorus compounds.
Group
Example
Abbreviation
D2EHPA
CHz . CH3
RO-P-OH
I
OR
DDPA
OPPA
RO-P-0-P-OR
HO OH
d) Dialkyl phosphinic acid
0
I
R-P-OH
I
R
e) Monoalkyl phosphonic acid
0
I
R-P-OH
Example
Tributyl phosphate
R is C,H,
Abbreviation
TBP
I
RO-P-OR
I
OR
b) Trialkyl phosphine oxide
0
I
R-P-R
I
R
c) Alkyl dialkyl phosphinate
0
I
R-P-OR
I
R
I
R-P-OR
I
OR
Phenols
Phenols, in which a hydroxyl group is attached to an aromatic nucleus, are
more strongly acidic than alcohols. Table 17-4 shows some phenols of
metallurgical interest. Polyol is used on commercial scale for boron extraction.
Esters
Esters are formed by the reaction of alcohols with inorganic acids. Those
used in extractive metallurgy are derived from phosphoric acid and can be
classified into acidic esters (Table 17-5) or neutral esters (Table 17-6).
Phosphoric acid is introduced in the form of P 2 0 5 or POCl,. A mixture of
products is generally obtained, and compounds formed from the hydrolysis
of the products are common. Moreover, dehydration of the alcohol by P 2 0 5
343
Solfient extraction
OH
OH
I
I
2 ROH + P 2 0 j +RO-P-0-P-OR
I
I
+ P 2 0 5+(RO)(H0)2PO + (RO),(HO)PO
+ P 2 0 5+2 (RO),PO
Ro-A-0-LOR
+ H,o
-r
2 Ro-A-OH
344
A few of the chelating agents that are used extensively in analytical chemistry
and may be of potential metallurgical importance are mentioned below:
,
Group
Primary
RNHz
Example
Abbreviation
or synonym
Trialkyl methylamine
Primene JM
CH3C(CH3)2CHzC(CH3)2CH2C(CH3)2CH2-
Dilaurylarnine
Arrneen 212
Amine S 24
Dodecenyltrialkylmethylamine
Amine 9D-178
346
Group
Abbreviation
or synonynl
Example
CH2CH3
NH
Tertiary
R
R"
Tri-11-octylamine
R
1
R N where
(TOA)
R/
CH3CH2CH2CH2CH2CH2CH2CH2Tri-iso-octylamine
CH3
N(CH2CH2CHCH2CHCH3)3
A mixture of tri-n-octylamine and tri-rr-decylamine
Butyldilaurylamine
CH3 CH3
(TIOA)
CH3
CH3CCH2CCH2CH=CHCH2
AH3 AH3
Tribenzylamine
Alamine 336
348
Solvent extraction may be physical or chemical in nature. Physical processes are very few and in these, Nernst's distribution law is usually obeyed.
Examples of such processes are the extraction of arsenic, antimony, germanium, and mercury from hydrochloric acid solutions by hydrocarbons or
chlorinated hydrocarbons such as benzene, carbon tetrachloride, or chloroform. Such solvents are usually used as diluents in other extraction systems
because of their inertness.
In the majority of cases, however, solvent extraction is a chemical process
and Nernst's distribution law is not obeyed. In these processes metal ions,
or uncharged species in the aqueous phase enter into interaction with the
extractant, and the reaction product (organometallic complex*) is soluble
in the organic phase. Interaction takes place in one of the following ways:
1) Ion-pair transfer In this case electrically neutral molecules interact
with the extractant to form an addition compound. The most suitable
extractants for such interaction are those having an oxygen atom with a lone
pair of electrons, e.g., ethers, alcohols, and the neutral phosphoric acid
esters. For example, diethyl ether extracts iron ,from hydrochloric acid
solution as follows:
CZH5
)O + HFeCI,
CZH5
C2H5
)O . HFeCI,
CZH5
where R
C,H,.
2 ) Iorl exchange In this type the metal is transferred from the aqueous
phase as a simple ion, and at the same time an ion from the extractant is
transferred stoichiometrically to the aqueous phase.
a) Cation exchange The extracted species is a positively charged ion
and the extractant is an acid, e.g., monoalkyl phosphoric acid, dialkyl
phosphoric acid, alkylpyrophosphoric acid, carboxylic acids, naphthenic
acids, etc. For example, the extraction of uranium by a monoalkyl phosphoric
* This'terrn should not be confused with organometallic compounds in which the metal
is attached directly to carbon.
It can.be seen that one uranyl ion is exchanged for two hydrogen idns.
b) Anion exchange The extracted species is a negatively charged ion
and the extractant is a base, e.g., an amine,
RNH,
+ HCI +RNH2CI-
CH3
C-OH
C-0
A
2 HC
CH3
+ BeZ++HC
0-C
\\
Be
;I
'.\
CH
+ 2H'
,/
Belonging to this group are the diketones, oximes, oxine, nitrosonaphthols, cupferron, and dithizone.
Stripping
In the stripping process, two purposes are achieved:
1) Recovery of the metal values from the organic phase.
2) Regeneration of the extractant for recycle.
When an organic molecule containing both acidic and basic functions combines with
a metallic ion, and if in the combination both functional groups are operative, a so-called
inner-complex or chelate salt is formed.
350
The higher the value of D' at equilibrium, the higher is the tendency of the
metal ion to be transferred to the aqueous phase. The stripping coefficient is
the inverse of the distribution coefficient D.
Stripping agents. depend on the mature of the extraction mechanismwhether ion-pair transfer or ion exchange. Ethers and neutral organic
phosphorus compounds such as TBP are readily stripped by water.
Acidic organophosphorus compounds may be shipped by acids or bases.
The acid method employs a concentrated acid to reverse the following
reaction :
+ H2X + M,X + 2 H+
MZ+
Thus for the stripping of uranium, the following acids are used:
a) 48 % H F In this case uranium is precipitated as UF,. Higher concentrations of H F result in excessive deterioration of the solvent. Lower
concentrations cause losses due to emulsion formation. Contact time should
be only 15 sec: longer contact should be avoided.
b) 20 % H F + 20 % H,S04 In this case the rate of deterioration decreases due to the lower concentration of H F used, and at the same time
phase separation is improved by the sulfuric acid added.
c) 10N HC1 This acid is not so effective a stripping agent as H F but
due to its lower deteriorating action on the extractant it is much used:
Excess acid is recovered by evaporation, and uranium is precipitated by
NH,OH.
351
Soluent extraction
(0)
Precipitation:
+ 4 Na2C03
+ Na4UO2(CO,),(,, + 2 Na2S04 + H 2 0 + C 0 2
~(R,NH)ZUO,(SO~);(O)+ 5 MgO
+ 4R3N(o) + MgUzO,(,) + 4 MgSO,(,, + 2 H z 0
+ 2 R,N(,,
Extraction isotherms
The plot of the concentration of the metal ion in aqueous phase versus its
concentration in the organic phase when the two phases are in equilibrium
Fig. 17-2. Metal extraction from 0.5Msulfate solutions with 0.1 M DZEHP
in kerosene [Blake et al. (1 958)l.
352
Principles of.extractiue~metallurgy
T H E O R G A N I C PHASE
Solvent loading
A certain weight of an extractant has a limited capacity for extracting a certain metal ion from solution. When this limit is reached theextractant is
then saturated with the metal ion and is said to have reached its maximum
loading. Maximum loading varies widely from one extractant to the other.
The organic phase increases in viscosity with increasing metal ion loading
(Fig. 17-3) and sometimes it is necessary to operate at a solvent loading substantially below the maximum loading of the extractant. Saturation concentration can be determined by cintacting the organic phase several times
with fresh aliquots of the.aqueous phase until the amount of metal in the
organic phase becomes constant. For example, Table 17-9 shows saturation
data for the extraction of thorium from sulfuric acid' solution by di-(2-ethyl
hexyl):phosphoric acid at different pH values.
.
353
Solvent extraction
'
"
"
'
0.4
0.8
1.2
Uronium concentration in TBP, M
3 54
Table 17-9. Saturation of the organic phase in the extraction of thorium. Organic phase:
10 ml of di (2-ethylhexyl) phosphoric acid in kerosene; aqueous phase: 10 ml of 0.1 M
H2S04containing 2 g/l Th [Tedesco el al. (1966)l.
pH
1.5
2.0
2.6
3.0
D2EHPA,
M
Wt. of D2EHPA
in 10 ml,
mM
Wt. of Th
extracted,
mM
Molar
ratio,
D2EHPA/Th
0.407
0.207
0.120
0.407
0.207
0.120
4.07
2.07
1.20
4.07
2.07
1.20
1.07
0.54
0.31
1.20
0.64
0.36
3.80
3.83
3.87
3.39
3.23
3.33
0.407
0.207
0.120
0.407
0.207
0.120
4.07
2.07
1.20
4.07
2.07
1.20
1.20
0.65
0.37
1.25
0.59
0.36
3.39
'3.18
3.24
3.25
3.57
3.33
It should be pointed out that when micro amounts are extracted (trace
concentrations), the extracted species may be different from those when
macro amounts are extracted. Thus Vdovenko et al. (1961) showed that,
when trace concentrations of thorium were extracted from H2S04 solutions
by primary octylamine, the extracted species was 2 (RNH,),SO,. Th(S04), .
When, however, macro amounts (0.0086-0.029M) were extracted by the
same solvent, the extracted compound when separated from the organic
phase analyzed as (RNH,), Th(S04), .
Infrared and nuclear magnetic resonance measurements are used extensively to identify the nature of the extracted species in the organic phase.
Polymerization of extractant
Some amines tend to associate in polar hydrocarbon diluents and remain in
stable colloidal dispersion (Brown el al., 1957).~~ialk~l~hos~horic
acids and
the dialkylphosphinic acids are often dimeric'in the organic diluent, presumably by hydrogen bonding (Baes et al., 195:):
In the case of the monoalkylphosphoric acids, ROP03H,, and the monoalkylphosphonic acids, RP03H,, larger polymers'have been found by Kosolopoff and Powell (1950). Such polymerization directly affects cation exchange, since the hydrogen atoms are not free to react.
Solvenr extraction
355
'
- -
System
Th4+-HzS04-octyl
amine
- -
Extracted species
Th(S04)~. (RNH3)z
FeOH(S04)2 . (R2NHz)z
UO:+-~~S0~-dioctylamine
UOzS04. 2 (R2NH2)2S04
HzPtC16-HzS04-trioctylamine
UO:+-~~S0,-trioctylamine
PtC16(R3NH)2
Deptula (1966)
~0:+-~~0~-trioctylamine
UO:+-HCI-trioctylamine
UO:+-HNO~-D~ethylether
U 0 2 S 0 4 2 (R3NH),S04
U 0 2 S 0 4 .'2 (R3NH)$04. 3 H 2 0
U 0 2 S 0 4 . 2 (R3NH),S04. n H 2 0
UO2(NO3j3 . R3NH
U02(N03)4 . (R3NH)z
UOzC14. (R3NH)z
2 TBP
~ r ( ~ ~ ) - ~ ~ l - t r i b u t HCr03CI.
~l
phosphate
La(N03)3 . 3 TBP
La(N03),-tributyl
phosphate
MO(1V)-HCI-tributyl
I M O O ~ C I2~TBP
.
phosphate
Niobium fluoride-tributyl HNbF6 . 3 TBP
phosphate
HNbOCI4. 3 TBP
NbC1,-HCI-tributylphosphate
HPtCI, - 3 TBP
Pt(1V)-HC1-tributyl
phosphate
HPtCI, . 2 TBP
H2TaF7 . 2 TBP
Tantalum fluoridetributyl phosphate
er
al. (1965)
356
Extracted species
U(N03), . 2 TBP
U 0 2 ( N 0 3 ) 2 ' 2 TBP
UC14-tri butyl
phosphate
UCI,. 2 TBP
UCIL. 3 TBP
HVOICll. 2 TBP
V(V)-HCI-tributyl
phosphate
W(V1)-HC1-tributyl
phosphate
/H'..
(RO)Z-P\ / O
/"\<
O > P-(0R)2
"."/
Dialkylphosphoric acid
dimer
R2-P / O
\P--R~
\o
0'
\H/
Dialkylphosphinic acid
dimer
Role of diluents
The diluents themselves are unable to extract metal ions from the aqueous
phase, but they greatly affect the extraction behavior of the solvent
(Tables 17-11 and 17-12). The reason is the interaction that may take place
between the diluent and the extractant. Further, some diluents favor thepolymerization of the extractants while others do not. Calorimetric measurements usually give a good indication about such interaction.
Afanasev et al. (1966) found that mixing tributyl phosphate with heptane,
nonane, and decane was accompanied by absorption of heat, while mixing
with' chloroform and carbon tetrachloride was accompanied by liberation
of heat. The endothermic effect in the first case is due to the dissociation of
TBP dimers in the hydrocarbon diluent, while the exothermic effect in the
second case is due to the association of TBP with the chlorinated hydrocarbons to form CHCl, . TBP and CCl, . 2TBP. Such a bond considerfbly
reduces the effective concentration of TBP in the organid phase, which is
Solvent extraction
Table 17-11. Effect of diluent on the extraction of uranium from
sulfate system by D2EHPA [Blake e! a/. (1958)l.
Kerosene
Carbon tetrachloride
Benzene
Chloroform
2-Ethylhexanol
Dielectric
constant
Distribution
ratio
2.0
- 2.2
2.3
4.8
10
135
17
13
3
0.1
the cause for the low extraction capability of TBP solutions in chloroform
and carbon tetrachloride.
Correlation between the effect of a diluent and its dielectric constant is
sometimes feasible. In extraction by cation exchange mechanism, the diluents
having the least dielectric constant, e.g., kerosene and CCl,, lead to the best
extractions (Table 17-11). This is because such diluents do not favor polyTable 17-12. Effect of diluents on the Extraction of uranium from sulfate system by
different amines [Coleman et al. (1958)l.
Distribution ratio
Dielectric
'Onstant
Kerosene
Benzene
Chloroform
Primene JM-T
Amine S-24
Tri-n-octylamine,
3
10
90
110
20
2
30
150
5
2 .O
2.3
4.8
- "1
1.0
10
Fig. 17-5. Metal extractions from 0.5M sulfate solutions with DZEHP in
kerosene; aqueous pH = 1 plake et nl. (1958)l.
Solvent extraction
103
lo2 -
10 -
1 -
-2 lo-' -
.-rn
(I
U
'C
L
a,
U
0
.-C0
+
L
II
0
ldZ-
1ci3-
10-3
10-~
lo-'
10
10
Concentrotion of tri-iso-octylomine in organic phose, M j l
'
K=
-
[MY nX]
[MY][XI"
-D
[XI"
+ constant
360
Principles
06extractive metallurgy
I
Blake et al. (1958) reported that when dialkyl phosphoric acid (RO),PO O H
is used in conjunction with certain neutral organophosphorus esters, such
as (RO)3P0, (R0)2HP0, (RO)H,PO and R 3 P 0 (R = 11-butyl), the extracting power of the mixture exceeds the sum of the extracting powers of the
components, as show11 in Fig. 17-7. This phenomena, called synergism, is
not confined to organic phosphorus compounds,-but applies to-many types
of organic solvents. Thus, Rosenbaum et al. (1958) reported that the combination of alkyl phosphoric acids with alkyl amines alsd showed a synergic
effect during the extraction of uranium and vanadium. Irving and Eddington
(1959-65) found similar results with mixtures of tributyl phosphate and
thenoyltrifluoroacetone (Fig. 17-8). Vdovenko and Krivokhatskii (1960) observed the same phenomenon when extracting uranyl nitrate by mixtures of
ethers (Fig. 17-9). Weaver (1961) found that a mixture of methyl isobutyl
ketone and diisobutyl ketone is a better extractant for niobium from HCI
than either of the solvents alone. Newman and Klotz (1961) found that a
mixture of TTA and tri-iso-octylamine in benzene extracts thorium from
2N HCI, whereas each of the reagents alone does not. This effect is also
dependent on the diluent.
0.1
0.2
'0
Concentrotion o f neufrol odditive, M / I
. Solvent extraction
0.5
Mole fraction of TSP
1.0
+ TB1'
M ~ x e dextractants
Dibutyl ethe!
I
100.
80
Dichlorodiethyl ether
60
40
20.
362
U01+ 4 HX +U02X2(HX)2 2 H+
U02X2(HX)2 B +U02X2(HX)2. B
This liberated solvent now can extract more ions from solution. The mechanism is supported by Dryssen (1960), Kennedy (1958), and Deane (1960).
Solvent extraction
363
this water, thus rendering the extracted species less hydrated, i.e., more
readily extracted :
, [UOlf (HzO),]
4 HX +UO2(H20), X2(HX), 2 Hf
U02(H20),X2(HX)2
+
+ JJ B +U02X,(HX)2 . J JB + x H z 0
'
Third-phase formation
Some amines, pa~ticularlythe tertiary, when in contact with mineral acids
form salts which are insoluble in the organic phase, thus a third-phaseliquid or solid-is formed during extraction. Third-phase formation also
depends on the diluent. For example, in the extraction of HNO, by methyl
dioctylamine, Choi and Tuck (1964) observed that a third phase was formed
when the amine was diluted with hexane, pentane, isopentane, and cyclohexane, and no third phase was formed when the amine was diluted with
benzene, nitrobenzene, CHCI,, and CCI,. The addition of a long chain alcohol such as n-decanol overcomes this difficulty.
The amount of decanol required to prevent the third-phase formation can
be determined in the following way: After equilibrating the organic phase
with the aqueous phase and allowing it to settle, the two organic phases are
separated and titrated with the alcohol till a single phase is formed. Usually
about 3 % alcohol is sufficient to prevent third-phase formation.
T H E AQUEOUS PHASE
Effect of metal ion concentration
For the process
MY(,,
+ nX,,,
z?MY . fix(,,
364
K[XIn
where [S] is the total concentration of extractant, and [MY nX] is the concitntration of the extractant bound to the metal species. This latter concentration increases with increasing metal ion concentratioil in the aqueous
phase. Therefore [XI and consequently D should decrease ,with increasing
metal ion concentration in the aqueous phase. his has been verified experimentally (Table 1'7-13).
Table 17-13. Distribution of
uranyl nitrate between 2M
HN03 and 40% vol.
TBP in kerosene
(Goldschmidt et al., 1956).
Soloenr exrraction
10
Concenfration of nitrate, M / I
Fig. 17-10. Extraction of uranyl nitrate by ethyl etiler using various saltingout agents [Furman el al. (1950)l.
0.1
0.2
0.3
sulfate medium by octylphosphoric acid, D decreases with increasing concentration of foreign cations, e.g., Fe3+ as shown in Fig. 17-12 (cation exchange).
0
1
2
3
4
lnitiol concentrotion o f ~ e ~ +aqueousphase,g/l
in
0.1
0
10
15
HNO, concentration, M -
Solvent extraction
367 .
2) Great excess of nitrate concentrations promotes the formation of unextractable anions such as [U02(N03),]-.
4
6
Phosphoric acid Concentration, M/ I
2
'
100
,. -
80
. ,
60
LO
20
0.01
0.1
1.0
Concentration of H3PO!,
'
, M/I
. 10.0
Solvent. ex fraction . .
369.
Effect of pH
Extraction by cationic 'solvents is greatly affected by the
of the aqueous
phase (Fig. 17-17), since H + ion's are taking part in the process:
MZ+
+ H;x>
MX
+ 2 H+
DH
370
.
,
% extraction into:
Acid
Kerosene
HN03
HBr
HCI
H2S04
H3P04
90.0
82.8;
66.0
51.1
0.7
Benzene
.
- -
97.6
95.2
85.2
86.8
25.3
Chloroform
99.0
98.5
84.8
. 92.3
, 64.4
.. .
'
. ....
'
'
372
5 o""~\~,
..2
U
D
:.
0.05 -
9
3
..-VI
0
1
50
100
150
Fig. 17-20. Effect of uranyl ion on the extraction of nitric acid by TBP
[Moore (1951)l; 0 2.5 M H N 0 3 ; A 5.0 M H N 0 3 .
1.
Mixed extractants
Diethyl ether ,
loo
ao s o
,
40.
Acetophenone
20
_.
Complexes are- also formed between the extractant and the acid in the
extraction process,. For example, the extraction of nitric acid by tributyl
phosphate can.bk represented by
:.'
.
HNO,
..
.. K =
[HNO, ."BPI(,)
: TBP,,,
'. .
..
..
supporting the above mechanism. Table 17-15 gives selected data on the
type of extracted species.
Extraction of water
During extraction processes, water is usually coextracted. Figure 17-23
shows the water content of tri-butyl phosphate when contacted with different mineral acids. Water content in the organic phase is usually determined
by titration with the Karl-Fischer reagent.
There appear to be no rules to predict the extractability of water.(Figs.
17-24 and 17-25). While water is coeitracted with uranyl perchlorate by tributyl phosphate, this is not the case with uranyl nitrate (Fig. 17-24).
374
Species
System
Reference
HC1. TBP
HNOJ . TBP
H 2 S 0 4 . TBP
HC104. TBP
H F TBP
H3BO3 ' 2 TBP
H 2 P 0 4 . TOAH
H P 0 4 . (TOAH)2
H N 0 3 . EHPA
HCI . 2 EHPA
HC104. 2 EHPA
HCI-TBP
HN03-TBP
H2S04-TBP
HCI04-TBP
HF-TBP
H3B03-TBP
H3P04-TOA
HN03-EHPA
HCI-EHPA
HCI04-EHPA
2
4 .
6
8
Acid concentrotion in organic phase,M/I
0 ,
..
,.
. . . ..
"
UO~[NO~)Z
L L
....
. ,
0.2
0.4
0.6
0.8
'
30
I .
z..0
E
w-
20 -
3-0
"
c
a
U
0
c
--
F
0
-C
0,
5
" 10.
0,
L
0
8
.6
No thor~umn~trate
Thorum n~trotepresent
10
E N G I N E E R I N G ASPECTS
.
percent extraction
If the original weight of the.solute in the aqueous phase is -w, and after extraction it is decreased to w , , then
ov - ~ 1 ) l V o
~ ~ JVaL I
where V o is the volume of the ,organic phase and Va is that of the aqueous
phase. From this equation it 'f6llows. tliit
376
Therefore
Percent extraction =
- W1
x 100
+ Val Vo
x100
Phase ratio
The volume ratio of the two phase is called the phase ratio. A high aqueous/
organic ratio is sometimes undesirable because it may lead to high solvent
losses. On the other hand, a high organic/aqueous ratio requires a large inventory of solvent, which may be a financial burden.
While the percent extraction is a function of the phase ratio, the distribution coefficient is not.
Separation factor
When two metal ions are to be extracted from an aqueous solution. by an
organic solvent, the separation factor of the two metal ions is defined by
= &ID,
where Dl and D, are the distribution ratios of the two metals. In order that
separation is possible B must not equal 1.
Multiple extractions
If Va = volume of aqueous phase containing w grams of the solute, Vo
= volume of organic phase, and after the first extraction w, = weight of solute
remaining in aqueous phase, then the equilibrium concentration in aqueous
phase = IV,/V~,and the equilibrium concentration in organic phase
= (w - w1)lVo:
Therefore
D = (w - w11lVo
w1lV.
Solvent extraction
Dlv, . Vo = V , I ~- V,IV,
( V,
+ D Vo)nl,
&\v
~ f t e the
r second extraction, w, = weight of solute remaining in aqueous
phase.; the equilibrium concentration in aqueous phase = ' I ~ J ,and
/v~
the;
.
.
equilibrium concentration in organic phase = (lo, - lo,)/ V .o ., ..
After n extractions,
I'
.378
Countercurrent extraction
379
Soluent extraction.
VI'
U
.-
trotion in extract,
P
0
C
.-
-2
C
.-0
0
a
0
Equipment
380.
a settling chamber where the mixed phases are given enough time to separate (Fig. 17-28). Each such unit composes a stage. The apparatus is very
efficient but its principal disadvantage is the large space required per stage.
-
Pregnant
oquex
Orqonic
outlet
&
Interface
Organicinlet
Grid
Aqueous
outlet
'
Solvent extractiorz
381
.
to an axial vertical shaft. Each rotor disk is spaced vertically midway betwe'en adjacent stator disks. Rotation of ;he central shaft provides controlled
dispersion of the-two phases. There
no- settling chambers, 'and the two
phases drift past one another in countercurrent flow;-separationtakes place
at the top of the tower.
Another type of c;lumn extractor is the pulse column. In this column the
two phases are dispersed in each other by pulsating action through stationary
perforated plates extending across the column. The pulsating action is supplied by leading a pulse leg from the-bottom of the column to the pulse generator, which may by simply a reciprocating pump with check valves removed. The pulsating action forces the two phases through the holes in the
plates, forming.bubbles. They rise (or fall) to the next plate, where they
coalesce to await the next pulse. If the pulsing is vigorous, the bubbles never
coalesce but are repeatedly forced through the holes in the various plates as
they work their way up and down the column. The passage of a bubble
through a hole in a plate deforms it considerably, and the internal agitation
thus produced improves the extraction.
Economic aspects
Clemmer el al. (1957) compared the solvent extraction of uranium with ion
exchange (Table 17-16) and concluded that the former is more economical
than the latter. Most uranium mills built in recent years have chosen the
arnine extraction process. A report from South Africa by Carr and Lloyd
(1963) was in favor of solvent extraction, and an estimate was given showing
that when 1 Ib of uranium is recovered by ion exchange it costs 18.7 cents
while by amine extraction it is only 5.2 cents. Agers and House (1965) estimate that uranium recovery by amines from a leach solution containing
1 g / l ~ ; 0 , would be about 4 centsllb of U 3 0 8including stripping and precipitation by ammonia.
Table 17-16. Solvent extraction of uranium versus ion exchange.
Ionexchange
Basis of comparison
Loading capacity
~roductioncapacity,
Ibs U308/day
Cost
~olven'textraction
1 cu ft
3-5 Ib U 3 0 8
1 cu ft 0.1Mextractant
'/4-'/2
Ib U3Os
2-3
$45
4-8
$3-4
382
-.
Beryllium
* Previously
Solvent extractioti
383
3) In the extraction of beryllium from sulfuric acid solutions by organophosphorus compounds, it was suggested by Surls and Grinstead (1967) to
strip the organic phase with.9 molar H 2 S 0 4 .Under these conditions, beryllium is precipitated as BeS0,-2H20 while aluminum remains in solution.
Boron
A process based on the use of a substituted phenol was developed at. Oak
Ridge National Laboratory for. the extraction of cesium from p.ollucite ore.
The extractant is 4-se~-butyl-2-(~-methylbenzyl)phenol
manufactured by the
Dow Chemical Company. This extractant is,highly selective for cesium (SeeFig. 17-19). Since the. phenol can be used only in alkaline medium, the
pollucite ore is opened by roasting with sodium'carbonate, and it is then
leached with
water. he process was originally developed for extracting radio. . .- . . - .
active cesium from reactor waste solutions.
Copper
3 84
further to yield a marketable product. It is not a particularly attractive material for handling because of its fineness and the difficulty of washing it free
from acid. Solvent extraction with subsequent hydrogen reduction under
pressure or electrodeposition of a marketable product offers a convenient
method of recovery. There is the added advantage that acid is liberated in
the recovery step and can therefore be used as a stripping solution in the
extraction process.
The most promising extractant is LIX-64 (see page 339). The process is
at present in a commercial scale at Bluebird Ranchers Company in Miami,
Arizona, and on pilot stage at Bagdad Copper Corp. and Duval Corp., both
in Arizona. Present data available show that the recycle of raffinate containing traces of the organic phase does not have a toxic effect on the bacteria
accelerating the leaching process, and that the organic entrainment in the
solutions going to electrolysis does not affect electrodeposition if proper
handling of solution is taken into consideration.
Thorium
Thorium is recovered on a commercial scale as a by-product of uranium ore
processing. The process, based on extraction by an organic phosphorus compound, would not be economical for thorium recovery alone in.such a low
concentration; but the operation is made feasible by the fact that the ore has ,
Table 17-17. Analysis of Elliot Lake ore and effluent from ion exchange
columns after uranium recovery [Vermeulen (1966)l.
Ore, %
v
Th
Rare Earth Ox~des
S
Fe
A1z03
SiOz
Effluent, g/l
0.11
0.028
0.057.
3.28
3.25
6.2
80.3
v
Th
Rare Earth Oxides
Fe3+
Fez+
Ti
SO:NO3
already been mined and leached by H2S04, and uranium is recovered by ion
exchange. The effluent from the ion exchange columns is processed'for thorium recovery. Table 17-17 gives an analysis of the ore from Elliot Lake,
.
Canada, and the analysis of the ion exchange effluent.
Pure thorium is prepared by dissolving the thorium-rich precipitate, obtained from monazite sand leach solution, in nitric acid and then extracting
t6e thorium with tributyl phosphate. The main impurities are the rare earths;
these are left behind, since their distribution coefficient is'very low as compared to that of thorium.
T~~ngsletz
'
Separation
An important application of solvent extraction is its. use in separating a
number of metals occurring together. This can usually be achieved by selecting the proper pH, adding a complexing agent in the aqueous phase, and
above all choosing a solvent that shows more selectivity for one metal than
for the other. For example, sulfuric acid leach solutions of monazite. sand
contain rare earths, thorium, and uranium. On examining the data shown
in Table 17-19, it would be seen as possible to devise a method for separation
based on extraction by amines.
25
Habashi, Metallurgy 11
Process
Remarks
Dapex process
3-5% D2EHP in kerosene and
about the same concentration
TBP (synergic effect). Stripping
by 10% Na2C0,. Uranium is
recovered from strip solution by
precipitation with NaOH-yellow cake.
Used in U.S.A. by Climax Uranium at Grand Junction, Colorado, and by Kerr-McGee Uranium at Shiprock, New Mexico.
DDPA process
0.1 M solution of DDPA in
kerosene. Stripping by ION
HC1. Strip solution is evaporated
to recover HCI, then uranium is
precipitated by NH,OH-yellow cake.
Amex process
Secondary 'or tertiary lauryl
amines are used as extractants.
Stripping by dilute NaCl solution.
Molybdenunl is coextractedwith
uranium but is not 'stripped
from the amine during uranium
stripping. Sodium carbonate or
ammonia strips molybdenum
and prevents its buildup in the
organic phase.
Phosphoric acid
OPPA in kerosene;
stripping by HCI.
Nitric acid
'
So1~;entextraction
Table 17-18, (cont.)
Medium
Process
~emarks'
(2) When uranium is recovered
by ion exchange and the resin
is eluted by nitrate-nitric
acid solution, the eluate is
treated with.lime to pH 3.5
to remove sulfate as gypsum
and precipitate iron and thorium. ~ i a n i u mcan then be
recovered from the solution
by TBP.
Primary amines
Thorium
Uranium
Rare earths
Very strong
Moderate
Moderate
Nil to weak
Nil
Secondary amines
Straight chain or
branching far from N-atom
branching near N-atom
Strong
Weak
Moderate
Strong
Tertiary arnines
Nil
Strong
Nil
1,
Sulfuric ocid,solution
containing U,Cu,Co,Ni,
Fe,and Al. pH=2.5
.
. I
3 % ~sodeconol
~ r o n i u r nextraction.
L-+tracesu of Fe
Aqueous phase:
iu
6.4g,i - - - - - - - - - - -
CO
5.1
Ni
2.8
10010 LIX-63
10% D 2 EHPA
-4;
pH
to 4- - - adjusted
-- - 10% L I X 63
10% D2 EHPA
Copper extraction
99% Cu recovery
CU
6.5 g/L
Organic
phase:
CO
0.017
Ni
0.014
-- ---
Cobalt extraction
90% recovery
organic phase:
Co 3,58g/1
Ni 0.16
To waste
. . . .
. .
Equilibrium pH,
Numerous schemes have been worked out to separate cobalt from nickel
and an extensive literature is available. Figure 17-32 shows the use of octyl
alcohol in separating the two metals from HCl solution. Separation can also
be achieved by using tertiary amines, e.g., tri-isooctyl amine. This separation
is based on the fact that cobalt forms an anionic complex, [COCI,]~-,
while nickel does not.
Equilibrium concentration of H ~ I
In aqueous phase
Hafniuni-zircoriiun~
The advantages of hafnium-free zirconium for nuclear reactors have resulted
in the development and application of solvent extraction for the separation
of the two metals on a conlmercial scale. Hexone is used to extract hafnium
and some zirconium from a hydrochloric acid solution containing both metals, to which thiocyanic acid has been'added. The organic phase is then
stripped with HCI to remove zirconium, and then with H,S04 to remove
hafnium. Both metals are next recovered from their respective aqueous solutions by precipitation as hydroxides by ammonium hydroxide. The hydroxides are filtered, washed, and then ignited to the oxides.
390
products
Solvent extraction
391
-bulk of the fission products remain in the aqueous phase. The organic phase
.
is then stripped in the following sequence:
a) By HNO, to remove any fission products extracted.
Small amounts of scandium are usually present in uranium ores and are
dissolved during acid leaching, yielding up to 0.001 g/l ScZO3.Scandium
was found to follow uranium in an organic phase composed of dodecyl
phosphoric acid and kerosene. However, it is not stripped with uranium in
10M HCl. After several'contacts of the extractant, scandium builds up into
the organic phase and can be stripped with HF. A fluoride precipitate
analyzing approximately 10% Sc203 and 20% Tho, is obtained. This
is then purified ,by digestion in 15% NaOH to convert it into hydroxides, and then digested with hydrochloric acid, the pH being adjusted to 4
.to remove Ti, Zr, Fe, and SiO,. Scandium is recovered from the solution
by precipitation with oxalic acid. The oxalate is calcined and the oxide is
further purified by dissolution in HC1 and solvent extraction; A description
The association of vanadium with uranium in many uranium ores, and the
ease with which a separation by solvent extraction could be accomplished,
led to the second major commercial application of solvent extraction, for
by-product vanadium recovery. Vanadium is extracted together with uranium by DDPA or HDPA. The addition of trialkylamine increases the extraction due to synergic effect. Vanadium is stripped first by 2M HCl, and
then uranium is stripped by 1OM HCI.
The loaded extractant can also be stripped with Na,CO, solution to give
a concentrated solution of uranium and vanadium, from which uranium can
be precipitated by NaOH, leaving a solution containing sodium vanadate.
LITERATURE*
Introduction
Ano.nyrnous,. "Solvent ~xtiactionGains in Hydrometallurgy", Chenl. Eng. News, 42,
48-50 (1 964).
D . W.Bridges and, J.B. Rosenbaum, "Metallurgical Applications of Solvent Extraction ",
U.S. Bl!realr of Mines I~lformario~l
Circlrlar 8139 (1962).
B.I.Brounshtein and A.S.Zheleznyak, Physico-Chemical Principles of Liquid Exrrac/iori
(in Russian), Leningrad, Khirniya, 1966.
K..B.Brown, and C.F.Colernan, "Solvent Extraction in Ore Processing", Progress in
Nlrclear Energy, Series 111, 2, 3-24, New York, Pergarnon, 1958.
A.S.Chernyak and M.L.Navtanovich, "Role of Organic Reagents in Hydrometallurgy",
Nalichrr..Tr. Irkursk. Nauchn.-Issled. Ins/. Redkikh ~ e t a l . 1961
;
(lo), 316-42; C A , 58,
8689d.
A.K.De, Separario~rof'Heavy Metals, London, Pergamon, 1961.
R.M.Diamond and D.G.Tuck, "Extraction of Inorganic Compounds into Organic
Solvents", pp. 109-192 in Progress of Ir~organicChemistry, Vol. 2, New York, Academic,
1960.
D.Dyrssen,"Metal Extraction with Liquid Anion Exchangers"; Suerlsk Kerii. Tidskr., 77,
287-99(1965); CA, 64, 2721f.
3 94
Extractants
'
Ethers
P.I.Artyukin et al., "Extraction of Certain Elements from Hydrochloride Solutions by
Means of /?,/?'-Dichlorodiethyl Ether", Dokl. Akad. Nauk SSSR, 169 (I), 98-9 (1966);
CA, 65, 16126h.
R. W.Dodson et al., "The ~ i t r a c t i o nof Ferric Chloride from Hydrochloric Acid Solutions
by Isopropyl Ether", J. Am. Chem. Soc., 58, 2573-7 (1936).
H. W. Vogel, "Spectroskopische Notizen", Ber. deutsch. Chenl. ~ e s . 12,2312-6
,
(1 879).
Alcohols
G.F.Asselin and E.W.Comings, "Extraction of Thorium and Rare Earths by Amyl
Alcohol", Ind. Etzg. Chem., 42, 1198-1205 (1950).
E.A.Belousov and ~ . ~ . ~ h a k h a e"Extraction
v,
of Rare Earth Nitrates by .SaturBted
Alcohols", Zh. Neorg. him.: 9, 2659-63 (1964).
Soluent extraction
395
A ldehydes
F.K.Cole and L.H.Brown, "Solvent ~ x t r a c t i o nof Heavy Metal Chelates with Furfural",
Ittd. Etig. Chetn., 51, 58-9 (1959).
N. I. Petunina and I. G. Chufarova, "Extraction of Tantalum, Niobium, and Titanium with
Furfural from sulfuric Acid Solutions in Presence of Ammonium Fluoride", Tr. Itist.
Khim., Akad; Nauk SSSR, Ural. Filial, No.10, 19-23 (1966).
'
Oximes
D. W. Agars et al., "Copper Recovery from Acid Solutions Using Liquid Ion Exchangers",
Tratrs. Soc. Mill. Etig. AIME, 235, 19 1-8 (1966); Min. Et~g.,17, 76-80 (1965).
Acids, carbosylic
R.Blumberg and P.Melzer, "Recovery of Common Metals by a Solvent Process, (a-Halo
Substituted Carboxylic Acid), Tratls. I~iterti.M i t ~ e r a l ~ r e s s iCot~gr.,
n~
1964, pp. 139-145
(pub. 1965).
A.W.Fletcher, D.S.Flett, and J.C.Wilson, "Solvent Extraction of Ferric Iron by a
Carboxylic Acid", Bltll. Ittst. Mill. Met., 696, 81-8 (1964).
A.W.Fletcher, D.S.Flett, and J.C.Wilson, "Solvent Extraction of Ferric Iron by a
Carboxylic Acid", Bull. Itlst. Min. Met., 693, 765-77 (1964).
L. M. Gindin, P. I. Bobikov, E. F. Kouba, and A. V. Bugajeva, Zh. Neorg. Khim., 5, 1868
(1960); 5, 2366 (1960); 6, 2797 (1961).
L.M.Gindin, P.I.Bobikov, and A. M.Rozen, Dokl. Akad. Nalrk SSSR, 128, 295(1959).
. .
E.M.Kuznetsov and G.A.Tsyganov, "Extraction of Metals from Aqueous Solutions with
Fatty Acids", Vestti. Karakalp. ilial la Akad. Nalrk Uz. SSR, 1964 (3), 42-6; CA, 64,
8984e, i 9 6 5 (3), 41-4; C A , 65, 16126f.
M. Kyrs, P.Selucky, and P.Pistek, Zh. Neorg. Khim., 10: 2764 (1965).
A.L. Markman, L. L.Galkina, and M. A. Grushetskaya, "Extraction of Rare Earth
Elements by Butyric Acid", Uzbeksk. Khini. Zh., 8 (4), 38-42 (1964); CA, 62, 9759a.
E.N.Merkin et+al.,"Extraction of Uranium, Thorium, and Related Elements by Mono.. caiboxylic Acids", Radiokliitniya, 8, 705-7 (1966).
M.Novak and H.Beranova, Extraction Agent for Uranium, Czech. Patent 112,738 (1964).
M.Novak and A.Havel, "Extraction of Metals by Fatty Acids", J. It~org.Ar~rcl.Chetn., 29,
531-9 (1967).
M.Olteanu and I.Moldovan, "New Processing Methods for Solutions Obtained from
Leaching of Pyrite Ash. Extraction of Metals from Solutions by Means of Carboxylic
Acid Sodium Salts in Nonpolar solventsV, Rev. Chitn. (Bucharest), 1 7 (I), 20-7
(1966).
396
A cicls, ~taplltkerlic
,
1
ark-~aith
Phertols .
W.D.Arnold, D.J.Crouse, and K.B.Brown, "Solvent Extraction of. Cesium (and ~ u b i dium) from'ore Liquors i i t h Substituted Phenols", Inn. Eng:Cltrtn., Process Des. aud
Deu., 4, 249-54 (1 965).
,D.E.Horner, D . J.Crouse, K.B.Brown, and B. Weaver, "Fission Product Recovery from
'Waste Solutions by Solvent Extraction", pp.545-563 in Unit Processes of Hydrome/allrrrgy, eds. Wadsworth and Lewis, New York, Gordon & Breach, 1965.
.M.Kyrs et al., Extraction Separation of Uranium, Plutonium, and Zirconium, Czech.
Patent 111,913 (1964).
....
Esters
-G:)E:Baes, Jr., '.The Extraction.of Metallic Species by Dialkylphosphpri~Acids", j.Itlorg.
Nucl. Cham., 24, 707-720' (1962).
'
398.
T.Ishimori, E.Akatsu, A.Kataoka, and T.Osakabe, "Solvent Extraction of Macroamounts of Elements in the Systems of Tributyl Phosphate with. Nitric Acid and with
.
, .
Hydrochloric Acid", J. Nucl. Sci. Tech. (Tokyo), 1 (I), 18-21 (1964).
T.Ishimori, K.Kimura, T.Fujino, and H.Murakami, "Solvent Extraction of Inorganic
Ions with ~ r i - n - b c t y Phosphine
l
Oxide", Nippon Genshiryoklr,Gokkni~hi,4 (2), 117-26
(1962) (Eng.); C A , 63, 14138f.
Z.Kolarik and H.Pankova, "Acidic Organophosphorus Extractants-I.
Extraction of
Lanthanides by Means of Dialkyl Phosphoric ~ c i d s - ~ f f e c t of Structure and Size of
Alkyl Group", J. Iriorg. Nricl. Chem., 28, 2325-33 (1966).
F.Krasovec and C.Klofutar, "Effect of the Reagent Structure on the Extraction of
Uranium VI with Different Phosphoric Acid Esters", Nucl. Inst. Stefan, Ljubljana,
Yugoslavia Rept. No. R427 (1964).
G.W.Mason, S.Lewey, and D.F.Peppard, "Extraction of Metallic Cations by Monoacidic
orthophosphate Esters in a Monomerizing Diluent", J. Inorg. Nucl. Cher~l.,26, 2271-84
(1964).
G. W. Mason and D. F. Peppard, "Types of Acidic Organophosphorus Extractants and
their Applications to ~ransurani'c,,~e~arations",
Nucl. Sci. Eng:, 17 (2), 247-51
(1963).
D.C.Madigan, "The Extraction of Certain Cations from Aqueous Solutions with Di-(2Ethyl Hexyl) Orthophosphate", Alis!ral. J. Chem., 13, 58-66 (1960).
H . A. C. McKay, "Tri-n-butyl Phosphate as an Extracting Agent for the Nitrates of the
Actinide Elements", Proc. htterr~.Con/. Peacefir1 Uses A!. Energy (Geneva, 1955), 7 ,
314-7, New York, ~nited'Nations, 1956.
H.A.C.McKay, "The Physical Chemistry of Tributyl Phosphate Solutions", Ir~d.Chirn.
Beige, 29, 1278-85 (1964).
A.V.Nikolaev, Yu.A.Dyadin, and I.I.Yakovlev, "Solubility of Water and Uranyl Nitrate
in Tributyl Phosphate at 0-100C", Dokl. Akad. Narrk SSSR, 158 (5), 1130-2 (1964);
CA, 62, 13918b.
A.V.Nikolaev et al., "Correlation Between the ~ x t r a c t i n g ' ~ o w eofr Organophosphorus
Extracting Agents and the [Hammett] 8 Constant of the Subs'tituents on the Phosphorus
Atom", Dokl. Akad. Nauk SSSR, 165 (3), 578-81 (1965).
Yu.F.Orlov and V.P.Shvedov, "Effect of the Composition of Organophosphorus
Compounds on the Extraction of Ce(II1) Nitrate", Radiokhirni-va, 8 (2), 139-45 (1966).
K.Oshima, "Solvent Extraction of Metals by Organophosphorus Compounds", Nippotr
Getrshiryokrr Gakkaishi, 4 (I), 8-16 (1962) (Eng.); C A , 63, 14137g.
K.Oshima, "Solvent Extraction of Metals by Organophosphorus Compounds", Nippor~
Genshiryokri Gakkaishi, 4 (3), 166-74 (1962); C A , 64, 13449b. .
D:F. peppard, G. W. Mason, and C. Andrejasich, "Two Mono-Octyl Phosphinic Acids
(R)(H)PO(OH), as Extractants for Metallic,Cations. Selected M(1II) and M(VI) Tracer
Studies", J. Inorg. Nucl. Chem., 28, 2347-2359 (1966).
D.F.Peppard, G. W. Mason, W. J.Driscoll, and R. J. Sironen, "Acidic Esters of Orthophosphoric Acid as Selective Extractants for Metallic Cations-Tracer Studies", J. lrrorg. .
Nrrcl. Chem., 7 , 276-85 (1958).
D . F.Peppard, G. W. Mason and G. Giffin, "Extraction of Selected Trivalent Lanthanide
and Actinide Cations by bis (Hexyloxyethyl)phosphoric Acid", J. Inorg. Nucl. Chem.,
27, 1683-91 (1965).
Soluent extraction
399.
Anlines
M.Abe and A.Yazawa, "Separation of Metals by Extraction with High Molecular Weight
Amines", Tohokrr Daigakrr Se~rkoSeiren Kenkyrrsho Iiio, 20 (I), 59-64 (1964); C A , 62,
14259d.
C.F.Goleman, "Amines as Extractants. Survey of the Descriptive and Fundamental
Extraction Chemistry", U.S. At. Energy Com~?i.
Rept. ORNL 3516 (1963).
C. F.Coleman, "Amine Extraction in Reprocessing", At. Energy Rev., 2 (2), 3-54 (1964).
C.F. Coleman, K.B.Brown, Jr., J.G. Moore, and K. A. Allen, "Amine Salts as Solvent
I
Extraction Reagents for Uranium and Other Metals", Proc. I~rter~i.
Cot$ Peaceful Uses
At. Etrergj~(Geneva, 1958), 28, 278-288, New York, United Nations, 1'958. '
G.Duyckaerts, J.Fuger and W.Mueller, "Liquid-Liquid Extraction by Trilaurylamine.
.
Hydrochloride", U.S. At. Energy Conim. Rept.. EUR-426.f (1963).
W.E.Keder and A.S.Wilson, "Amines as Extractants: The Organic Phase", .U.S. At.
Energy Comm. Rept: HW-SA-2797 (1962).
. .
W.E.Keder, A.S. Wilson, and L.L.Burger, "Amine Systems in Solvent Extraction'', U.S;
At. .Energy Conmi. Rept. HW-SA-2959 (1963).
.
.
A.S.Kertes, "Solubility Parameters.of Long-Chain Alkylamines and, their Activities in
Organic Solvents'', J. I~iorg.~ u c l : ~ h e n ;26,
. , 1764-6 (1964).
H.Ch. Ma and C. M.Ni, "Amine Extractants in Analytical Chemistry", Hrra Hsrreh Tung
Pao, 1964 (12), 705'15, 746.
F.L.Moore, "Liquid-Liquid Extraction With High Molecular Weight Amines", Nat.
Acad. Sci., Nat. Res. Council Monograph NAS-NS-3101, Dec. 15, 1960.
A.A.Nemodruk, "Extraction of Uranium in the Form, of Uranyl Acetate with Aniline
and its Solutions in Organic Solvents", Tr. Komis. po A ~ ~ a l Khim.,
it.
Akad. Nauk SSSR,
Inst. Geokhim. i Analit. Khim., 14, 141-7 (1963); CA, 59,. 13346d.
Other extractants
J.F:Flagg, Organic Reagetits -Used it1 Grauirnetric arid Vol~inletricAt~alysis,New York,
I nterscience, 1948.
. .
F. J.Welcher, Orga~licA~lal)~tical
Reagents, 4 vols., New York, Van Nostrand, 1947-48.
The organic'phase
Sollielit loading
E,Hesford and H.A.C.McKay, "The Extraction of Uranyl Perchlorate by Tri-11-Butyl
Phosphate", J. h o r g . Nucl. Chern., 13, 165-173 (1960).
P.H.Tedesco, V.B.DeRumi, and J.A.Gonzalez-Quintana, "Extraction of Tetravalent
' Metals with D-(2-Ethyl Hexyl) Phosphoric Acid. I. Thorium", J. Inorg. Ntrcl. Chenl.,
28, 3027:33 (1966).
Solvent extraction
40 1
26 Habashi, Metallurgy I1
402
Extraction of Uranyl Nitrate with TBP (Tributyl Phosphate)", Tokyo Kogyo Shikensho
Hokokli, 57 (4), 171-8 (1962); CA,.61, 15623e.
K. Ohwada and T.lshihara, "Infra-Red Spectrophotometry of Uranyl NitratelTri-11-Butyl
Phosphate in Organic Solvents", J. Iriorg. Nircl. Chem., 28, 2343-45 (1966).
T.Sato, J. hiorg. Niicl. Cherri., 24, 1277-76 (1962); 25, 441-6 (1963); 26, 171-9 (1964);
26, 181-9 (1964).
T.Sato, "The-Complexes formed in the.Extraction of Uranium (VI) .from Sulfuric and
Nitric Acid Solutions by Tri-n-Octylamine", Naturwiss., 52 (lo), 258-9 (1965).
T. Sato, "Extraction of Uranium (VI) from Nitric Acid Solutions by Long-Chain Aliphatic
Amines", J. Appl. Cheni. (London), 15, 92-8 (1965).
T.Sato, "Uranium (VI) Extraction from Hydrochloride Acid Solutions by Tri-11-Octyl, amine", Naturwiss., 5 3 (2), 37 (1966).
V.B. Shevchenko, V. S. Schmidt, and E. A. Nenarokomov, Zh. Neorg. Khir~i.,5, 2354-62
(1960).
L.V.Shikheeva, "Composition of Compounds Formed in the Extraction of Cobalt (11)
.
with Naphthenic Acid", Zh. Neorg. Khim., 10, 1486-9 (1965).
V.N.Startsqv and E.I.K;~~OV,
"Extraction of Niobium (V) from Hydrochloric Acid
Solutions by Tributyl Phosphate in the Presence of Some Salting Agents", Zh: Neorg.
Khirn., 11, 2820-2 (1966).
V. M.Vdovenko, M. P. Koval'skaya, and E. V. Shirvnskii, '.'Extraction of .Thorium with
Octylamine from Sulfuric Acid Solutions", Radiokhirniya, 3, 3-6 (1961).
V.M.Vdovenko, M.P.Kovalskaya, and Ye. A. Smirnova, Radiokhirrriya, 3,403-410 (196 1).
V. M.Vdovenko, M. G.Kuzina, .and. A. A.Lipovskii, "Stoichiometry of. the Compounds
of.Uranyl Nitrate with Tioctylammonium Nitrate", Radiokhir~riya,6, 121-3 (1964).
V.M.Vdovenko, A.A.Lipovskii, and S.A.Nikitina, Radiokhirniya, 3, 396-402 (1961);
4, 625-32 (I 962).
V. M. Vdovenko, I. G. Suglobova, I. N. Ladygin, and D. N. Suglobov, "Extraction of
Uranyl Nitrate from Neutral Solutions by Trioctylamine (TOA)", Radiokhhniya, 5,
737-9 (1963).
. .
J. M. P. J. Verstegen, J. Inorg. N~icl.Chem., 26, 25-35 ( 1964).
J.L.Woodhead and H.A.C.McKay, "Uranium (IV) Nitrate and Perchlorate Species in
Tributyl Phosphate Solutions", J. hiorg. Nircl. Chem., 27, 2247-54 (1965).
O.E. Zvyaginstev, Yu. G. Frolov, and B. N. Sudarikov, "The Mechanism of Extraction of
Quadri- and Sexivalent Uranium Sulfates with Tri and Di-n-Octylamine", 77. Mosk.
.
K1iini.-Tekhn. Inst. No. 47, 134-9 (1964); CA, 64, 9191 a.
Polymerization of the'extractarit
K.A.Allen, "Aggregation of Some of the Amine Extraction Species in Benzene", J. Phys.
Chem., 62, 1119-23 (1958).
M.Asano, Y.Okajima, and T.Nishi, "Thermodynamics for the Solvent Extraction of
Several Uranyl Compounds by bis(2-Ethylhexyl)phosphoric acid (D2EHPA)", Tech.
Rept. Big. Res. Irlsr., Kyoto Univ., 13, 117-26 (1963); CA, 61, 7904f.
C. F. Baes, Jr., R. A. Zingaro, and C. F. Coleman, "The Extraction of Uranium VI from
Acid.Perchlorate Solutions by Di(2-Ethylhexyl) Phosphoric Acid in 11-Hexane", J. Phys.
Chern., 62, 129 (1958).
Role of Dilue?its
Y U. A. Afanasev, A. V.Nikolaev, and T.I. Koroleva, "Thermochemistry of Binary Systems.
I-The Tributyl Phosphate-Solvent System", Radiokhiiiliya, 8, 6 9 6 9 (1966).
J.Aggett, "The Extraction of Anionic Beryllium Complexes by Tri-isooctylamine..IIEffest of the Diluent", Atistral. At. Energy Comm. Rept. AAEC/TM-238 (1964).
C.A.Blake, Jr:;et a/., "Solvent Extraction of Uranium and Other Metals by Acidic and
Neutral Organophosphorus Compounds", Proc. Intern. Cot$ Peaceful Uses At.
Energy (Geneva, 1958), 28, 289-298, New York, United Nations, 1958.
C.Dubuquoy, R.Guillauniont, and G.Bouissieres, "Extraction of.Mono-, Di-, and Trivalent Elements in Various Solvents in the Presence of Bis(2-Ethylhexyl) Phosphate",
. .
..
Radiochim; Acta, 8, 49-57 (1967).
D.Dyrssen and- Dj.Petkovic, "Distribution Studies of Tripropyl Phosphate-Between
Different Organic Diluents and Water", J. Iilorg. Nlrcl. Chein., 27, 1381-93 (1965).
404
'
Effect of extractant c o ~ ~ c e ~ ~ t r a t i o ~ z
C.A.Blake, Jr., et al., "Solvent Extraction of Uranium and Other Metals. by ~ c i d ' a n d
Neutral Organophosphorus Compounds"., Proc. Itltertl. Cot6 ~eace>rlUses At. Erlergy
(Geneva), 28, 289-298, New York, United Nations, 1958.
.
~
Solvent extraction
405
406
Soluent. extraction
407
Neutral Phosphine Oxides", Daeharl Hwahak Hwoejee, 7 (4), 245-50 (1963) (Eng.);
CA, ,61; 7766g. - .
. .
. .
T.Sato, "The Synergic Effect of Tributyl Phosphate in the Extraction of Uranium (VI)
from Sulfuric Acid Solutions by bis(2-Ethylhexyl) Phosphoric Acid", J. Inorg. Nucl.
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V.S.Smelov and A.V.Strakhova, "Extraction of Uranium by a Mixture of Trioctylamine
and Diisoamylphosphoric Acid", Radiokhirniya, 7, 718-19 (1965).
M.Tanaka and I.Kojima, "Synergic Extraction of Vanadium (V) 8-Quinolinolate in the
Presence of Alcohol, as Explained by the Esterification", J. Inorg. N~rcl.Chern., 29,
1769-75 (1967).
V.M.Vdovenko and -A.S.Krivokhatskii, "Extracting Properties of Mixed Solvents", Zh.
Neorg. Khirn., 5, 494-498 (1960).
W. R. Walker and N. C.Li, "Metal Complexes Involved in Solvent Extraction and Their
Role in the Synergistic Effect", J. Irzorg. N I I C ~
Chem.,
.
27, 41 1-17 (1965).
S.M.Wang, W.R.Walker, and N.C.Li, "Metal Complexes in Solvent Extraction. IVSynergism and Destruction of Synergism with Thenoyltrifluoroacetone and Hexafluoroacetylacetone", J. Inorg. N~rcl.Cherri., 28, 876-86 (1966).
B. Weaver, U.S. At. Energy Con'7rri. Rept. O R N L 3194 (1961).
M.Zangen, "Some Aspects of Synergism in Solvent Extraction. 111-Am(11I) and Am(V1)
in Nitric Acid", J. Irrorg. Nucl. Cheni., 28, 1693-9 (1966).
R.A.Zingaro and oldman, man, "Synergism and Diluent Effects in the Extraction of
Cesium by 4-sec-Butyl-2-(Methylbenzyl) Phenol (BAMBP)", J. Irlorg.'N~rcl.Chenl., 29,
1287-300 (1967).
Tliird-phase formation
S.S.C~O
and
~ D.G.Tuck, "'Third Phase' Phenomena in the Extraction of Nitric Acid by
Methyldioctylamine", J. Plrys. Chern., 68, 2712-14 (1964).
T.Erben, "The Physical Chemistry of Third-Phase Formation", AEC Accession No.
39378, Rept. No. NP-12619 (1961).
E.M.Indikov et al., "Solubility in the ZnC12-H20-Tributyl Phosphate-Solvent System",
Zh: Neorg. Khirrl., 12, 1 4 1 3 4 (1967).
A. S. Kertes and Y. E. Habousha, "Miscibility Gap in Extraction ~ystenis'1n~olving
Alkyl
Amines", ,Proc. Irrterrr. COIIJPeacefir1 Uses At. Energy (Geneva, 1964), 10, 392401,
New York, United Nations, 1965.
A.Kolbe, "Association Equilibriums of Systems Between Tertiary Amines and Alcohols",
Ber.Bunser~ges.Plrys. Cheni., 70, 883-91 (1966).
J. M.P. J.Verstegen, "The Third Phase in Amine System", J. Irrorg. Nrrcl. Chetn., 27; 201-7
(1965).
'
408
Principles of extractive'metallurgy
'
'
EfJ'ect of foreign i o m
C.F.Coleman et al., "Amine Salts as Solvent Extraction Reagents for Uranium and Other
Metals", Proc. Intern. Cotif: Peacefir1 Uses At. Etiergy (Geneva, 1958), 28, 278-288,
New York, United Nations, 1958.
D.A.Ellis et al., "Recovery of Uranium from Colorado Plateau Ores by Solvent Extrac. .
tion", U.S. Ar. Etiergy Comm. Rept. DOW 131 (1955).
N.F.Furman et al., "The Distribution of Uranyl Nitrate from Aqueous Solutions to
Diethyl Ether", U.S. At. Energy Cotntn. Rept. AECD-2938 (1950).
L.Genov, "Extraction of Thorium by Diethyl Ether from Nitrate Medium. ElTe'ct of
Salting-Out Agents", Monatsh. Chetn., 95, 1121 (1964).
G.Kaiser and E.Merz, "Distribution of Uranium (VI) and Thorium Between Alkali
Metal Nitrate Solutions and 5 Volume O/:, Tri-11-Butyl Phosphate", Z. Atral. Chem., 229,
81-9 (1967).
E.Medvedeva and B.V.Gromov, "Extraction of U(V1) by Solutions of Tri-ti-Octylamine
in the Presence of Aluminum Tons", Tr. Mosk. Khitn.-Tekhnol. Ztist., No.47, 140-4
(1964); CA, 64, 8984g.
E.Medvedeva, T.M.Starobina, and B.V.Gromov, "Study of the Extraction of U" by
Solutions of Tri-11-Octylaminein thepresence of Fez+ and Mn2 Ions", Tr. Mosk. ~11ini., Tekhttol. Inst., No.47, 145-50 (1964); CA, 64, 9190g.
R.L. Moore, " ~ e c h a n i s m 'of Uranium .Extraction by Tri-:Butyl Phosphate", U.S. At.
Energy Comm. Rept. AECD 3196 (1951).
A. V. Nikolaev, A. I.Ryabinin, and Yu. A. Afanas'ev, "Mutual Interactions of Uranyl
Nitrate and Thorium Nitrate During Their ~oextractihnwith Tributyl Phosphate",
Zzv. Sibirs!.
Otd. Akad. Narrk SSSR, Ser. Khim. Nauk, 1964 (3), 60-2; CA, 63,
1257b.
V.N.Startsev and E.I.Krylov, "Extraction of Niobium (V) from Hydrochloric Acid
Solutions by Tributyl Phosphate in the Presence of Sonie Salting Agents", Zh: Neorg.
Khirn., 11, 2820-2 (1966).
M. Stern and M. Chatelet, "Liquid-Liquid Equilibriums Extraction of Zirconium Nitrate
by Tributyl Phosphate. 1-ElTect of Sulfate Ions on the Extraction", J. Cllinr. Phys., 63,
506-1 1 (1966).
V.I.Tikhomirov, A. A. Kuznetsova, and E.D.Batoroyskaya, "Extraction of Uranium (VI)
by Trioctylamine in the Presence of Some Cations. I-Nitrate Solutions, 11-Chloride
Solutions, 111-Sulfate
Solutions", Radiokhimiya, 6, 173-81, 182-7, 187-91 (1964).
+
Solvent extraction
409
A. W. Gardner, H.A. C.McKay,, A.R. Mathisen, and T.D. Warren, "The Partition of
Uranyl Nitrate Between Water and Organic Solvents'?, Trans. Faraday Soc., 47, 428
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F.Habashi, "Die Vorgange bei der Gewinnung von Uran aus Phosphorsaure", J. Inorg.
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T. Ishimori, B. Akatsu; W. P. Cheng, K. Tsukuechi, ,and T. Osakabe, "Data on Inorganic
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T.Ishimori and E.Nakamura, "Data of Inorganic Solvent Extraction. I.", Japan At.
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H. A. C. McKay, "The Physical Chemistry of Uranyl Nitrate Solutions", Chem. Ind.,
1549 (1954).
H.A.C.McKay and T.H.Healy, "Tri-n-Butyl Orthophosphate (TBP) as an Extractant",
pp.54656, in Vol. 2 of Progress bi Nuclear Energy, Series 111. New York, Pergamon,
1958.
A.R. Selmer-Olsen, "Solvent Extraction of Chlorocomplexes by Triisooctylamine-Carbon
Tetrachloride from Hydrochloride Acid Medium", Acta Chem. Scarzd., 20, 1621-5
(1966).
Effect of pH
D.J.Bauer and R.E.Lindstrom, "Naphthenic Acid Solvent Extraction of Rare Earth
Sulfates", U.S. Bureau of Mines Rept. b h e s t . , 6396 (1964).
C.A.Blake, et at., "Solvent Extraction of Uranium and Other Metals by Acid and Neutral Organophosphorus Compounds", Proc. bzterri. Corf. Peacejitl Uses At. Energy
(Geneva, 1958), 28, 289-298, New York, United Nations, 1958.
C.F.Coleman, et a]., "Amine Salt; as Solvent Extraction Reagents for uranium and
Other Metals", Proc. Intern. CoriJ Peaceful Uses At. Energy (Geneva, 1958), 28, 278,
288, New York, United Nations, 1958.
410
Pririciples o f extractive'metallurgy
D.W.Agers, .et a / . , "The Purification of Inorganic Acids by the Amine Liquid Ion Ex-
. change Process", pp. 5 15-27 in Unit Processeso.f Hydrometallurgy, eds. Wadsworth and
..,. .
J.Goffart and G.Duyckaerts, "Nitric Acid Extraction with Some Diphosphine Dioxides",
Anal. Chirn. Acta, 39, 57-71 (1967).
Z.Sh. Golyiiko, D.I. Skorovarov, V.F. Smirnov, and N.V. Skvortsov, "Extraction of
Phosphoric Acid with Oxygen-containing Organic Solvents", Zlz. Prikl.. 'Khitn.,.'38,
271-5 (1965).
D.Gourisse, "Mechanism of Extraction of Nitric Acid and Water by Organic Solutions
of Tertiary Alkylamines", Cotntiiis. Etierg. At. (Fratrce) Rapp., R3005 (1966): .
W.H.Hardwick and P.F.Wace, '.'HF Recovery of Amine Solvent .Extractionu, Clieni.
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E.Hesford and H.A.C.McKay, "The Extraction of Mineral Acids by Tri-n-Butyl Phosphate (TBP)", J. Iriorg. Nucl. Cherii., 13, 1 5 6 6 4 (1960).
E.Hogfeldt, "Distribution of Nitric Acid Between Water and Organic Solvents", J. Inorg.
N~rci.Cheri~.,27, 27 (1965).
E.Hogfeldt and B.Bolander, "Extraction of Water.and Nitric Acid. by Mixtures of Tiilaurylamine and I-Octanol Dissolved in n-Octane or r?-Dodecane", Trans. ROJJ.Itzst.
Tech. (Stockholm), No. 224, 3-31 (1964); C A , 61, 7757b.
E.Hogfeldt and K.Rasmusson, "The Extraction of Water and Hydrochloric Acid by
Aromatic Hydrocal.bons", Suerlsk Kern. Tidskr., 78, 490-9 (1966). .
R.Imoto, T.Sakomuna, and M.Kikuchi, ~ h o s ~ h o r Acid,
ic
German Patent 1,235,869
(1967).
.
.
W.E.Keder and A.S.Wilson, Niicl. Sci. Erlg., 17, 287-97 (1963).
A. S. Kertes and 1.T. Platzner, J. Irrorg. Nricl. Cherli., 24, 1417-28 (1962).
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2075-91 (1965).
Yu.I.Kol'tsov, S.S.Korovin, and A.M.Reznik. "Extraction of Hydrochloric Acid by
Tributyl Phosphate in the Presence of Sulfuric Acid", Zh. Neorg. Khirn., 11,.2308-11
(1966).
S. S. Korovin, Yu. 1. Kol'tsov, T.A. Apraksin, and A.M. Reznik, "Extraction of Hydrofluoric Acid and-Sulfuric.-Acid by-Tributyl-phosphate in- Their- Joint Presence", Zh.
Neorg. Khirii., 11, 948-9 (1966).
S. S. Korovin, Yu.1. Kolt'sov, A. M. Reznik, and I. A. Apraksin, "Extraction of Hydrofluoric Acid by Tributyl Phosphate", Zh. Neorg. Kliirii.,' 11,180-3 (1966). . . .' .
S. S. Korovin, A.M. Reznik, E. N.Lebedeva, and N. A. Spasskaya, 'tTri-n-Butyl Phosphate
Extraction of Perchloric and Hydrochloric Acids in the Presence of One Another",
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. .
S.S.Korovin, V.G.Yurkin, and A.P. Mironenko, "Extraction of Boric Acid by Tributyl
Phosphate", Zh. Neorg: Kliirii., 11, 1910-13 (1966).
.
Y.Kurokawa a n d N.Yui, Tech. Rept. Tohoku Uriic;.,29, 221 (1965):
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J.H. Miles, "Infrared'Spectra of Inorganic Acids in Tri-n-Butyl Phosphate Solutions as a
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412
R.Mitamura, S.Nishimura, and Y.Kondo, "System Sulfuric Acid-Water-Tributyl Phosphate", Mem. Fac. Etlg. Kyoto Utlio., 28 (2), 198-212 (1966); CA, 65, 16121d.
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.
~ h e t l ? .3;
,
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I.Ya.Sabaev, I.N.Shokin, and S.A.Krasheninnikov, "Extraction Equilibria of Phosphoric Acid by Alcohols", Zh. Prikl. Khim., 37, 874 (1964).
J.E.Sarvlaineu, "The Primary Extraction Mechanisms of HNO, and Thorium Nitrate,
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,
Formation Between Tributyl
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G.Scibona, B. Scuppa, and M.ZifTerero, "Some Observations on the Extraction of H N 0 3
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,
D. G.Tuck, Disc~rssiortsFaraday Soc., 24, 231 (1957).
D. G.Tuck, "Solvent Extraction Studies. Part I1 - The System Nitric Acid-Water-Tri-nButyl Phosphate", J. Chenl. Soc., 2783-9 (1958).
Solvent extraction
413
Union Chimique-Chemische Bedrijven and Produits Chimiques Pechiney, Process for the
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V. M.Vdovenko, M. P. Koval'skaya, and Ye. A. Smirnova, Radiokhilniyia, 3, 403-10
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E.E.Vinogradov and L.A.Azarov, "Extraction of Boric Acid by Organic Solvents", Zh.
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.
traction", 61d. Errg. Cl~ern.,47, 2114-22 (1955).
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F. G. Zharovskii and V. F. Mil'nik, "Extraction of Nitric, Sulfuric, and Phosphoric Acids
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O.E.Zvyagintsev, et al., "Extraction of Mineral Acids by tr-Octylaniline", Zh. Neorg.
Khitn., 10, 512 (1965).
Extraction of water
~ . ~ u k u t o m T.Kojima,
i,
and H.Kakihana, "Extraction of Water by Trioctylamine",
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.
.
E.Hogfeldt and B.Bolander, "Extraction of Water and Nitric Acid with Mixtures of Trilaurylamine and n-Octanol in 11-Octane or 11-Dodecane Solution", Trans. Royal I t ~ s t .
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414
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,
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'
Engineering aspects
D.W.Agers and J.E.House, "Basic Economic and Technical Considerations in the Extraction of Metals Using Amine Solvents", pp. 836-48, in Ut~itProcesses ofHydrotilera1Irir.g~;,.eds.
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. .
D.S.Arnold and B.G.Ryle, "Reactor Grade Uranium by Extraction of Slurries", Chenl.
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.
D.S.Arnold, B:G.Ryle, and J.O.Davis, ','Metal Refining by Solvent Extraction of Leach
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K.L.Black, J.Koslon, and J.D. ~ o o r e "Design
;
and Operation of a Uranium,Processing
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D.A.Ellis, R.S.Long, and J.B.Byrne, "Entrainment Studies on Solvent Extraction of
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T.D.Heath and R.S. Wiener, "The Use of Cyclones in ~ i q u i d - ~ i q u ~xtrac'tion
id
Processes", Paper presented at AIChE Meeting, Cleveland, Ohio, May 1961.'
P. J . L ~ ' and
o~~
M.K.Oerte1, "A Theoretical asi is for the Evaluation of ~ o " gchain mine
Extractants and Its Application in Design Calculations for Separation Efficiencies and
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. .
~ : ~ . ~ ; e ; b a~l ,i q u i d~ . ~ t r a c f i o(2nd
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,
Bery Iliunz
C. E. L. Bamberger, H.,F. McDuffie, and C. F.Baes, Jr., "The Preparation of Pure Beryllium Oxide by Solvent Extraction with Acetylacetone in the Presence of Ethy!enediamine'
41 5
Solvent extraction
Tetraacetic Acid"; U.S. At. Energy Cotntn. Repr., ORNL-3733 (1964); Nrrcl. Sci. Eng.;
22, 14 (i96sj.
.
.
W. J.Biermann, Recovery of Beryllium, Belgian Patent 633,118 (1963).
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. , . . .. .
R.W.Cattrall, "kxtraction of Beryllium from Sulfuric Acid Solution by Alkylorthophosphoric Esters", Austral. J. Chenz., 14, 163 (1963).
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R;R.Grinstead and J.P.Surls, Jr., "Preparation of High-Purity ~ e j l l i u mCompounds
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W. J. McDowell and C. F. Coleman, "Extraction of Alkaline Earths from Sodium Nitrate
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..
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W.G.Scribner, M.J.Borchers, and W.J.Treat, "Solvent Extraction of Berylliuin with
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A.K.Sundaram and S.Banarjee, "Extraction of Cations as Salts ?f Fatty Acids: Beryllium
..
as Butyrate", Ana1.v. Chim. Actcr, 8, 526-29 (1'953).
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- .
by Solvent Extraction", Nrtcl. Sci. Eng., 28, 338-45 (1967).
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'
. : I
41 6
Boron
. .
. .
'
Cesium
W.D.Arnold, D.J.Crouse, and K.B.Brown, "Solvent Extraction of Cesium (and Rubidium) from Ore Liquors with Substituted Phenols", bid. Er~g.Chem. Process Des.
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Copper
. .
'
Soluent extraction
41 9
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J.J.v.Aartsen and A.E.Korvezee, "The System Uranyl Nitrate-Water-Tributyl Phosphate-Carbon Tetrachloride", Trar~s.Faraday Soc., 60, 510-18 (1964).
K.A.Allen, "The Uranyl Sulfate Complexes from Tri-n-Octylamine Extraction Equilibrium", J. An?. Cheni. Soc., 80, 4133-7 (1958).
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.
.
M.Asano and T.Nishi, "Extraction of Uranium from Aqueous Nitric Acid Solution by
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.
C.Deptula, "Uranium (VI) Extraction from ~ u l f i ~ r iAcid
c
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.
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,
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A.J.Gilmore, V.M.McNamara, and R.Simard, "Tri-n-Butyl Phosphate Extraction of
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S o l ~ e n textraction
'
421
B.N. Laskorin and V. F. Smirnov, "Extraction of Uranium from Phosphoric Acid Solu- .
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B.N.Laskorin and V.F.Smirnov, "Extraction of Uranium(1V) by bis(2-Ethylhexyl) Phosphoric (DZEHPA) and Monolaurylphosphoric Acids (MLPA) from Solutions of
Phosphoric Acid", Zh. Prikl. Khin~.,38, 2226-32 (1965); cf. CA, 55, 6232d.
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. .
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.
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I
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Solfienr extraction
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Hafiiium-zircotiium
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~olierttextraction
42 5
Niobium-tarttalun~
A. G.Babkin and Ya. G . Goroshchenko, "The Mechanism of Niobium and Tantalum
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'
426
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,
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'
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.
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,
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