# US 11,077,408 B2 · Selective extraction film for mining application

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- Number: US 11,077,408 B2
- Document ID: US11077408B2
- Status: Granted
- Kind: B2
- Application number: 16/470,433
- Filed: 2017-12-21
- Published: 2020-04-09
- Granted: 2021-08-03
- Earliest claimed: 2016-12-23
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Yoke Lim Lim; Natalia Widjojo; Richard Grant Macoun; Natalia Emeliyanova; Ulf Baus
- Web page: https://patentgrep.com/patent/US11077408B2

## CPC

- B01D 67/00091: {by evaporation}
- B01D 71/30: Polyalkenyl halides
- B01D 61/20: Accessories; Auxiliary operations
- B01D 67/00111: {Polymer pretreatment in the casting solutions}
- B01D 69/06: Flat membranes
- B01D 71/301: {Polyvinylchloride}
- B01D 71/40: Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- C22B 3/20: Treatment or purification of solutions, e.g. obtained by leaching (C22B3/18 takes precedence)
- C22B 3/22: by physical processes, e.g. by filtration, by magnetic means {, or by thermal decomposition} (treatment or purification of solutions by liquid-liquid extraction C22B3/26)
- C22B 23/0453: {Treatment or purification of solutions, e.g. obtained by leaching (C22B23/0407 takes precedence)}
- B01D 2311/12: Addition of chemical agents
- B01D 2311/18: pH control
- B01D 2315/08: Fully permeating type; Dead-end filtration
- B01D 2323/06: Specific viscosities of materials involved
- B01D 2323/12: Specific ratios of components used
- B01D 2323/20: Plasticizers
- B01D 2323/2182: Organic additives
- B01D 2323/21828: Ammonium Salts
- C02F 2103/06: Contaminated groundwater or leachate
- C02F 2103/10: from quarries or from mining activities
- C02F 2103/16: from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
- Y02P 10/20: Recycling
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS
- C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention is related to a polymer membrane for the selective extraction of cobalt (II) ions as well as a method for extracting cobalt (II) ions using said polymer membrane.

## Claims

### Claim 1

A polymer membrane, comprising
i) about 5.0 to about 33.0 wt.-% of a base polymer (B),
ii) optionally at least about 18 wt.-% of a plasticizer (P),
iii) at least about 22 wt.-% of an extractant (E), and
iv) at least about 26 wt.-% of a modifier (M) comprising an aromatic or aliphatic ester of phosphoric acid,
each based on the overall weight of the polymer membrane,
comprising the base polymer (B) and the extractant (E) in a weight ratio w(B)/w(E) in the range of 0.1 to 0.7, wherein w(B) is the overall amount of the base polymer (B) in wt.-% and w(E) is the overall amount of the extractant (E) in wt.-%, based on the overall weight of the polymer membrane, respectively.

### Claim 2 (depends on 1)

The polymer membrane according to claim 1, wherein the base polymer (B) comprises at least one polymer selected from the group consisting of cellulose, cellulose acetate, cellulose triacetate, polyvinylchloride (PVC), polyethylene, polypropylene, polystyrene, polyacrylonitrile, polymethylacrylate, polymethylmethacrylate, polybutadiene, polyisoprene, polysulfone and polyethersulfone.

### Claim 3 (depends on 2)

The polymer membrane according to claim 2, wherein the base polymer (B) comprises polyvinylchloride (PVC).

### Claim 4 (depends on 1)

The polymer membrane according to claim 1, wherein the extractant (E) comprises a tertiary amine or a quaternary ammonium compound.

### Claim 5 (depends on 1)

The polymer membrane according to claim 1, wherein the base polymer (B) comprises polyvinylchloride (PVC), and wherein the extractant (E) comprises a tertiary amine or a quaternary ammonium compound.

### Claim 6 (depends on 1)

The polymer membrane according to claim 1, comprising the plasticizer (P), wherein the polymer membrane comprises the extractant (E) and the plasticizer (P) in a weight ratio w(E)/w(P) below 1.6, wherein w(E) is the overall amount of the extractant (E) in wt.-% and w(P) is the overall amount of the plasticizer (P) in wt.-%, based on the overall weight of the polymer membrane, respectively.

### Claim 7 (depends on 1)

The polymer membrane according to claim 1, comprising the plasticizer (P), wherein the plasticizer (P) comprises at least one compound selected from the group consisting of 2-nitro-phenyl octyl ether (2-NPOE), 2-nitro-phenyl pentyl ether (2-NPPE), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), di-2-ethylhexyl phthalate (DEHP), and 1,2-cyclohexanedicarbonacid-diisononylester.

### Claim 8 (depends on 1)

The polymer membrane according to claim 1, wherein the extractant (E) comprises at least one compound selected from the group consisting of trioctylmethylammonium chloride (Aliquot 336®), tetra-n-butylammonium bromide, tetramethylammonium chloride, dimethyldioctadecylammonium chloride, N,N-dioctyl-1-octanamine (Alamine 336®), and Tri-n-octylamine (Alamine 308®).

### Claim 9 (depends on 1)

The polymer membrane according to claim 1, Wherein the modifier (M) comprises at least one compound selected from the group consisting of triphenylphosphate, tri-n-butylphosphate, tri-sec-butylphosphate, tri-tert-butylphosphate, triethylphosphate, trimethylphosphate, tri-n-propylphosphate, triisopropylphosphate and tri-n-hexylphosphate.

### Claim 10 (depends on 1)

A method for separating cobalt from other metals, comprising:
a) providing a container comprising a first chamber and a second chamber separated by a polymer membrane according to claim 1,
b) feeding a composition comprising cobalt and/or at least one salt thereof and at least one further metal other than cobalt and/or at least one salt of a further metal other than cobalt into the first chamber,
c) adding thiocyanic acid and/or a salt thereof to the composition of b) in the first chamber,
d) optionally adding a pH-buffer to the composition obtained in c) the first chamber, and
e) feeding a stripping solution (S) into the second chamber.

### Claim 11 (depends on 10)

The method according to claim 10, wherein the stripping solution (S) comprises ammonia (NH3) and triethanolamine (TEA) in a molar ratio in the range of about 2:1 to about 1:2.

### Claim 12 (depends on 10)

The method according to claim 10, wherein ammonium thiocyanate (NH4SCN) is applied in c).

### Claim 13 (depends on 10)

The method according to claim 10, wherein
i) the pH-buffer comprises acetic acid and ammonium acetate and/or
ii) the pH value of the composition obtained in d) is in the range of 2 to 6.

### Claim 14 (depends on 10)

The method according to claim 10, wherein the cobalt salt comprises at least one compound selected from the group consisting of cobalt (II) chloride (CoCl2), cobalt (II) bromide (CoBr2), cobalt (II) iodide (CoI2), cobalt (II) fluoride (CoF2), cobalt (II) sulfate (CoSO4), cobalt (II) sulfite (CoSO3), and cobalt (II) nitrate (Co(NO3)2).

### Claim 15 (depends on 10)

The method according to claim 10, wherein the at least one salt of a further metal other than cobalt comprises at least one compound selected from the group consisting of nickel (II) chloride (NiCl2), nickel (II) bromide (NiBr2), nickel (II) iodide (NiI2), nickel (II) fluoride (NiF2), nickel (II) sulfate (NiSO4), nickel (II) sulfite (NiSO3), and nickel (II) nitrate (Ni(NO3)2).