close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3082091

код для вставки
3,082,081
1
United States Patent 0 "ice
Patented Mar. 19, 1963
2
1
3,082,081
SELECTIVE SEPARATION OF LUTEO COBALT
FROM AMMONIACAL SOLUTIONS CONTAIN
ING DIVALEN-T COPPER AND/0R DIVALENT
NICKEL BY PREFERENTIAL ABSORPTION ON
A CHELATING RESIN
Joseph H. Howe, Freeland, and Leo R. Morris, Midland,
case, contact time is varied as desired for a wante<
separation. In either case, a simple test run suffices to de
termine the contact time of a metals solution with a give]
chelating resin. The preferentially adsorbed cobalt, to
gether with a minor amount of copper and/or nickel, i
thereafter removed with a ‘dilute mineral acid eluant
advantageously 1-molar hydrochloric acid. The prefer
Mich., assignors to The Dow Chemical Company, Mid
ence of the given chelating resins is shown when a calcula
land, Mich., a corporation of Delaware
tion is made of the metal preference ratio, hereafte
Filed May 19, 1960, Ser. No. 30,107
10 M.P.R. The M.P.R. is the ratio of the molar concentra
3 Claims. (Cl. 75-119)
tions of the metals in the resin eluate corrected for Th4
molar concentration in the original metal liquor, i.e.,
This invention concerns a method for separating cobalt
from copper or nickel or from copper and nickel. More
particularly, it concerns a method for separating cobalt
from copper and/or nickel in an ammoniacal medium
wherein the cobalt is in the luteo form by adsorption on a
where
'" B6
(
X
A0
)
(Ae)-=molar concentration of metal A in resin eluate
chelating resin wherein the cobalt is preferentially ad
(Be)-=molar concentration of metal B in resin eluate
sorbed by the chelating resin and the copper and/ or nickel
(A°).=molar concentration of metal A in original meta
are thereby readily separated from the cobalt. ‘More par
liquor, and
ticularly, the method of this invention consists in separat~ 20
(B0) :molar concentration of metal B in original meta
ing cobalt from copper and/ or nickel by adsorption on a
liquor
chelating resin in the ammonium salt form having car
boxymethylthio, -—S——CH2CO2H, or 1,2-dicarboxyethyl
The M.P.R.’s for a ternary system can be derived b
thio, -—S-—CH(CH2CO2H)CO2H, substituent groups
combining the M.P.R.’s calculated for any two pairs 0
wherein cobalt is preferentially held and thereafter eluting 25 the three metals in the system. With batch (equilibrium
and simultaneously regenerating the loaded resin with a
operation, the M.P.R.’s of CozNizCu approximate 5:1:
mineral acid wash to recover a cobalt concentrate.
In the past use of ion exchange and chelating resins,
various procedures have been developed for concentrating
metals as their conventional or complex ions.
In the
process of this invention, a separation has been developed
wherein the order of selectivitiy for cobalt, copper and
nickel has been reversed from that of previously known
procedures wherein either copper or nickel is bound by
with a (thio)acetic chelating resin crosslinked with 1
weight percent divinylbenzene and approximate 20:3:
wih a (thio)succinic chelating resin crosslinked with 1
weight percent divinylbenzene. With column operatior
the M.P.R.’s of Co:Ni:Cu approximate 12:1 :1 both for
(thio)acetic and a (thio)succinic chelating resin whici
are 4 percent crosslinked \with divinylbenzene.
The (thio)acetic and (thio) succinic chelating resins ma
the separating means in preference to cobalt. This newly 35 be prepared by reacting a water-wet poly(vinylaryl sul
discovered preferential adsorption of cobalt is quite ad
fonium) anion exchange resin, as described in US. Paten
vantageous in the metals separation of ore leach liquors
2,895,925 and in U .S. patent application Serial Nr
containing binary or ternary luteo cobalt mixtures of the
769,545, ?led October 27, 1958, with a stoichiometri
above metals where it is desired to hang up or concentrate
equivalent of disodium thioglycollate or of trisodium mei
the cobalt, particularly when the cobalt is present in small 40 captosuccinate, respectively, by heating the reactants o
amounts relative to copper and/or nickel. The use of
such a cobalt selective resin lowers the frequency of re
generation when a low-cobalt ore leach liquor is to be
processed and thereby reduces operating costs.
a steam bath for a time su?icient to displace sul?de wit‘
carboxymethylthio or with ‘1,2-dicarboxyethylthio group:
respectively. This generally takes from 1 to 2 days. Th
45 resulting (thio)acetic or (thio)succinic chelating resir
The process of this invention employs a chelating resin
usually in the sodium salt form, is separated from the re
of the groups of resinous polymeric (vinylbenzylthio)
action medium, rinsed with water and with concentrate
acetic acid,
hydrochloric acid and given a ?nal water rinse. Befor
use,
the resin is changed to the ammonium salt form.
prototype poly(-—-CHT—CH——CuH4-—CHQ—S—OH2C 02H)
The following non-limitative examples describe con
50
and polymeric (vinylbenzylthio) succinic acid,
pletely speci?c embodiments of the inventive process an
set forth the best mode contemplated by the inventors c
I
prototype p01y[—CH2—CH—CuH4—CH2—S——CH(CH2C 02H) 0 02H]
carrying out their invention.
EXAMPLE 1
crosslinked with about 1-8 mole percent, total polymer
basis, ‘of a conventional crosslinking agent such as divinyl~ 55 A small quantity (1.6 g.) of a (thio)-acetic chelatin
benzene, divinyltoluenes, divinylnaphthalenes, divinyl
resin, 2 percent crosslinked with divinylbenzene, pn
' ethyl benzenes, divinylxylenes, diacrylate esters, dirn'eth
pared as described above, was equilibrated in ca. l-molz
acrylate esters, diallyl esters and the like. The aryl nu
NH4OH for an hour. The NH4OH was decanted and tl
cleus can also be substituted with non-reactive substituent
resin was contacted with an ammoniacal metal liquor (
60
groups, e.g., lower alkyl up to 3 carbon atoms and halo
the following composition:
gen. These resins will be referred to hereafter as (thio) ‘
M
acetic and (thio)succinic chelating resins. They are used
in the ammonium salt form.
In practice, an ammoniacal solution containing a min
eral acid salt of luteo cobalt, divalent copper and/or di 65
valent nickel is contacted at room temperature with a
(thio)acetic or a (thio)succinic chelating resin in the am-_
monium salt form. The ammonium salt forms of these
CuSO4-5H2O _____________________________ __ 0.02
NiSO4'6H2O _____________________________ .__ 0.03
[CO('NH3)6]2(-SO4)3 ----------------------- .._
in an aqueous solution of l-molar NH4OH.
After 24 hours of solution-resin contact with constai
agitation,
the excess metal solution was poured oil ar
resins can be preformed, advantageously by equilibration
with ammonium hydroxide, or can be formed in situ by 70 the resin was Washed several times with l-molar NH4O£
{followed by several water washes. There was no obser'
passing through the ammoniacal metals solution. Either
able removal of metals by these washes. ‘The resin w:
a batch type or a column operation can be used. In either
3,082,081
3
4
eluted with l-molar hydrochloric acid and the eluate was
and a blue-green color below. After 43 ml. of clear
e?luent was collected, frequent cuts of the e?luent were
analyzed polarographically.
EXAMPLE 2
The procedure of Example 1 was repeated with a
made and analyzed polarographically. The ?gure
graphically illustrates this separation and shows the pref
(thio)succinic chelating resin, 4 percent crosslinked with
washed with very dilute ammonium hydroxide and Water
erence of the resin for luteo cobalt. The column was then
divinylbenzene, prepared as described above.
Following Table I gives results of the evaluations of
Examples 1 and 2.
until the effluent was clear, after which the resin column
was eluted with l-normal hydrochloric acid and the
eluate was analyzed.
Table I
EQUILIBRIUM RESIN EVALUATION FOR SEPARATION OF AMMONIACAL Cu++~Ni++-C+++
(LUTEO)
Resin
Dry
weight
Resin
vol.1
(15-)
(1111-)
Metal preference ratio
,
Cu++ : N1++ : Cot’r+
Po1y[(vinylbenzylthio)acetic acid] X22..1’oly[(vinylbenzylthio)succinic acid] X4__
1.6
0.5
Capacity
5.4
1. 8
1.2
1
1
2. 6
Mmole/g. Mmo1e./ml.
5. 3
20.1
1.2
3.0
0. 4
0.9
1 Equilibrated in ca. l-molar NHiOH.
2 X=crosslinked, number=pereent combined divinylbenzene.
EXAMPLE 3
EXAMPLE 5
25
The procedures of Examples 1 and 2 were repeated
The procedure of Example 4 was repeated with a
with similar resins but with one-hour contact time and
(thio)acetic chelating resin.
with an approximately equimolar Ni++—-Co+++(luteo)
The analyses of the eluates of Examples 4 and 5 are
liquor. Results are given in following Table II.
given in following Table III.
Table III
COLUMN RESIN EVALUATION FOR SEPARATION OF AMMONIACAL Cu++~-Ni+"——C0+++
(LUTEO)
Resin
Dry
weight
Resin
Vol.1
(2-)
(ml-l
Metal preference ratio
_
Cu++ : Ni++ :Co+++
Po1y[(viny1bcnzy1thio) acetic acid] X41__._
Po1y[(vinylbenzylthio)suceinic acid] X4..
3. 5
3. 8
r.
Capacity
11.0
11.3
1
1
1. 2
1.3
11.6
11.1
Mmolejg. Mm01e./ml.
1.5
1. 9
0.5
0. 6
1 Equilibrated in ca. l-molar NHiOH.
1 X =crosslinked, numbcr=percent combined divinylbcnzene.
Table II
45 In these examples only enough metal solution was con
tacted with the resin to indicate a separation of the
PARTIAL EQUILIBRIUM RESIN EVALUATIONS FOR SEPA
Co+++(luteo) from the Cu++ and Ni++, and, therefore,
RATION OF AIVIMONIACAL Co't’r?LUTEO)——Ni+’r
the resin was only partially equilibrated. ‘Flow rates
varied from I().1—0.3 gal./ft.2/rnin.
What is claimed is:
1. Method for separating luteo cobalt from copper and
nickel by contacting an ammoniacal solution of luteo
Luteo C0+++——Ni++l
Resin
Co+++lNi++
pref. ratio
Capacity,
Mmole/g.
(Thio)suecinie acid X1 k
12. 4
1. 4
(Thio)acetie acid X1. . . _
13. 4
0.6
1 One-hour
equilibrium
test
with
Co(NHa)a+++—Ni++..
approximately
_
cobalt also containing at least one member of the group
consisting of divalent copper and divalent nickel with a
55 chelating resin of the group consisting of resinous poly
meric (vinylbenzylthio)acetic acid and resinous polymeric
(vinylbenzylthio)succinic acid, crosslinked with about
1 to 8 mole percent, total polymer basis, of a crosslinking
agent whereby the luteo cobalt is preferentially adsorbed
equimolar
_
2 X1=erosslinked with one mole percent divmylbenzene.
EXAMPLE 4
60 and the cobalt is concentrated on the resin and eluting the
loaded resin with a mineral acid to remove a concen
trated cobalt tfraction from the resin.
2. The method of claim 1 wherein the loaded resin is
The (thio)succinic acid resin referred to in Example
2 was evaluated for a column separation of the
65
system. The liquor was similar to that described in
Example 1 with the exceptions of a slight variation in
eluted with one-molar hydrochloric acid.
3. Method for separating luteo cobalt from copper and
nickel by passing an ammoniacal solution of luteo cobalt
also containing at least one member of the group consist
ing of divalent copper and divalent nickel through a col
umn of an ammonium hydroxide-equilibrated chelating
the metal concentrations and the presence of 0.25 molar
(NH4)2SO4. The resin (13 ml.) was equilibrated with 70 resin of the group consisting of resinous polymeric
(vinylbenzylthio)acetic acid and resinous polymeric
l-rnolar NH4OH in a column (‘A inch diameter). Then
a total of 150 ml. of the metal liquor was passed down
(vinylbenzylthio)succinic acid, crosslinked with about 1
through the resin column at a ?ow rate varying between
to 8 mole percent, total polymer basis, of a crosslinking
0.1-.2 ml./min. During the loading cycle a sharp color
agent whereby the luteo cobalt is preferentially adsorbed
separation was observed on the resin, a yellow color above
and the cobalt is concentrated on the resin and eluting the
3,082,081
5
6
loaded resin with a mineral acid to remove the cobalt as
OTHER REFERENCES
a concentrate and simultaneously to regenerate the resin.
.
-
~
Hale: Research paper V01. ‘9 1956 pages 104408 (en.
-
References Clted m the ?le of thls patent
UNITED STATES PATENTS
v titled Ohelating Resins), published by Chemical Research
5
Laboratory, Teddington, England, Ion Exchange Digest
Gregor et al.: Industrial and Engineering Chemistry
2,848,322
Conn et a1 ____________ __ Aug. 19, 1958
V01. 44, N0. 12, 1952, pages 2834-2838 (entitled Chelatc
2,964,276
Hazen _______________ __ Sept. 27, 1960
Ion Exchange Resin), Ion Exchange Digest.
Документ
Категория
Без категории
Просмотров
0
Размер файла
357 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа