Process for selective adsorption and recovery of lithium from natural and synthetic brines
This invention relates generally to a process for selective adsorption and recovery of lithium from natural and synthetic brines, and more particular to a process for recovering lithium from a natural or synthetic brine solution by passing the brine solution through a lithium selective adsorbent in a continuous countercurrent adsorption and desorption circuit.
1 . A continuous countercurrent adsorption and desorption process for recovery of an enhanced lithium product solution from a lithium-containing brine solution, said process comprising the cyclical and sequential steps of:
pumping fluid flow through a continuous countercurrent adsorption and desorption circuit comprising an adsorption displacement zone, an adsorption loading zone, an entrainment rejection zone, and an elution zone, each of said zones comprising one or more adsorbent beds or columns having a lithium selective adsorbent; said process further comprising:
a) recycling a portion of a lithium product eluate from the elution zone to the adsorption displacement zone and displacing residual feed brine from the one or more adsorbent beds or columns in the adsorption displacement zone to form a displacement feed brine;
b) pumping the displacement feed brine from the adsorption displacement zone and the lithium-containing brine solution through the adsorption loading zone to adsorb lithium in the displacement feed brine and the lithium-containing brine solution on the lithium selective adsorbent in the one or more adsorbent beds or columns and form a lithium-depleted brine raffinate;
c) pumping the lithium-depleted brine raffinate from the adsorption loading zone through the entrainment rejection zone and displacing a latent eluate solution from the one or more adsorbent beds or columns in said entrainment rejection zone using a portion of said lithium-depleted brine raffinate;
d) pumping said displaced latent eluate solution and a portion of an eluant solution through said elution zone to desorb a portion of the lithium on the lithium selective adsorbent in the one or more adsorbent beds or columns and form said lithium product eluate; and
e) collecting a portion of said lithium product eluate as an enhanced lithium product solution.
2 . The process of claim 1 wherein said elnant solution comprises lithium chloride and water at a concentration of up to about 1000 mg/kg lithium.
3 . The process of claim 1 further comprising recovering lithium from said enhanced lithium product solution.
4 . The process of claim 3 further comprising selectively converting said recovered lithium to lithium carbonate, lithium hydroxide, or both.
5 . The process of claim 3 further comprising dewatering said enhanced lithium product solution using membrane separation.
6 . The process of claim 5 wherein said membrane separation comprises reverse osmosis or nanofiltration.
7 . The process of claim 6 wherein said dewatered enhanced lithium product solution has a concentration from about 3000 to about 5000 mg/kg lithium.
8 . The process of claim 5 further comprising concentrating said dewatered enhanced lithium product solution to produce a high lithium concentration, enhanced lithium product solution and a recycle eluant solution.
9 . The process of claim 8 further comprising providing said enhanced lithium product solution, said high lithium concentration, enhanced lithium product solution, or both to a lithium solvent extraction and electrowinning process, a solvent extraction and membrane electrolysis process, or a recovery process for production of high purity lithium hydroxide and lithium carbonate for battery production.
10 . The process of claim 8 wherein said dewatered and concentrated enhanced lithium product solution has a concentration from about 5000 to about 30000 mg/kg lithium.
11 . The process of claim 3 wherein said enhanced lithium product solution has a concentration of greater than 3000 mg/kg lithium.
12 . The process of claim 1 wherein said lithium-containing brine solution comprises a natural brine, a synthetic brine, a polished brine, or a combination thereof.
13 . The process of claim 1 wherein said lithium-containing brine solution comprises a continental brine, a geothermal brine, an oil field brine, a brine from hard rock lithium mining, or a combination thereof.
14 . The process of claim 1 wherein said lithium selective adsorbent is a lithium alumina intercalate prepared from hydrated alumina, a lithium aluminum layered double hydroxide chloride, a layered double hydroxide modified activated alumina, a layered double hydroxide imbibed ion exchange resin or copolymer or molecular sieve or zeolite, layered aluminate polymer blends, a lithium manganese oxide, a titanium oxide, an immobilized crown ether, or a combination thereof.
15 . The process of claim 1 wherein said continuous countercurrent adsorption and desorption circuit comprises a multi-port valve system.
16 . The process of claim 15 , wherein the multi-port valve system is a rotary multi-port valve system.
17 . The process of claim 16 wherein said fluid flow through said adsorption displacement zone, said adsorption loading zone, said entrainment rejection zone, and said elution zone of said continuous countercurrent adsorption and desorption circuit is controlled by pumping flow rates, predetermined indexing, or a combination of both of said rotary multi-port valve system.
18 . The process of claim 17 wherein:
said adsorption displacement zone is positioned upstream with respect to fluid flow of said adsorption loading zone;
said adsorption loading zone is positioned upstream with respect to fluid flow of and in fluid communication with said entrainment rejection zone;
said entrainment rejection zone positioned upstream with respect to fluid flow of and in fluid communication with said elution zone; and
said elution zone in fluid communication with said adsorption displacement zone.
19 . The process of claim 18 further comprising passing said lithium-containing brine solution through said adsorption loading zone for a predetermined amount of contact time.
20 . The process of claim 17 further comprising pumping said fluid flow through said adsorption displacement zone, said adsorption loading zone, said entrainment rejection zone, and said elution zone of said continuous countercurrent adsorption and desorption circuit in a direction countercurrent to the predetermined indexing of said adsorbent beds or columns through said adsorption displacement zone, said adsorption loading zone, said entrainment rejection zone, and said elution zone of said continuous countercurrent adsorption and desorption circuit.
21 . The process of claim 1 wherein said eluant solution comprises lithium chloride and water at a concentration of up to about 1000 mg/kg lithium and at temperatures of about 5° C. to about 100° C.
22 . A continuous countercurrent adsorption and desorption process for recovery of an enhanced lithium product solution from a lithium-containing brine solution, said process comprising:
1) pumping fluid flow cyclically and sequentially through a continuous countercurrent adsorption and desorption circuit comprising a multi-port valve system having a plurality of process zones, said process zones comprising an adsorption displacement zone, an adsorption loading zone, an entrainment rejection zone, and an elution zone, each of said process zones comprising one or more adsorbent beds or columns having a lithium selective adsorbent, said pumping fluid flow through said adsorption displacement zone, said adsorption loading zone, said entrainment rejection zone, and said elution zone is countercurrent relative to predetermined indexing of said adsorbent beds or columns through said adsorption displacement zone, said adsorption loading zone, said entrainment rejection zone, and said elution zone, introducing the lithium-containing brine solution into the adsorption loading zone; said process further comprising:
a) recycling a portion of a lithium product eluate from the elution zone to the adsorption displacement zone and displacing residual feed brine solution from the one or more adsorbent beds or columns in the adsorption displacement zone to form a displacement feed brine
b) pumping said displacement feed brine from the adsorption displacement zone and the lithium-containing brine solution through the adsorption loading zone to adsorb a portion of lithium in said displacement feed brine and the lithium-containing brine solution on the lithium selective adsorbent in the one or more adsorbent beds or columns and form a lithium-depleted brine raffinate;
c) pumping the lithium-depleted brine raffinate from the adsorption loading zone through the entrainment rejection zone and displacing a latent eluate solution from the one or more adsorbent beds or columns in said entrainment rejection zone using a portion of said lithium-depleted brine raffinate;
d) pumping said displaced latent eluate solution and a portion of an eluant solution through said elution zone to strip a portion of the lithium adsorbed on the lithium selective adsorbent in the one or more adsorbent beds or columns and form a lithium product eluate; and
e) collecting a portion of said lithium product eluate as an enhanced lithium product solution.
23 . The process of claim 22 wherein said eloant solution comprises lithium chloride and water at a concentration of up to about 1000 mg/kg lithium.
24 . The process of claim 22 further comprising recovering lithium from said enhanced lithium product solution.
25 . The process of claim 24 further comprising selectively converting said recovered lithium to lithium carbonate, lithium hydroxide, or both.
26 . The process of claim 24 further comprising dewatering said enhanced lithium product solution using membrane separation.
27 . The process of claim 26 wherein said membrane separation comprises reverse osmosis or nanofiltration.
28 . The process of claim 27 wherein said dewatered enhanced lithium product solution has a concentration from about 3000 to about 5000 mg/kg lithium.
29 . The process of claim 26 further comprising concentrating said dewatered enhanced lithium product solution to produce a high lithium concentration, enhanced lithium product solution and a recycle eluant solution.
30 . The process of claim 29 further comprising providing said enhanced lithium product solution, said high lithium concentration, enhanced lithium product solution, or both to a lithium solvent extraction and electrowinning process, a solvent extraction and membrane electrolysis process, or a recovery process for production of high purity lithium hydroxide and lithium carbonate for battery production.
31 . The process of claim 29 wherein said dewatered and concentrated enhanced lithium product solution has a concentration from about 5000 to about 30000 mg/kg lithium.
32 . The process of claim 24 wherein said enhanced lithium product solution has a concentration of greater than 3000 mg/kg lithium.
33 . The process of claim 22 wherein said lithium-containing brine solution comprises a natural brine, a synthetic brine, a polished brine, or a combination thereof.
34 . The process of claim 22 wherein said lithium-containing brine solution comprises a continental brine, a geothermal brine, an oil field brine, a brine from hard rock lithium mining, or a combination thereof.
35 . The process of claim 22 wherein said lithium selective adsorbent is a lithium alumina intercalate prepared from hydrated alumina, a lithium aluminum layered double hydroxide chloride, a layered double hydroxide modified activated alumina, a layered double hydroxide imbibed ion exchange resin or copolymer or molecular sieve or zeolite, layered aluminate polymer blends, a lithium manganese oxide, a titanium oxide, an immobilized crown ether, or a combination thereof.
36 . The process of claim 22 , wherein the multi-port valve system is a rotary multi-port valve system.
37 . The process of claim 36 wherein said fluid flow through said adsorption displacement zone, said adsorption loading zone, said entrainment rejection zone, and said elution zone of said continuous countercurrent adsorption and desorption circuit is controlled by pumping flow rates, predetermined indexing, or a combination of both of said rotary multi-port valve system.
38 . The process of claim 37 wherein:
said adsorption displacement zone is positioned upstream with respect to fluid flow of said adsorption loading zone;
said adsorption loading zone is positioned upstream with respect to fluid flow of and in fluid communication with said entrainment rejection zone;
said entrainment rejection zone positioned upstream with respect to fluid flow of and in fluid communication with said elution zone; and
said elution zone in fluid communication with said adsorption displacement zone.
39 . The process of claim 38 further comprising passing said lithium-containing brine solution through said adsorption loading zone for a predetermined amount of contact time.
40 . The process of claim 22 wherein said eluant solution comprises lithium chloride and water at a concentration of up to about 1000 mg/kg lithium and at temperatures of about 5° C. to about 100° C.