Concentrating lithium carbonate after regeneration of lithium sorbent

Patent metadata

Field	Value
Publication number	US-2019134607-A1
Application number	US-201816230808-A
Country	US
Kind code	A1
Filing date	Dec 21, 2018
Priority date	Aug 18, 2016
Publication date	May 9, 2019
Grant date	—

Abstract

A system and method that includes flowing brine containing a metal ion through a reactor that includes porous particles having metal ion imprinted polymer having selective binding sites. The system and method further include discharging the brine from the reactor, contacting the porous particles with water, and pressurizing the reactor with carbon dioxide. The carbon dioxide reacts with the adsorbed metal ions to form a metal carbonate solution, where the metal carbonate solution can then be continuously purified with ion exchange. The method can include recycling eluent from the ion exchange back into the system for re-use. The method further includes depressurizing the reactor to precipitate metal carbonate from the metal carbonate solution and discharging the metal carbonate solution from the reactor.

First claim

What is claimed is:

1 . A system comprising:
a reactor comprising:
a reactor vessel;
a brine inlet through which brine is introduced into the reactor vessel;
a brine outlet through which brine is discharged from the reactor vessel;
a water inlet through which water is introduced into the reactor vessel;
a carbon dioxide inlet configured to receive carbon dioxide from a carbon dioxide source, the carbon dioxide used to pressurize the reactor vessel and depressurize the reactor vessel;
a metal bicarbonate solution outlet through which metal bicarbonate is discharged from the reactor vessel;
porous particles in the reactor vessel, wherein the porous particles comprise a metal ion imprinted polymer formed from a hydrophilic co-monomer, a cross-linking agent and a metal containing polymerizable compound that includes at least one metal chelating ligand, wherein the metal ion imprinted polymer comprises a plurality of metal ion selective binding sites; and
at least a first and a second ion exchange columns in fluid communication with the metal bicarbonate solution outlet configured to work in tandem to remove impurities from the metal carbonate solution, wherein the system is capable of switching the first and the second ion exchange columns between a first mode of removing impurities from the metal carbonate solution and a second mode of reconditioning the first or the second ion exchange column in preparation to further receive metal bicarbonate solution and remove impurities therefrom.

2 . The system of claim 1 , further comprising corresponding ion exchange column outlets wherein used eluent is collected recycled back into the system for conditioning prior to re-use or wherein purified metal carbonate solution is collected.

3 . The system of claim 1 , wherein the metal ion imprinted polymer comprises a lithium ion imprinted polymer.

4 . The system of claim 1 , further comprising a crystallizer configured to convert metal bicarbonate collected from the first or second ion exchange column to metal carbonate and crystallize the metal carbonate.

5 . The system of claim 1 , wherein the metal ion imprinted polymer includes at least one β-diketone corresponding to the metal ion selective binding sites.

6 . A system comprising:
a reactor comprising:
a reactor vessel;
a brine inlet through which brine is introduced into the reactor vessel;
a brine outlet through which brine is discharged from the reactor vessel;
a water inlet through which water is introduced into the reactor vessel;
a carbon dioxide inlet configured to receive carbon dioxide from a carbon dioxide source, the carbon dioxide used to pressurize the reactor vessel and depressurize the reactor vessel;
a metal bicarbonate solution outlet through which metal carbonate is discharged from the reactor vessel;
porous particles in the reactor vessel, wherein the porous particles comprise a metal ion imprinted polymer formed from a hydrophilic co-monomer, a cross-linking agent and a metal containing polymerizable compound that includes at least one metal chelating ligand, wherein the metal ion imprinted polymer comprises a plurality of metal ion selective binding sites; and
an array of ion exchange columns in fluid communication with the metal bicarbonate solution outlet configured to work in tandem to remove divalent ions from the metal bicarbonate solution and recover water to reuse in the system, wherein the system continuously switches between a portion of the array of ion exchange columns removing divalent ions from the metal bicarbonate solution while a remaining portion of the array of ion exchange columns is being regenerated to again receive metal bicarbonate solution to remove divalent ions, and wherein used eluent used in running the array of ion exchange columns are recycled back into the system to be purified and re-used to elute the metal carbonate solution and divalent ions.

7 . The system of claim 6 , wherein the metal ion imprinted polymer comprises a lithium ion imprinted polymer.

8 . The system of claim 6 , further comprising a crystallizer configured to receive purified metal bicarbonate solution output from the array of ion exchange columns and to convert the metal bicarbonate solution to metal carbonate, and to crystallize the metal carbonate.

9 . The system of claim 7 , wherein the metal bicarbonate solution is lithium bicarbonate.

10 . The system of claim 6 , wherein the metal ion imprinted polymer includes at least one β-diketone corresponding to the metal ion selective binding sites.

11 . A method comprising:
flowing brine containing a metal ion through a reactor comprising porous particles to remove metal ions from the brine, wherein the porous particles comprise a metal ion imprinted polymer formed from a hydrophilic co-monomer, cross-linking agent and a metal containing polymerizable compound that includes at least one metal chelating ligand, wherein the metal ion imprinted polymer comprises a plurality of metal ion selective binding sites; discharging the brine from the reactor; contacting the porous particles with water; pressurizing the reactor with carbon dioxide, wherein the carbon dioxide reacts with the adsorbed metal ions to form a metal carbonate solution; depressurizing the reactor to precipitate metal carbonate from the metal carbonate solution; discharging the metal bicarbonate solution from the reactor; and running the metal bicarbonate solution through a series of ion exchange columns to remove impurities, wherein the series of ion exchange columns is switchable between a purification mode and a regeneration mode.

12 . The method of claim 11 , wherein a first portion of the series of ion exchange columns is in the purification mode while a remaining portion of the series of ion exchange columns is in the regeneration mode.

13 . The method of claim 11 , wherein the metal ion is lithium and the metal bicarbonate is lithium bicarbonate.

14 . The method of claim 11 , further comprising converting the metal bicarbonate to metal carbonate and crystallizing the metal carbonate.

15 . The method of claim 11 , wherein the metal ion imprinted polymer includes at least one β-diketone corresponding to the metal ion selective binding sites.

16 . The method of claim 11 , further comprising a step of recycling ion exchange column eluent generated from running the metal bicarbonate solution through the series of ion exchange columns such that the ion exchange column eluent can be reused to elute more brine containing metal ions through the reactor and ion exchange columns.

17 . The method of claim 16 , further comprising one or more steps for purifying the eluent wash prior to reusing the eluent for eluting more bring containing metal ions through the reactor and ion exchange columns.

Assignees

• Stanford Res Inst Int

Inventors

• Hornbostel Marc
• Ventura Susanna
• Bhamidi Srinivas
• Nagar Anoop

Classifications

• B01J20/267

  Cross-linked polymers · CPC title

• B01J20/3064

  Addition of pore forming agents, e.g. pore inducing or porogenic agents · CPC title

• B01J20/043

  Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite · CPC title

• B01J20/3475 Primary

  in the liquid phase · CPC title

• C22B26/12

  Obtaining lithium · CPC title