Patent Application
20250207497
This patent application is generally related to the area of lithium recovery. Specifically, processes and apparatus for detecting lithium, and determining lithium concentration underground are described.
Metals are valuable commodities. Demand for metals continuously increases for their physical, chemical, and electrical properties. Lithium is a prime example.
Lithium is a key element in energy storage. Electrical storage devices, such as batteries, supercapacitors, and other devices commonly use lithium to mediate the storage and release of chemical potential energy as electrical current. As demand for renewable, but non-transportable, energy sources such as solar and wind energy grows, demand for technologies to store energy generated using such sources also grows.
According to the United States Geological Survey, global reserves of lithium total 26 million tons (metric) of lithium content, with Chile, Australia, Argentina, and China accounting for about 78% of global reserves. U.S. Geological Survey, Mineral Commodity Summaries, January 2023. Reuters reports that lithium supply is forecast to be 964 kT LCE in 2023, up from 737 kT in 2022. According to S&P Global Commodity Insights, lithium demand is expected to outpace supply by 3% in 2023, and every year thereafter until 2027. By 2028, global lithium demand is expected to double to over 2,000 kTa, while production is set to rise to 2,100 kTa. While lithium prices are quite volatile as the global market develops, lithium prices are expected to remain high through 2030. The incentive for more lithium production could not be clearer.
Manufacturers are exploring direct extraction methods of recovering metals, including lithium, from aqueous sources. Such extraction methods may involve contacting an aqueous source having metal ions with a selective medium that withdraws target ions from the aqueous source into the medium. The ion-loaded medium is then contacted with a material that removes the ions from the medium. The selective withdrawal medium can be liquid or solid, and the material that removes the ions from the selective withdrawal medium is typically an aqueous medium that can be pure water or water with acid, base, salt, or combination thereof. Ions removed from the selective withdrawal medium can then be processed into any convenient form, such as salts. In the example of lithium, extracted lithium can be converted into lithium carbonate or lithium hydroxide for battery applications.
Aqueous sources of lithium can be found underground, but effective and reliable methods of detecting lithium in aqueous sources underground, and of ascertaining concentration of lithium in such sources, are needed.
Embodiments described herein provide a method that includes introducing a selective sorbent material that selectively captures an element of interest into contact with an aqueous formation material at a subterranean location; recovering the selective sorbent material; and determining an amount of the element of interest in the recovered selective sorbent material.
Other embodiments described herein provide a method comprising introducing a plurality of selective sorbent materials that selectively capture one or more elements of interest into contact with an aqueous formation material at a plurality of subterranean locations; recovering the plurality of selective sorbent materials; and determining an amount of an element of interest of the one or more elements of interest in each of the recovered selective sorbent materials.
Lithium, or other elements of interest, can be detected in aqueous underground sources by introducing a selective sorbent material into a subterranean location to contact an underground aqueous material, recovering the selective sorbent material, and determining whether the recovered selective sorbent material has the element of interest, and if so how much. The selective sorbent material is a solid particulate material that selectively adsorbs or absorbs one or more elements of interest, such as lithium, from an aqueous material. The selective sorbent material can be a resin treated, coated, or impregnated with materials such as aluminum hydroxide, manganese oxide, or titanium oxide, which are lithium-selective materials. The particulate selective sorbent material is dispersed in a carrier fluid, which may be selected based on properties of the subterranean location to which the selective sorbent material is to be introduced.
The conduit 104 extends roughly along a central axis of the well 102, such that an annular passage 106 is defined between the conduit 104 and the inner well wall 108. The conduit 104 is extended to a desired depth above the bottom of the well 102, such that fluids can be pumped through the conduit 104 into the well 102 and then displaced into the annular passage 106 to flow toward the surface.
A treatment material 110, comprising a carrier fluid having a particulate selective sorbent material 112 dispersed therein, is pumped down the conduit 104 into the well 102, for example from a vessel 113 using a pump 115. The particulate selective sorbent 112 can be a solid material that includes a support portion and a sorbent portion. The support portion can be any material that does not adversely affect lithium, or other materials, in the formation. The sorbent portion is a material like those described above that is selective for adsorbing or absorbing lithium from an aqueous material. The selective sorbent can be coated on an outer surface of the support material, interspersed with the support material, or interspersed with a portion of the support material, such as an outer shell of the selective sorbent particle. The selective sorbent particles can also be Janus particles in some cases having outer surfaces with different areas having different compositions. The selective sorbent can also be, or include, agglomerates of particles that have selectively sorbent material.
Particle size of the selective sorbent can be selected based on characteristics of the formation to be tested. For example, particle sizes can be selected that would not become lodged in cracks and passages in the formation, which could reduce the possibility of mass transport within the formation. Particle sizes can also be selected that are likely to penetrate the formation in some cases, for example if an isolated zone is to be tested by flowing selective sorbent through a formation from a source well to a receiving well.
The carrier fluid can be a fluid compatible with the formation and selected to interact with fluids, potentially lithium bearing fluids, of the formation in selected ways. The carrier fluid can be water, for example fresh water, sea water, or a combination thereof. The carrier fluid can also include other components selected to provide desired properties of the treatment material and/or interact with formation materials in desired ways. For example, the carrier fluid can include additives, such as surfactants, viscosifiers, emulsifiers, dispersants, solvents, acidifiers, de-acidifiers, color materials, and the like.
Temperature sensors can be included in the treatment material 110 to record temperature evolution of the treatment material 110 as it flows through the formation. The thermal history of the material can inform analysis of sorbed elements in the selective sorbent following recovery. Such temperature sensors are known and commonly used in the art.
The treatment material 110 is pumped into the well 102 to a diversion point 114, which may be at the bottom of the well 102, as shown here, or a location above the bottom of the well 102. For example, isolation structures known in the art can be deployed within the well to divert the treatment material 110 at a diversion point 114 selected based on a desired analysis of the formation. The treatment material 110 is flowed into the annular passage 106. The treatment material 110 comes into contact with lithium, and other elements, in the formation, and the selective sorbent 112 adsorbs or absorbs one or more elements for which the sorbent is selective from the formation to form a loaded sorbent 118 that forms, with the carrier fluid, a loaded treatment material 120. The loaded treatment material 120 flows in the annular space 106 up to the surface where it is collected, for example in a vessel 116. Collection of the loaded treatment material 120 can be organized in any desired way. For example, aliquots of the treatment material can be isolated by time, such that elements of interest collected by the selective sorbent at different times can be differentiated and compared.
The collected loaded sorbent 118 is analyzed for element content. The analysis can use any suitable method. For example, the loaded sorbent 118 can be subjected to direct spectral analysis such as NMR (nuclear magnetic resonance) to yield information about elemental content. The loaded sorbent 118 can also be mixed with an extraction fluid of known composition to remove any removable elements from the loaded sorbent 118. Optionally, in such cases, the loaded sorbent 118 can be separated from any fluid surfaced with the loaded sorbent, for example using a shaker or other bulk separation tool, and optionally dried or subjected to additional fluid separation, such as centrifuging, before introducing the loaded sorbent 118 to the extraction fluid. The extraction fluid extracts any extractable materials in or on the loaded sorbent 118 to form an extract containing the element or elements of interest. The extract can then be analyzed for content of elements of interest using any suitable method. Methods including density analysis, conductivity analysis, and spectral analysis can be used. Examples of such methods include flame photometry, NMR, and capillary electrophoresis. Such methods can be used to ascertain lithium composition of a subterranean aqueous material.
A sample point 122 can be provided along the flow path from the well 102 to the tank 116 where samples of the loaded sorbent 120 can be collected, if desired. Such samples can be taken at advantageous times to provide a pinpoint indication of conditions at a certain time within the wellbore and how such conditions may be changing with time.
After extraction, the loaded sorbent 118 can become selective sorbent 112 that can be reused, for example by introducing the unloaded particles, following extraction, into the treatment fluid 110. Over many loading and unloading cycles the sorbent particles can become degraded and unable to adsorb or absorb elements of interest. In such cases, the sorbent particles can be regenerated by exposing the sorbent particles to hot wash fluids, such as water, a solvent, or a combination thereof. Lower alcohol solvents, such as butanol, can be used, alone or with water, to regenerate the sorbent particles. The sorbent particles can also be exposed to hot gases and vapors such as steam to enhance the regeneration process. Following regeneration, the sorbent particles can be exposed to hot gas to dry the sorbent particles and remove any residual solvent material before reuse. The regenerated sorbent particles can then be used as selective sorbent 112 by introducing them into the treatment material 110.
Quantity of an element of interest, such as lithium, found in the loaded sorbent can be used to ascertain content of the element of interest within the aqueous formation material into which the sorbent was introduced. Quantity of the element of interest found in the loaded sorbent can be paired with flow information, obtained for example from the pump 114 or from sensors disposed in the flow path between the vessels 113 and 116, and temperature information, for example using readings from temperature sensors included in the treatment material, and with known sorption characteristics of the selective sorbent, to ascertain aqueous concentrations of the element of interest encountered by the selective sorbent in the formation. Sorption characteristics of the selective sorbent can be predetermined by testing the selective sorbent in aqueous solution, potentially at different concentrations, to define a relationship between time, temperature, and quantity of the element of interest captured by the selective sorbent, and aqueous concentration encountered by the selective sorbent.
Multiple tests using known selective sorbents can be conducted to ascertain distribution of elements of interest within the formation. For example, selective sorbents can be pumped to different depths in the formation on different occasions, and the results compared to ascertain any stratification of concentration within the formation. Such programs can be conducted as a well is extended downward within the formation, and/or using isolation tools deployed at different depths within the well. Accordingly, a drilling fluid can be used as carrier fluid for selective sorbents and for temperature sensors. Tests using different flow rates of the selective sorbent through the formation, potentially also at different depths, can also be used to identify structure and contours of elemental concentration within the formation. Tests using geographically spaced wells can also be used to ascertain dispersion and contours of elemental concentration within the formation. One or more tests using selective sorbent material can also involve stationary residence time varied flow rate (i.e. pumping speed) within the formation. For example, if lithium concentration is expected to be low, selective sorbent can be allowed to rest within the well for a residence time selected to increase detection of low levels of lithium. After the residence time, the selective sorbent can be flowed to the surface for analysis. In other cases, multiple tests using different selective sorbents having different known sorption characteristics, potentially for different forms of lithium that might be present in the formation, can be used to ascertain any differences in forms of lithium within the aqueous material in the formation. In other cases, multiple tests using different flow rates of treatment material through a formation can be used to improve concentration data recovered from a subterranean zone of interest.
The selective sorbent material can be circulated while a well is drilled into a formation. For example, the selective sorbent can be dispersed into drilling fluid, which can serve as a carrier fluid for the selective sorbent, and the drilling fluid circulated within the well as the well is extended into the earth. Where the treatment material 110 is circulated during drilling, the diversion point 114 changes with time as the well is extended, so the contact between selective sorbent particles and aqueous formation material changes as drilling progresses. Collection time of drilling fluid at the surface is commonly associated with depth of the well. Ascertaining content of elements of interest retrieved using the selective sorbent material, and associating the results with well depth can give information about variation in concentration with depth.
As drilling progresses, the well 206 gets deeper and the drillstring 202 extends further into the earth moving the diversion point 214 to a different location. Thus, the diversion point 214 is a first diversion point at a first location and a first time, and as drilling progresses the diversion point moves to a second diversion point 224 at a second location and a second time. The drilling fluid 210 typically circulates within the well continuously as drilling progresses, so new sorbent 112 is continuously brought into contact with the formation at new locations and new times. The loaded sorbent 118 emerging at different times can be correlated with depth of the well 206, and analysis of loaded sorbent 118 collected at different times can be used to ascertain information about elements of interest at different depths as the well 206 is drilled. As with the activity diagram of
The results obtained using such tests can be compiled into a log showing concentration of one or more elements of interest as a function of one (for example where the treatment material 110 or 210 is circulated in one vertical wellbore), two, or three dimensions (for example where the treatment material 110 or 210 is circulated in a plurality of wellbores). Such methods are commonly used where hydrocarbon resources are mapped within a formation based on cuttings and drilling fluid collection at the surface, and are applicable to the mapping of aqueous elemental resources as well.
In one embodiment, a first treatment material having a first selective sorbent is pumped into and through a well at a first flow rate to a first diversion point within the well to form a first loaded sorbent. The first loaded sorbent is collected and analyzed to determine a first loading. A second treatment material having a second selective sorbent is pumped into and through the well at a second flow rate to a second diversion point within the well to form a second loaded sorbent. The second loaded sorbent is collected and analyzed to determine a second loading. The first and second selective sorbents can be the same or different. The first and second flow rates can be the same or different. The first and second diversion points can be the same or different. The first and second loadings are used, along with the first and second flow rates, to determine concentration of lithium within water contacted within the well. Where the first and second flow rates are different, but all other variables are the same, the results can provide a clearer understanding of content of one or more elements of interest, such as lithium, particularly where content of the element of interest is low and loading at the higher flow rates might be so low as to be unreliable. Use of different first and second selective sorbents can ascertain concentrations of different species. Use of different first and second concentrations and flow rates can also indicate any evolution in lithium concentration within the well.
In one embodiment, a treatment material may contain a first selective sorbent material selective for a first element of interest and a second selective sorbent material selective for a second element of interest. A single treatment material of this sort can be used, in a single treatment of a formation, to form a first loaded sorbent and a second loaded sorbent. The first and second loaded sorbents can be collected, separated, and analyzed to ascertain information about content of the first and second elements of interest in the aqueous formation material.
In another embodiment, a first treatment material containing a first selective sorbent material selective for a first element of interest, and a second treatment material containing a second selective sorbent material selective for a second element of interest, can be obtained or formed as described herein. The first and second treatment materials can be sequentially circulated through the well, optionally with a spacer material between the two treatment materials, to yield a first loaded sorbent and a second loaded sorbent. The two loaded sorbents can be analyzed to ascertain information about content of the first and second elements of interest in the aqueous formation material.
In general, analysis of loaded sorbent materials can provide concentration of one or more elements of interest, or can provide a parameter related to concentration of one or more elements of interest. Also, it should be noted that, where two different selective sorbents are used, in some cases, the two selective sorbent materials may be selective for the same element of interest. In such cases, the two selective sorbent materials may have different temperature selectivity profiles or different temperature sorption profiles, or different sorption capacities or different temperature-sorption capacity profiles, or other performance differences that can be used to ascertain additional information about content of the element of interest in the aqueous formation material.
It should be noted that the description above focuses on lithium, but that any target ion can be subjected to the processes herein to ascertain concentration within a subterranean aqueous material. As noted above, different selective sorbents can be used, in separate treatment materials or in the same treatment material, to ascertain concentrations of different species. For example, a treatment material can include a first selective sorbent selective for a first ion and a second selective sorbent selective for a second ion. Loading of the first selective sorbent with the first ion can indicate concentration of the first ion in the subterranean aqueous material, and loading of the second selective sorbent with the second ion can indicate concentration of the second ion in the subterranean aqueous material.
The disclosure relates to a method, comprising introducing a selective sorbent material that selectively captures an element of interest into contact with an aqueous formation material at a subterranean location; recovering the selective sorbent material; and determining an amount of the element of interest in the recovered selective sorbent material.
In an embodiment, introducing a selective sorbent material into contact with an aqueous formation material at a subterranean location comprises dispersing a solid particulate selective sorbent material into a carrier fluid to form a treatment mixture and pumping the treatment mixture into a well. In such an embodiment, the method further comprises circulating the selective sorbent material to a diversion point within the well and recovering the selective sorbent material at the surface.
In an embodiment, determining an amount of the element of interest in the recovered selective sorbent material comprises disposing the selective sorbent material into an extraction fluid, extracting the element of interest from the selective sorbent into the extraction fluid to form an extract, and determining a concentration of the element of interest in the extract. In such an embodiment, the method may further comprise determining a parameter related to a concentration of the element of interest in the aqueous formation material based on the concentration of the element of interest in the extract. Determining the parameter may also be based on a flow rate of the treatment material in the well.
In an embodiment, the method may further comprise dispersing one or more temperature sensors into the carrier fluid, wherein recovering the selective sorbent material comprises recovering a sample containing a portion of the selective sorbent material and at least one temperature sensor.
In an embodiment where a paremeter related to concentration is determined and the method further comprises dispersing temperature sensor into the carrier fluid, determining the parameter is based on a temperature sensed by the at least one temperature sensor.
In an embodiment, the selective sorbent material is a first selective sorbent material, the subterranean location is a first subterranean location, and the amount of the element of interest in the first selective sorbent material is a first amount. The method may further comprise introducing a second selective sorbent material into contact with the aqueous formation material at a second subterranean location; recovering the second selective sorbent material; and determining a second amount of the element of interest in the second selective sorbent material. In such an embodiment, determining the parameter related to the concentration of the element of interest in the aqueous formation material is also based on the second amount.
In an embodiment, the carrier fluid is a drilling fluid.
In an embodiment, wherein the selective sorbent material is configured to capture a first element of interest and a second element of interest, and wherein determining the amount of the element of interest comprises determining an amount of the first element of interest in the selective sorbent material and determining an amount of the second element of interest in the selective sorbent material.
The disclosure also relates to a method comprising introducing a plurality of selective sorbent materials that selectively capture one or more elements of interest into contact with an aqueous formation material at a plurality of subterranean locations; recovering the plurality of selective sorbent materials; and determining an amount of at least an element of interest of the one or more elements of interest in each of the recovered selective sorbent materials. Such a method may further comprise logging a parameter related to a concentration of a selected element of interest of the one or more elements of interest in the aqueous formation material based on the amount of the selected element of interest in each of the recovered selective sorbent materials.
In any of the methods described in relation to the disclosure, the element of interest may be lithium.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the present disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
| Number | Date | Country | |
|---|---|---|---|
| 63613242 | Dec 2023 | US |
