SYSTEM FOR RECOVERY OF LITHIUM FROM A GEOTHERMAL BRINE
This invention relates generally to a system and process for recovery of select minerals and lithium from a geothermal brine. The system and process are configured for the sequential recovery of zinc, manganese, and lithium from a Salton Sea Known Geothermal Resource Area brine. The system and process includes: 1) an impurity removal circuit; then 2) a continuous counter-current ion exchange (CCIX) circuit for selectively recovering lithium chloride from the brine flow and concentrating it using a CCIX unit; and then 3) a lithium chloride conversion circuit for converting lithium chloride to lithium carbonate or lithium hydroxide product.
1 . A system for recovery of lithium from a lithium-containing brine, said system comprising:
optionally, an impurity removal circuit configured for selectively removing silica, iron and certain metals from said brine to produce a clarified or polished brine;
a continuous counter-current ion exchange circuit positioned downstream of said impurity removal circuit; said continuous counter-current ion exchange circuit configured for selectively recovering lithium chloride from said polished brine; said continuous counter-current ion exchange circuit further configured for concentrating lithium chloride into a lithium chloride solution; and
a lithium chloride conversion circuit positioned downstream of said continuous counter-current ion exchange circuit; said lithium chloride conversion circuit configured for converting lithium chloride in said lithium chloride solution to lithium carbonate or lithium hydroxide product.
2 . The system of claim 1 wherein said brine is a geothermal brine.
3 . The system of claim 1 wherein said impurity removal circuit comprises:
a first set of reaction tanks;
a first clarifier positioned downstream of said first reaction tanks; said first clarifier configured to selectively remove precipitated silica and iron from said brine to form a substantially iron and silica free brine;
a second set of reaction tanks positioned downstream of said first clarifier;
a second clarifier positioned downstream of said second reaction tanks; said second clarifier configure to selectively remove precipitated metal oxides and/or hydroxides from said substantially iron and silica free brine to form a substantially zinc and manganese free brine.
4 . The system of claim 1 further comprising a manganese and zinc solvent extraction circuit positioned downstream of said impurity removal circuit and upstream of said continuous counter-current ion exchange circuit.
5 . The system of claim 4 wherein said manganese and zinc solvent extraction circuit comprises:
a manganese zinc extraction circuit comprising a zinc extraction stage having a first stage contactor, a zinc scrubbing stage having a second stage contactor, and a zinc stripping stage having a third stage contactor; and
a manganese solvent extraction circuit comprising a manganese extraction stage having a first stage contactor, a manganese scrubbing stage having a second stage contactor, and a manganese stripping stage having a third stage contactor.
6 . The system of claim 1 wherein said continuous counter-current ion exchange circuit comprises a continuous counter-current ion exchange lithium extraction unit having a plurality of ion exchange beds or columns containing a lithium selective adsorbent or resin.
7 . The system of claim 6 wherein said continuous counter-current ion exchange lithium extraction unit further comprises a plurality of sequential, individual process zones.
8 . The system of claim 7 wherein each of said process zones said ion exchange beds or columns configured in parallel, in series, or in combinations of parallel and series, flowing either in up flow or down flow modes.
9 . The system of claim 8 wherein fluid flow through said continuous counter-current ion exchange lithium extraction unit is controlled by pumping flow rates and a predetermined timing of a rotating or indexing manifold valve system, whereby said ion exchange beds or columns continually cycle through said process zones.
10 . The system of claim 6 wherein said lithium chloride selective absorbent or resin is a manufactured resin-based alumina imbibed adsorbent, a lithium alumina intercalates adsorbent, an alumina imbibed ion exchange resin, or an alumina-based adsorbent.
11 . The system of claim 1 wherein said lithium chloride conversion circuit comprises:
a third set of reaction tanks;
a third clarifier positioned downstream of said third reaction tanks; said third clarifier configured to selectively remove precipitated calcium and magnesium from said lithium chloride solution to form a substantially calcium and magnesium free brine;
a boron ion exchange circuit positioned downstream of said third clarifier; said boron ion exchange configured to selectively capture boron from said substantially calcium and magnesium free brine to form a substantially calcium, magnesium and/or boron free brine; and
a monovalent or divalent ion exchange circuit positioned downstream of said boron ion exchange circuit; said divalent ion exchange configured to selectively removing any remaining monovalent ions, divalent ions or a combination of both from said substantially calcium, magnesium and/or boron free brine.
12 . The system of claim 11 wherein said lithium chloride conversion circuit further comprising lithium crystallization circuit configured to selectively converting said lithium chloride in said substantially calcium, magnesium and/or boron free brine to lithium carbonate.
13 . The system of claim 11 wherein said lithium chloride conversion circuit further comprising a solvent extraction and electrolysis circuit configured selectively converting said lithium chloride in said substantially calcium, magnesium and/or boron free brine to lithium hydroxide.
14 . A system for recovery of lithium from a lithium-containing brine, said system comprising:
a continuous counter-current ion exchange circuit configured for selectively recovering lithium chloride from said brine; said continuous counter-current ion exchange circuit further configured for concentrating lithium chloride into a lithium chloride solution; said continuous counter-current ion exchange circuit comprising a continuous counter-current ion exchange lithium extraction unit having a plurality of ion exchange beds or columns containing a lithium selective adsorbent or resin; and said continuous counter-current ion exchange lithium extraction unit further comprising a plurality of sequential, individual process zones.
15 . The system of claim 14 wherein said brine is a geothermal brine.
16 . The system of claim 14 further comprising an impurity removal circuit positioned upstream of said continuous counter-current ion exchange circuit, and said impurity removal circuit configured for selectively removing silica, iron and certain metals from said brine to produce a clarified or polished brine.
17 . The system of claim 16 wherein said impurity removal circuit comprises:
a first set of reaction tanks;
a first clarifier positioned downstream of said first reaction tanks; said first clarifier configured to selectively remove precipitated silica and iron from said brine to form a substantially iron and silica free brine;
a second set of reaction tanks positioned downstream of said first clarifier;
a second clarifier positioned downstream of said second reaction tanks; said second clarifier configure to selectively remove precipitated metal oxides and/or hydroxides from said substantially iron and silica free brine to form a substantially zinc and manganese free brine.
18 . The system of claim 14 further comprising a manganese and zinc solvent extraction circuit positioned downstream of said impurity removal circuit and upstream of said continuous counter-current ion exchange circuit.
19 . The system of claim 18 wherein said manganese and zinc solvent extraction circuit comprises:
a manganese zinc extraction circuit comprising a zinc extraction stage having a first stage contactor, a zinc scrubbing stage having a second stage contactor, and a zinc stripping stage having a third stage contactor; and
a manganese solvent extraction circuit comprising a manganese extraction stage having a first stage contactor, a manganese scrubbing stage having a second stage contactor, and a manganese stripping stage having a third stage contactor.
20 . The system of claim 14 wherein said process zones comprise said ion exchange beds or columns containing said lithium selective adsorbent or resin.
21 . The system of claim 20 wherein said ion exchange beds or columns of said process zones are configured in parallel, in series, or in combinations of parallel and series, flowing either in up flow or down flow modes.
22 . The system of claim 21 wherein fluid flow through said continuous counter-current ion exchange lithium extraction unit is controlled by pumping flow rates and a predetermined timing of a rotating or indexing manifold valve system, whereby said ion exchange beds or columns continually cycle through said process zones.
23 . The system of claim 14 wherein said lithium chloride selective absorbent or resin is a manufactured resin-based alumina imbibed adsorbent, a lithium alumina intercalates adsorbent, an alumina imbibed ion exchange resin, or an alumina-based adsorbent.
24 . The system of claim 14 further comprising a lithium chloride conversion circuit positioned downstream of said continuous counter-current ion exchange circuit; said lithium chloride conversion circuit configured for converting lithium chloride in said lithium chloride solution to lithium carbonate or lithium hydroxide product.
25 . The system of claim 24 wherein said lithium chloride conversion circuit comprises:
a third set of reaction tanks;
a third clarifier positioned downstream of said third reaction tanks; said third clarifier configured to selectively remove precipitated calcium and magnesium from said lithium chloride solution to form a substantially calcium and magnesium free brine;
a boron ion exchange circuit positioned downstream of said third clarifier; said boron ion exchange configured to selectively capture boron from said substantially calcium and magnesium free brine to form a substantially calcium, magnesium and/or boron free brine; and
a divalent ion exchange circuit positioned downstream of said boron ion exchange circuit; said divalent ion exchange configured to selectively removing any remaining divalent ions from said substantially calcium, magnesium and/or boron free brine.
26 . The system of claim 24 wherein said lithium chloride conversion circuit further comprising a crystallization circuit configured to selectively converting said lithium chloride in said substantially calcium, magnesium and/or boron free brine to lithium carbonate.
27 . The system of claim 24 wherein said lithium chloride conversion circuit further comprising a solvent extraction and electrolysis circuit configured selectively converting said lithium chloride in said substantially calcium, magnesium and/or boron free brine to lithium hydroxide.