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1. (WO2019000095) METHOD AND APPARATUS FOR THE TREATMENT OF WATER WITH THE RECOVERY OF METALS
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Claims:

1. A method of recovering lithium from energy process water, comprising: removing alkaline earth metals from the water to form a treated water; passing the treated water through a reactor column to contact the treated water with a titanium oxide molecular sieve to adsorb lithium ions in the molecular sieve; draining the treated water from the reactor column while the molecular sieve remains in the reactor column; eluting the lithium ions from the molecular sieve using a strong acid solution to desorb the lithium ions into an eluate fluid; and collecting the eluate fluid from the reactor column, the eluate fluid being rich with lithium ions.

2. The method of claim 1, wherein the water is at a temperature less than 100°C and the titanium oxide molecular sieve includes pellets of titanium oxide in a polyacrylamide matrix and the reactor column includes an outlet screen with a passage size smaller than the pellets.

3. The method of claim 1, wherein the water is at a temperature more than 100°C and the titanium oxide molecular sieve includes pellets of titanium oxide in a zeolite or aerogel matrix and the reactor column includes an outlet screen with a passage size smaller than the pellets.

4. The method of claim 1, wherein removing includes initially treating to remove hydrocarbons by froth flotation.

5. The method of any one of claims 1 or 4, wherein removing alkaline earth metals comprises precipitating alkaline earth metals ions and filtering the precipitate by replaceable skin layer membrane filtration to obtain the treated water.

6. The method of claim 5, wherein removing hydrocarbons occurs before precipitating.

7. The method of claim 6, wherein the energy process water is produced water from oil and gas operations.

8. The method of claim 1 wherein the energy process water is thermal energy process water and the water has a temperature greater than 100°C.

9. An apparatus for recovering lithium from energy process water, comprising:

a system for removing alkaline earth metals from the water to form a treated water;

a reactor for removing the lithium ions from the treated water, the reactor including at least one column, the column including:

an inlet;

an outlet;

a diffuser core at the inlet through which fluid flows from the inlet into an inner volume of the column, the diffuser core tapered from a wider base to a narrow inner end and the diffuser core including a first screen through which the fluid flows;

an outlet tube at the outlet through which fluid exits the inner volume of the column, the outlet tube including a mounted end, a narrower tip and walls that taper from the mounted end to the narrower tip, the walls including a second screen through which the fluid flows; and

a titanium oxide molecular sieve configured to adsorb lithium ions, the titanium oxide molecular sieve retained in the inner volume between the diffuser core and the outlet tube and having a size unable to pass through the second screen;

an eluting system configured to contact the molecular sieve with a strong acid solution to desorb lithium ions into an eluate fluid; and

a collecting system to collect the eluate fluid, the eluate fluid being rich with lithium ions.

10. The apparatus of claim 9, wherein the titanium oxide molecular sieve includes pellets of titanium oxide in a polyacrylamide matrix and the second screen has a passage size smaller than the pellets.

1 1. The apparatus of claim 9, wherein the titanium oxide molecular sieve includes pellets of titanium oxide in a zeolite or aerogel matrix and the second screen has a passage size smaller than the pellets.

12. The apparatus of claim 9, wherein the system for removing alkaline earth metals includes a replaceable skin layer membrane filtration unit to remove a precipitate of the alkaline earth metals.

13. The apparatus of claim 12, further comprising upstream of the system for removing alkaline earth metals, a froth flotation apparatus configured for removal of hydrocarbons.