Selective lithium extraction chemistry for geothermal brine

Patent metadata

Field	Value
Publication number	US-2023166992-A1
Application number	US-202117538858-A
Country	US
Kind code	A1
Filing date	Nov 30, 2021
Priority date	Nov 30, 2021
Publication date	Jun 1, 2023
Grant date	—

Abstract

A method for selective extraction of lithium from geothermal brines using host-guest complexes of host molecules such as calixarene, dendrimeric polymers, hyper-branched polymers, and/or acid-catalyzed resins complexed with synergists such as organic acids, condensation polymers, olefin/maleic anhydride copolymers, and/or chelants.

First claim

What is claimed is:

1 . A method for selectively extracting lithium from geothermal brine, the method comprising:
contacting a geothermal brine containing lithium with a host-guest complex in an effective amount and for an effective period of time to selectively extract lithium from the geothermal brine; and extracting lithium from the geothermal brine into the host-guest complex.

2 . The method of claim 1 where the host-guest complex comprises a host molecule selected from the group consisting of calixarene, dendrimeric polymers, hyper-branched polymers, acid-catalyzed resins, and combinations thereof.

3 . The method of claim 2 where the acid-catalyzed resins are selected from the group consisting of:
alkoxylated p-t-alkyl phenol resins where the alkyl group is selected from the group consisting of methyl, ethyl, propyl, butyl, and combinations thereof;
resins of formula (I):

where x ranges from 1 to 12, y ranges from 1 to 300, and n is such that the weight average molecular weight ranges from about 100 to about 15,000;

resins of formula (II):

where R is hydrogen or methyl, m ranges from 1 to 100, and p ranges from 1 to 50.

4 . The method of claim 1 where the host-guest complex comprises a synergist selected from the group consisting of:
an organic acid having from 1 to 7 carbon atoms;
a condensation polymer that is the reaction product of:
at least one alkyl phenol having from 1 to 30 carbon atoms,
at least one aldehyde having from 1 to 4 carbon atoms, and
at least one polyamine of the general formula (III):
R 11 R 12 N(R 13 NR 14 ) z NR 15 R 16   (III)

where R 11 , R 12 , R 15 , and R 16 are independently hydrogen or C1-C4 alkyl and R 13 and R 13 are independently —(CH 2 ) q — where q ranges from 1-6 and where z ranges from 1 to 5;

olefin/maleic anhydride copolymers having the formula (IV):

where R 1 , R 2 , R 3 , and R 4 are independently hydrogen, C1-C30 straight chain or branched alkyl; R 7 , R 8 , R 9 , R 10 are independently hydrogen, hydroxyl or C1-C4 alkyl; R 5 and R 6 are independently hydrogen, C1-C30 branched or straight chain alkyl; and a, b, and c are independently 0 to 100 where at least two of a, b, and c are each at least 1;

chelants selected from the group consisting of phosphonic acid and its esters, phosphoric acid and its esters, amino phosphonates, polycarboxylic acids and their esters, ethylenediaminetetraacetic acid (EDTA) derivatives chelants, succinic acids, malic acids, sulfosuccinic acids and their esters, citric acid-based chelants, oxalic acid and its esters; and combinations thereof; and
combinations thereof.

5 . The method of claim 4 where the organic acid is selected from the group consisting of malic acid, succinic acid, tannic acid, glucaric acid, gluconic acid, tartaric acid, and combinations thereof.

6 . The method of claim 1 where the host-guest complex comprises a host molecule and a synergist and the molar ratio of synergist to the host molecule in the host-guest complex ranges from 1:1 to about 0.001:1.

7 . The method of claim 1 where the effective amount of host-guest complex is a mole ratio ranging from about 0:001:1 to about 100:1 based on the moles of lithium in the geothermal brine.

8 . The method of claim 1 where the host-guest complex is incorporated into a porous membrane.

9 . The method of claim 8 where the membrane comprises:
a membrane matrix comprising a polymer selected from the group consisting of polyimides, polyvinylacetate, polyethers, polysulphones, polypyrrole, polythiophenes, polyacetylenes, derivatized perfluoro alkylated polymers, polyamides, and combinations thereof;
a conducting medium selected from the group consisting of bucky paper, graphite, exfoliated graphite, functionalized graphite, metal-doped graphite, carbon nanotubes, nanofibers, nanosheets, functionalized carbon nanoparticles, crosslinked carbon nanotubes, fiber mats, quantum dots doped with heteroatoms selected from the group consisting of nitrogen, phosphorus, boron, and combinations thereof; and
a plasticizer selected from the group consisting of fatty acids, phthalates, esters, and combinations thereof.

10 . The method of claim 1 where contacting the geothermal brine with the host-guest complex comprises additionally contacting the geothermal brine with an organic carbonate effective for lithium dissolution, and the method further comprises application of an anodic potential.

11 . A method for selectively extracting lithium from geothermal brine, the method comprising:
contacting a geothermal brine containing lithium with a host-guest complex in an effective amount and for an effective period of time to selectively extract lithium from the geothermal brine, where:
the host-guest complex comprises a host molecule selected from the group consisting of calixarene, dendrimeric polymers, hyper-branched polymers, acid-catalyzed resins, and combinations thereof; and
the host-guest complex comprises a synergist selected from the group consisting of:
an organic acid having from 1 to 7 carbon atoms;
a condensation polymer that is the reaction product of:
at least one alkyl phenol having from 1 to 30 carbon atoms,
at least one aldehyde having from 1 to 4 carbon atoms, and
at least one polyamine of the general formula (III):
R 11 R 12 N(R 13 NR 14 ) z NR 15 R 16   (III)

where R 11 , R 12 , R 15 , and R 16 are independently hydrogen or C1-C4 alkyl and R 13 and R 13 are independently —(CH 2 ) q — where q ranges from 1-6 and where z ranges from 1 to 5;

olefin/maleic anhydride copolymers having the formula (IV):

where R 1 , R 2 , R 3 , and R 4 are independently hydrogen, C1-C30 straight chain or branched alkyl; R 7 , R 8 , R 9 , R 10 are independently hydrogen, hydroxyl or C1-C4 alkyl; R 5 and R 6 are independently hydrogen, C1-C30 branched or straight chain alkyl; and a, b, and c are independently 0 to 100 where at least two of a, b, and c are each at least 1;

chelants selected from the group consisting of phosphonic acid and its esters, phosphoric acid and its esters, amino phosphonates, polycarboxylic acids and their esters, ethylenediaminetetraacetic acid (EDTA) derivatives chelants, succinic acids, malic acids, sulfosuccinic acids and their esters, citric acid-based chelants, oxalic acid and its esters; and combinations thereof; and
combinations thereof; and

extracting lithium from the geothermal brine into the host-guest complex.

12 . The method of claim 11 where the host molecule is an acid-catalyzed resin selected from the group consisting of:
alkoxylated p-t-alkyl phenol resins where the alkyl group is selected from the group consisting of methyl, ethyl, propyl, butyl, and combinations thereof;
resins of formula (I):

where x ranges from 1 to 12, y ranges from 1 to 300, and n is such that the weight average molecular weight ranges from about 100 to about 15,000;

resins of form

Assignees

• Baker Hughes Oilfield Operations Llc

Inventors

• Murugesan Sankaran
• Felipe Mary Jane Legaspi
• Weers Jerry J
• Ugono Onome
• Ekoue-Kovi Kekeli A
• Pinappu Sai Reddy

Classifications

• C02F2101/10

  Inorganic compounds · CPC title

• C02F1/44

  by dialysis, osmosis or reverse osmosis {(general membrane separation processes B01D61/00, membrane modules B01D63/00, electrodialysis C02F1/4693, combination of membrane modules and bioreactors C02F3/1268)} · CPC title

• Y02P10/20

  Recycling · CPC title

• C02F1/68 Primary

  by addition of specified substances, e.g. trace elements, for ameliorating potable water (medicinal water A61K) · CPC title

• C02F1/683 Primary

  by addition of complex-forming compounds · CPC title