(12) Patent Application Publication (10) Pub. No.: US 2016/0130682 A1 Bakke (43) Pub

Home , Caesium lithium borate, Pezzottaite

US 20160130682A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2016/0130682 A1 Bakke (43) Pub. Date: May 12, 2016

(54) METHODS FOR RECOVERING CESUMOR Publication Classification RUBDIUMIVALUES FROM ORE OR OTHER MATERLALS (51) Int. Cl. C22B 26/10 (2006.01) (71) Applicant: Cabot Corporation, Boston, MA (US) (52) U.S. Cl. CPC ...... C22B 26/10 (2013.01) (72) Inventor: Bart F. Bakke, Houston, TX (US) (57) ABSTRACT Appl. No.: 14/868,415 (21) A method to liberate and recover cesium, rubidium, or both from ore or other material is described. The method involves (22) Filed: Sep. 29, 2015 heating the ore or other material in the presence of at least one reactant. The heating is such that it liberates at least a portion Related U.S. Application Data of the cesium or rubidium or both from the ore. Cesium or (60) Provisional application No. 62/078,431, filed on Nov. rubidium or both resulting from the method are further 12, 2014. described. Patent Application Publication May 12, 2016 Sheet 1 of 2 US 2016/O130682 A1

FIG. 1

Cesium/Rubidium Bearing Ore/Material

Cesium/Rubidium Ore/Material and Reactant in Owen Or Furnace

Liberate Cs and/or Rb from Ore/Material

Convert to Cs/Rb Salts/Products Patent Application Publication May 12, 2016 Sheet 2 of 2 US 2016/O130682 A1

FIG. 2

Cesium/Rubidium Bearing Ore/Material

Cesium/Rubidium Ore/Material and - Reactant H-> Reactant in Oven 16 or Furnace

Liberate Cs and/or Rb from Ore/Material

React Salt with Cesium and/or Rubidium

Scrub with

Water or Acid Convert to Liquid Salt Solution or Salt of 42 the Acid added ------Y------| Evaporate/Concentrate 44-?: the Solution US 2016/0130682 A1 May 12, 2016

METHODS FOR RECOVERING CESUMOR method involves heating ore or other material containing at RUBDIUMIVALUES FROM ORE OR OTHER least cesium, rubidium, or both with at least one reactant. The MATERALS reactant is an oxide of a metal, or a carbonate of a metal, or a hydroxide of a metal, or a hydrate of a metal, that is capable 0001. This application claims the benefit under 35 U.S.C. of displacing cesium oxide, rubidium oxide, or both from the S119(e) of prior U.S. Provisional Patent Application No. ore or other material. The heating is at a temperature Sufficient 62/078,431, filed Nov. 12, 2014, which is incorporated in its to liberate at least a portion of the cesium, rubidium, or both entirety by reference herein. from the ore or other material. For instance, this temperature BACKGROUND OF THE INVENTION can be 1.000°C. or higher. Examples of the reactant include, but are not limited to, lime, hydrated lime, lime in solution, or 0002 The present invention relates to liberating and/or calcium carbonate, or any combinations thereof. recovering at least one metallic element from ore. More par 0010. The present invention further relates to cesium ticularly, the present invention relates to methods for recov oxide or rubidium oxide or both obtained from any of the ering cesium, rubidium, or both from ore or other material. methods of the present invention. 0003 Cesium salts, such as cesium formate, are increas 0011. It is to be understood that both the foregoing general ingly being discovered as useful components or additives for description and the following detailed description are exem a variety of industrial applications, such as in the hydrocarbon plary and explanatory only and are intended to provide a recovery areas. However, deposits of “primary' ore, that is, further explanation of the present invention, as claimed. ore that contains high amounts of cesium with insignificant 0012. The accompanying drawings, which are incorpo amounts of undesirable impurities, are rare, and operators rated in and constitute a part of this application, illustrate have long sought techniques to enhance recovery of cesium some of the features of the present invention and together with and/or rubidium from known deposits of ore, such as primary the description, serve to explain the principles of the present ore and secondary ore, or other materials containing cesium invention. The descriptions are not intended to limit the scope and/or rubidium. It would be highly desirable to develop or the spirit of the invention. methods that work well no matter what the cesium and/or rubidium content is in the ore. In other words, it would be BRIEF DESCRIPTION OF DRAWINGS useful to have methods that work well with primary ore and/or secondary ore, or other materials containing cesium and/or 0013 FIG. 1 is a flow diagram showing one process of the rubidium. present invention for recovering cesium, rubidium, or both, 0004. However, cesium-containing secondary ore, while from ore. available, presents major problems with regard to recovering 0014 FIG. 2 is a flow diagram showing a further process the cesium from Such ore. For instance, the expense of recov of the present invention for recovering cesium, rubidium, or ering significant amounts of cesium from low yield ore can be both. quite time consuming and expensive based on known meth ods. These same problems also can exist with rubidium con DETAILED DESCRIPTION OF THE PRESENT taining ore or ore containing cesium and rubidium. INVENTION 0005 Accordingly, there is a need in the industry to 0015 The present invention relates to methods for recov develop methods for recovering the highly sought and valued ering at least cesium, rubidium, or both from ore or other minerals bearing cesium, rubidium, or both, from ore, such as material containing cesium and/or rubidium. The present primary and/or secondary ore (also referred to as cesium invention also relates to cesium oxide or rubidium oxide containing secondary ore) or other materials. obtained from these methods. 0016. In more detail, the cesium and/or rubidium can be of SUMMARY OF THE PRESENT INVENTION any form in the ore or other material containing the cesium 0006. A feature of the present invention is to provide a and/or rubidium. For instance, the cesium can be present in method to effectively recover cesium, rubidium, or both, from any ore or other material as a cesium oxide. The rubidium can all types of cesium bearing ore and/or rubidium ore, whether be present in any ore or other material as rubidium oxide. high yield bearing ore or low yielding bearing ore. Preferably, the ore includes cesium, such as pollucite (a 0007. A further feature of the present invention is to pro cesium aluminosilicate ore) with the preferred formula of vide methods to utilize the cesium, rubidium, or both, recov CSAlSiO. In many cases, the cesium aluminosilicates also ered from ore in the production of cesium-containing fluids, include rubidium. The ore can be a high-assay ore or a low Such as cesium formate and the like. assay ore. A low-assay ore, also considered a secondary ore, 0008. Additional features and advantages of the present can comprise 25 wt % Cs-O or less based on the overall invention will be set forth in part in the description that weight of the ore. follows, and in part will be apparent from the description, or (0017. The ore (overall) can be or include 20 wt % Cs-O or may be learned by practice of the present invention. The less, 15 wt % Cs-O or less, 10 wt % Cs-O or less, from 1 wt features and other advantages of the present invention will be % to 15 wt % Cs-O, from 1 wt % to 10 wt % Cs-O, from 0.25 realized and attained by means of the elements and combina wt % to 5 wt % Cs-O, less than 1 wt % Cs-O or about 0.1 wt tions particularly pointed out in the description and appended % Cs-O or more or other low amounts of cesium containing claims. ore, or other amounts within or outside of any one of these 0009. To achieve these and other advantages, and in accor ranges based on the total wt % of the ore. The Rb O can be dance with the purposes of the present invention, as embodied present in these same amounts alone or with the CSO. and broadly described herein, the present invention relates to (0018. The ore (overall) can be or include 20 wt % Cs-O or methods to recover cesium, rubidium, or both from ore and/or more, 25 wt % Cs-O or more, 35 wt % Cs-O or mores, from other materials containing cesium and/or rubidium. The 20 wt % to 35 wt % Cs-O, from 21 wt % to 35 wt % Cs-O, US 2016/0130682 A1 May 12, 2016

from 25 wt % to 35 wt % Cs-O or more or other higher 0025. In lieu of ore, examples of “other material’ that amounts of cesium containing ore, or other amounts within or contain at least cesium and/or rubidium that can be subjected outside of any one of these ranges based on the total wt % of to the methods of the present invention include, but are not the ore. The RbC) can be present in these same amounts alone limited to, tailings, and recycled material. or with the CSO. 0026 Regarding the at least one reactant that is heated 0019. The ore can include, comprise, consist essentially with the ore or other material containing cesium and/or of or consist of pollucite, nanpingite, carnallite, rhodozite, rubidium, as indicated, this reactant can be one or more reac peZZottaite, rubicline, borate ramanite, beryls, Voloshonite, tants. The reactant can be an oxide of a metal, or a carbonate cesstibtantite, avogadrite, margaritasite, kupletskite, naliv of a metal, or a hydroxide of a metal, or a hydrate of a metal. kinite, petalite, spodumene, lepidolite, biotite, mica, musco The reactant is capable of displacing cesium oxide, rubidium vite, feldspar, microcline, Li-muscovite, lithiophilite, oxide, or both from the ore or other material. Examples of the amblygonite, illite, cookeite, albite, analcime, squi, amphib reactant include, but are not limited to, lime, hydrated lime, oles, lithian mica, amphibolite, lithiophospahe, apatite and/or lime in solution, or calcium carbonate or any combination londonite, or any combinations thereof. The ore can com thereof. The reactant can be an oxide and/or hydrate and/or prise, consist essentially of, or consist of pollucite, an alumi hydroxide and/or carbonate of calcium. The reactant can be nosilicate mineral having the general formula (CSDNa) an oxide of strontium, an oxide of barium, an oxide of lithium, AlSiOHO. The ore can have at least 1 wt % pollucite or any combination thereof. The reactant can be an oxide based on the weight of the ore, or from 1 to 5 wt % pollucite and/or hydrate and/or hydroxide and/or carbonate of stron based on the weight of the ore, or at least 3 wt % pollucite tium, and/or can be an oxide and/or hydrate and/or hydroxide based on the weight of the ore. Other amounts are from 1 wt and/or carbonate of barium, and/or can be an oxide and/or % to 40 wt % or from 1 wt % to 35 wt %, or from 1 wt % to hydrate and/or hydroxide and/or carbonate of lithium. The 30 wt %, or from 1 wt % to 25 wt % pollucite based on the reactant is not magnesium oxide. weight of the ore. 0027. The reactants can be present as a powder or particu 0020. The ore or other material containing at least cesium lates or particles or in otherforms. The reactant can be present and/or rubidium can be in any shape or size. Preferably, the as particulates or particles having a size of -200 mesh or ore or other material is in the form of particulates, powder, or smaller. For instance, at least 50% by weight (e.g., or at least a plurality of particles. The ore or other material can be of a 60%, or at 70%, or at least 80%, or at least 90%, or at least size of -200 mesh or smaller. For instance, at least 50% by 95%, or at least 100% by weight) of the reactant can have a weight (or at least 60 wt %, at least 70 wt %, at least 80 wt %, size of -200 mesh. The reactant can be present as particulates at least 90 wt %, at least 95 wt %, from 50 wt % to 100 wt %) having an average particle size of from about 1 mm to about of the ore or other material can be present as a powder or 15 mm, or from about 2 mm to about 12 mm. particulates having a mesh of -200 mesh. 0028. Since the at least one reactant and the ore or other 0021. The ore or other material can be present as particu material containing the cesium and/or rubidium are heated lates or powder and have an average particle size of from together, it is advantageous that the ore or other material and about 1 mm to about 15 mm. For instance, the average particle the reactant have similar or the same particle sizes. For size can be from about 2 mm to about 12 mm. instance, the ore or other material and the reactant can each 0022. If the ore or other material containing at least cesium have a particle size (e.g., average particle size) that is within and/or rubidium is recovered as large pieces, such as over 15 50% of each other or within 25% of each other, or within 10% mm in size, this ore or other material can be reduced to of each other, or within 5% of each other. particulates (for instance, to the sizes mentioned above) by 0029. For the heating of the reactant with the ore or other crushing, milling, or other techniques. material containing the cesium and/or rubidium, preferably 0023. With regard to the crusher, any crusher can be used the ore or other material is in intimate contact with the reac that can reduce large rocks into Smaller rocks or individual tant. This can be achieved by mixing the ore or other material pieces. Examples of crushers that can be used include, but are with the reactant so that the reactant is substantially uni not limited to, a jaw crusher, a gyratory crusher, a cone formly distributed throughout the ore or other material. Alter crusher, an impact crusher, such as a horizontal shaft impac natively, the reactant can be non-uniformly distributed tor, hammer mill, or vertical shaft impactor. Other examples throughout the ore or other material. of crushers that can be used include compound crushers and 0030 The ore or other material and the at least one reactant mineral sizers. As an option, a rockbreaker can be used before can be used in various weight ratios. Preferably, the ore or crushing to reduce oversized material too large for a crusher. other material and the at least one reactant have a weight ratio Also, more than one crusher can be used and/or more than one ofore or other material: reactant of from about 15:85 to about type of crusher can be used in order to obtain desirable sizes 85:15 or, for instance, from about 5:95 to about 95:5 or from and processing speeds. about 40:60 to about 60:40. 0024. In an optional crushing step, preferably, the ore can 0031. The ore or other material and the reactant(s) can be be crushed to obtain crushed ore that is or includes powder or mixed together prior to and/or during the heating step. Any particles or particulates, where at least 50% by weight (e.g., or mixer can be used to accomplish the mixing of the two. Such least 60% or at least 70% or at least 80%, or at least 90%, or as an auger, mixer, blender, and the like. at least 95% or 100% by weight) of the crushed ore has a size 0032 Regarding the heating step, the heating is generally capable of passing through a mesh/screen of 200 mesh, or at a temperature of 1,000° C. or higher. The temperature is a passing through a mesh/screen of 175 mesh, or passing reference to the average temperature achieved by the ore or through a mesh/screen of 150 mesh, or passing through a other material. The temperature can be from about 1,000° C. mesh/screen of 125 mesh, or passing through a mesh/screen to about 3,000°C. or more, for instance, from about 1,025°C. of-200 mesh, but not passing through +100 mesh (all U.S. to about 1,750°C., or from about 1,000°C. to about 2,000°C., mesh sizes). or from about 1,025°C. to about 3,000° C., or the temperature US 2016/0130682 A1 May 12, 2016

of the heating can be at a temperature sufficient to Volatize being introduced into the furnace, or can be mixed in the said cesium, rubidium, or both, that is present in the ore or furnace. Further, the reactant and/or cesium/bearing material other material, and this can be temperatures as stated here or can be introduced as batches, continuously, semi-continu above 3,000° C. ously, and the like. Heat (18) is then introduced to the material 0033. The heating can be accomplished in any apparatus and then cesium and/or rubidium are liberated or displaced or device typically used to heat minerals or ore. For instance, (20) Such as cesium oxide and/or rubidium oxide. As an the heating can occur in a furnace (e.g., rotary furnace) or in option, the cesium oxide/rubidium can be liberated as a gas. an oven and the like. The cesium/rubidium is separated from the remaining ore? 0034. The heating that is used in the present invention can material (22). The remaining ore/material can be discarded, be a single step heating process or staged heating or have or returned to the process (10 and/or 14) and/or for further multiple heating steps. The heating temperature can be processing. The liberated cesium and/or rubidium (24) can achieved by ramping up the temperature. For instance, the then be converted to a liquid or subjected to condensation (28) ramping of the temperature to the desired temperature to and then converted to cesium and/or rubidium salts or other achieve liberation can be ramped up at least 1° C. per minute, products such as cesium formate, cesium hydroxide, cesium at least 5°C. perminute, at least 10° C. per minute, or at least sulfate (32), and the like. Similar rubidium materials can be 15° C. per minute, or more. formed from rubidium when rubidium is the source material. 0035. The heating can be done under pressure or under an 0041 As an option, the ore/material can contain one or inert atmosphere or in an oxygen-containing atmosphere, or more salts. The one or more salts can be naturally part of the under vacuum or under a reductive environment (such as in a ore/material (present in the starting ore/material). In the alter bed of carbon). native, or in addition, the one or more salts can be added to the 0036. The heating can be for a period of 5 minutes or more, ore/material before and/or during the process of the present such as from about 5 minutes to 100 hours or more. Generally, invention. The presence of one or more salts can permit a the heating occurs until the available amount (or portion further reaction between the liberated cesium, rubidium, or thereof) of cesium and/or rubidium is liberated from the ore or both, and the salt, and this can form cesium salts and/or other material. Generally, the process can liberate at least rubidium salts, such as but not limited to, cesium Sulfate 50% by weight, at least 60% by weight, at least 70% by and/or rubidium Sulfate. The adding of one or more salts can weight, at least 80% by weight, at least 90% by weight, at be done prior to liberating of the cesium, rubidium or both least 95% by weight, at least 98% by weight, at least 99% by from the ore or other material, and/or can be done during the weight, or 100 wt % of all available cesium and/or rubidium liberating of the cesium, rubidium or both, and/or can be done present in the ore or other material. after the liberating of the cesium, rubidium, or both. Prefer 0037. During the heating process, the cesium and/or ably, the one or more salts are added before or during the rubidium can be liberated, for instance, in the form of a gas. liberating of the cesium, rubidium, or both. For instance, as The gas can be typically a cesium oxide and/or rubidium the ore or other material is heated with at least one reactant, oxide. The cesium or rubidium or both, in the form of a gas, the cesium and/or rubidium begin to decompose and eventu can be recovered using various techniques. For instance, the ally are liberated. If one or more salts are present, the cesium cesium and/or rubidium gas can be recovered by Scrubbing and/or rubidium being release from the ore or other material the gas with an aqueous Solution or non-aqueous solution. will then react with the one or more salts. The cesium and/or The scrubbing of the gas can be done with water or a salt rubidium, for instance, can begin to decompose and be avail solution or other solution. The recovery of the cesium oxide able to react with any salt present at temperature of about or rubidium oxide from the gas formed can be done by sub 1080° C. to 1090° C. and higher. The reaction of the cesium jecting the gas to condensation temperatures, for instance, and/or rubidium from the ore or other material generally spraying the gas with water or other aqueous or non-aqueous reacts completely and quickly attemperatures of 1100° C. or Solutions. higher. Generally, if a salt(s) is present, it will not react until 0038. In the present invention, the ore or other material, the cesium and/or rubidium is decomposed or liberated from after the cesium and/or rubidium are liberated, can be at least the ore or other material (e.g., when the cesium and/or partially converted to calcium silicate, calcium aluminosili rubidium is present as an oxide), or, otherwise rendered avail cate, or both, when calcium is used as one of the reactants or able for further reaction with a salt. Generally, the reaction of as all of the reactant. the salt with cesium and/or rubidium is best conducted when 0039. With the present invention, the reaction efficiency of the salt reaction is advanced to and beyond temperatures that liberating cesium and/or rubidium values from the ore or where liquid phase diffusion is promoted, or enabled, and/or, other material can be to a yield that is near complete extrac up to Such temperatures that promote the vapor phase release tion of the cesium oxide and/or rubidium oxide values that are of the comprised cesium and/or rubidium inventory (e.g., present in the ore or minerals or other materials. when the inventory of cesium and/or rubidium is in the vapor 0040 FIG. 1 sets forth a block diagram showing the vari phase and the salt is in the vapor phase). ous steps of the methods of the present invention including 0042. As an option, beforehand, water can be added to the optional steps. The blocks or rectangles defined by dashed ore or other material to leach any salt present in the ore or lines are optional steps. Referring to FIG. 1, cesium bearing other material and as an option, the ore or other material can or ore material and/or rubidium bearing or ore material is be heated to concentrate the salt solution that was formed obtained (10) and optionally subjected to crushing or milling from the leaching. For instance, the salt solution can be con to reduce the size of the material (12) preferably to the particle centrated to 30% to 50% by weight in solution or more. sizes mentioned herein. Then, the material is introduced into 0043. The salt that can be naturally present or added (to the an oven or furnace or other heating device (14) and a reactant ore or other material) can be, for instance, a Sulfate salt, like (16) is also introduced. As indicated, optionally the reactant a sulfate salt from Group I or IIa or IIb of the Periodic Table and cesium/rubidium bearing material can be mixed prior to of the Elements, such as, for example, Li, Na, K, Rb, Cs, Mg, US 2016/0130682 A1 May 12, 2016

Ca,Sr., and/or Basulfates. The salt can be a metal chloride salt ing ore/material can be discarded, or returned to the process (Li, Na, K, Rb, Cs, Mg, Ca,Sr., and/or Bachloride). The salt (10 and/or 14) and/or for further processing. The cesium used can be in any shape or size. Preferably, the salt is in a salt(s) and/or rubidium salt(s) can be recovered (48). The form that is capable of being in intimate contact with the cesium salt(s) and/or rubidium salt(s) can be scrubbed with liberated cesium and/or rubidium. The salt can be in powder water or acid oran organic liquid (40) to obtain a solution (42) form, wherein at least 80 wt % of the powder is about -200 (e.g., a salt Solution, a salt of the acid solution, an cesium mesh. To react the liberated cesium and/or rubidium with the and/or rubidium organic Solution). The solution can be Sub salt, the two reactants can be mixed together. If added, the jected to evaporation or other techniques to concentrate the weight ratio of salt to liberated cesium and/or rubidium is solution (44). Similar rubidium materials can be formed from from 30% to about 85% by weight liberated cesium or rubidium when rubidium is the source material. rubidium to 15% to about 70% by weight salt. The mixture of 0046. As an option, the method can maintain a slight CO salt and liberated cesium and/or rubidium can be subjected to presence (e.g., 1 wt % or less, such as 500 ppm or less in the heat and up to temperature of from 500° C. to 3,000° C. or Solution, based on wt of solution), which can be advantageous higher. This can be done by rotary kiln, or heating device or to facilitate the recovery of the cesium and/or rubidium. furnace. The heating time can be from minutes to hours (e.g., 0047. The type of reactions that can be achieved with 10 minutes to 10 hours or more). The cesium and/or rubidium various cesium-containing minerals are provided below. salt formed from this second reaction can then be subjected to However, it is to be appreciated that while Pollucite is the evaporation techniques to concentrate the cesium salt and/or mineral portrayed in the exemplary reaction shown below, rubidium salt (e.g., cesium sulfate) so as to precipitate out the other cesium-bearing minerals or ores can be used. Further, cesium salt and/or rubidium salt for easier recovery. while calcium oxide is used as the preferred reactant, again, it 0044. Once the starting material is suitably decomposed, is to be appreciated that other reactants can be used. and the cesium and/or rubidium inventory (e.g., cesium salt, rubidium salt, or both) is reacted, formed, liberated, and released, if this occurs, the cesium and/or rubidium values, Reaction #1 (Larinite): and/or, the cesium salt and/or rubidium salt, which can be in the vapor phase, can be scrubbed or otherwise contacted with > 1150° C. water to form a salt Solution, which can then be concentrated --> Ca2Al2SiO7 + 3 Ca2SiO4 + Cs2O as a salt Solution by heating to remove or evaporate Some of Lightly Gehlenite Larnite the water. Orasan option, the cesium and/or rubidium values, Sintered liberated as a vapor phase can be scrubbed or otherwise contacted with an acid (e.g., formic acid, acetic acid, etc. . . . ) to form a formate or acetate of the cesium and/or rubidium, and the like (e.g., cesium formate, cesium acetate, rubidium formate, and/or rubidium acetate). Or, as an option, the Reaction #2 (Rankinite): cesium and/or rubidium values, liberated as a vapor phase can Cs-O Al2O4SiO2 + 6% CaO -> be scrubbed or otherwise contacted with a base. > 1150° C. --> Ca2Al2SiO7 + 1% CaSiO + Cs2O 0045 FIG. 2 further sets forth a block diagram showing Lightly Gehlenite Rankinite the various steps of the methods of the present invention Sintered including optional steps involving the presence and/or addi tion of salts to the process. The blocks or rectangles defined by dashed lines are optional steps. Referring to FIG. 2, cesium bearing or ore material and/or rubidium bearing or ore mate rial is obtained (10) and optionally subjected to crushing or Reaction #3 (Wollastonite): milling to reduce the size of the material (12) preferably to the Cs-O Al2O3 4SiO2 + 5 CaO -> particle sizes mentioned herein. Then, the material is intro > 1150° C. duced into an oven or furnace or other heating device (14) and - -> Ca2Al2SiO7 + 3 CaSiO3 + Cs2O a reactant (16) is also introduced. One or more salts (36) can Lightly Gehlenite Wollastonite be introduced at any point or multiple points in the process as Sintered shown by the dashed arrows. One or more of these locations can be used to add salt. In the alternative, or in addition, salt(s) 0048. As an option, the recovered Cs-O can then be pro can be present as part of the ore or material (10). As indicated, cessed for a variety of uses. For instance, the Cs-O can be optionally the reactant and cesium/rubidium bearing material used to form cesium compounds. Such as cesium formate. For can be mixed prior to being introduced into the furnace, or can instance, the Cs-O can be recovered and subjected to further be mixed in the furnace. Further, the reactant and/or cesium/ recovery processes by reacting the CSO with at least one salt, bearing material can be introduced as batches, continuously, where the salt is capable of recovering at least one metallic semi-continuously, and the like. Heat (18) is then introduced element, such as cesium, to form a reaction product that to the material and then cesium and/or rubidium (e.g., cesium includes at least one metallic element. For instance, the salt oxide and/or rubidium oxide) are liberated or displaced (20). can be a sulfate salt. Details of this further processing step can As an option, cesium oxide/rubidium can be liberated as a be found in U.S. Pat. No. 7,323,150, incorporated in its gas. Then, the cesium and/or rubidium (20) reacts with the entirety by reference herein. By using this process, the cesium salt(s) (38) to form cesium salt(s) and/or rubidium salt(s). The can be converted to a precursor salt, Such as cesium sulfate, cesium salt(s) and/or rubidium salt(s) can be formed in the from which other cesium salts are produced. Other method vapor phase. The cesium salt and/or rubidium material is ology similarly can produce alternative cesium salts from separated from the remaining ore/material (22). The remain precursors like cesium hydroxide and cesium carbonate. As US 2016/0130682 A1 May 12, 2016

described, for instance, in U.S. Pat. No. 7,759,273, the cesium 11. The method of any preceding or following embodiment/ can be formed into a cesium formate which Subsequently can feature/aspect, wherein said ore or other material is present as then be converted to a different cesium metal salt. Another particulates and having an average particle size of from about process to form cesium salts is described in U.S. Pat. No. 1 mm to about 15 mm. 6,652,820, which is incorporated in its entirety by reference 12. The method of any preceding or following embodiment/ herein. This method involves forming a cesium salt by react feature/aspect, wherein said ore or other material is present as ing cesium sulfate with lime to form cesium hydroxide which particulates and having an average particle size of from about can then be converted to a cesium salt, Such as cesium for 2 mm to about 12 mm. mate. As stated, the cesium compounds can be very desirable 13. The method of any preceding or following embodiment/ as drilling fluids or other fluids used for hydrocarbon recov feature/aspect, wherein said reactant is present as particu ery, such as completion fluids, packer fluids, and the like. lates. 0049. The processes described in U.S. Pat. No. 6,015,535 14. The method of any preceding or following embodiment/ can also be used to form desirable cesium compounds, such as feature/aspect, wherein said reactant is present as particulates cesium formate. The various formulations and compositions and having a size of about -200 mesh or smaller. described in the following patents can be used with the 15. The method of any preceding or following embodiment/ cesium or cesium compounds recovered by the processes of feature/aspect, wherein said reactant is present as particulates the present invention and each of these patents are incorpo and having at least 50% by weight of -200 mesh. rated in their entirety by reference herein: U.S. Pat. Nos. 16. The method of any preceding or following embodiment/ 7,407,008; 7,273,832; 7,211,550; 7,056,868; 6,818,595; feature/aspect, wherein said reactant is present as particulates 6,656,989; and 6,423.802. and having an average particle size of from about 1 mm to 0050. The present invention includes the following about 15 mm. aspects/embodiments/features in any order and/or in any 17. The method of any preceding or following embodiment/ combination: feature/aspect, wherein said reactant is present as particulates 1. A method for recovering at least cesium, rubidium, or both and having an average particle size of from about 2 mm to from an ore or other material, said method comprising: about 12 mm. 0051 heating a) said ore or other material, and b) at least 18. The method of any preceding or following embodiment/ one reactant together, feature/aspect, wherein said ore or other material and said 0052 wherein said heating is at a temperature sufficient to reactant or both are in particulate form and each have an liberate at least a portion of said cesium, rubidium, or both average particle size that is within 50% of each other. from said ore or other material, and 19. The method of any preceding or following embodiment/ 0053 said reactant is an oxide of a metal, or a carbonate of feature/aspect, wherein said ore or other material and said a metal, hydroxide of a metal or a hydrate of a metal, that is reactant or both are in particulate form and each have an capable of displacing cesium oxide, rubidium oxide, or both average particle size that is within 25% of each other. from said ore or other material. 20. The method of any preceding or following embodiment/ feature/aspect, wherein said ore or other material and said 2. The method of any preceding or following embodiment/ reactant or both are in particulate form and each have an feature/aspect, wherein said reactant is lime, hydrated lime, average particle size that is within 10% of each other. lime in Solution or calcium carbonate or any combination 21. The method of any preceding or following embodiment/ thereof. feature/aspect, wherein said ore is present and Subjected to 3. The method of any preceding or following embodiment/ said heating. feature/aspect, wherein said reactant is an oxide or hydroxide 22. The method of any preceding or following embodiment/ or hydrate or carbonate of calcium. feature/aspect, wherein said ore is present and is cesium 4. The method of any preceding or following embodiment/ bearing ore. feature/aspect, wherein said reactant is an oxide of strontium, 23. The method of any preceding or following embodiment/ an oxide of barium, an oxide of lithium, or any combination feature/aspect, wherein said ore is present and is silicate thereof. based ore. 5. The method of any preceding or following embodiment/ 24. The method of any preceding or following embodiment/ feature/aspect, wherein said temperature of said heating is feature/aspect, wherein said ore is present and is aluminosili 1,000° C. or higher. cate-based ore. 6. The method of any preceding or following embodiment/ 25. The method of any preceding or following embodiment/ feature/aspect, wherein said temperature of said heating is feature/aspect, wherein said ore or other material is in inti from about 1,000° C. to about 2,000° C. mate contact with said at least one reactant. 7. The method of any preceding or following embodiment/ 26. The method of any preceding or following embodiment/ feature/aspect, wherein said temperature of said heating is feature/aspect, wherein said ore or other material and said at from about 1,025°C. to about 1,750° C. least one reactant have a weight ratio of said ore or other 8. The method of any preceding or following embodiment/ material to said reactant of from about 15:85 to about 85:15. feature/aspect, wherein said ore or other material is present as 27. The method of any preceding or following embodiment/ particulates. feature/aspect, wherein said ore or other material and said at 9. The method of any preceding or following embodiment/ least one reactant have a weight ratio of said ore or other feature/aspect, wherein said ore or other material is present as material to said reactant of from about 5:95 to about 95:5. particulates in a size of about -200 mesh or smaller. 28. The method of any preceding or following embodiment/ 10. The method of any preceding or following embodiment/ feature/aspect, wherein said ore or other material and said at feature/aspect, wherein said ore or other material is present as least one reactant have a weight ratio of said ore or other particulates having at least 50% by weight of -200 mesh. material to said reactant of from about 40:60 to about 60:40. US 2016/0130682 A1 May 12, 2016

29. The method of any preceding or following embodiment/ 49. The method of any preceding or following embodiment/ feature/aspect, wherein said ore or other material and said at feature/aspect, wherein at least one salt comprises a sulfate. least one reactant are mixed together prior to or during said 50. The method of any preceding or following embodiment/ heating. feature/aspect, wherein said method further comprises add 30. The method of any preceding or following embodiment/ ing at least one salt prior to or during said heating. feature/aspect, further comprising recovering said cesium or 51. The method of any preceding or following embodiment/ rubidium or both. feature/aspect, wherein said at least one salt reacts with said at 31. The method of any preceding or following embodiment/ least a portion of said cesium, rubidium, or both to form a feature/aspect, further comprising recovering cesium or cesium salt or a rubidium salt or both. rubidium or both in the form of a gas. 52. The method of any preceding or following embodiment/ 32. The method of any preceding or following embodiment/ feature/aspect, wherein said cesium salt or rubidium Saltcom feature/aspect, further comprising recovering said cesium or prises cesium sulfate, cesium chloride, rubidium Sulfate, or rubidium or both in the form of a gas and converting said gas rubidium chloride. to a liquid solution containing cesium or rubidium or both. 53. The method of any preceding or following embodiment/ 33. The method of any preceding or following embodiment/ feature/aspect, wherein said cesium salt or rubidium Saltcom feature/aspect, further comprising recovering cesium or prises cesium sulfate, cesium chloride, rubidium Sulfate, or rubidium or both in the form of a gas, wherein said cesium or rubidium chloride. rubidium or both are in the form of an oxide. 34. The method of any preceding or following embodiment/ 54. The method of any preceding or following embodiment/ feature/aspect, further comprising scrubbing said gas with an feature/aspect, wherein method further comprises scrubbing aqueous solution or non-aqueous solution. said cesium salt or rubidium salt or both in vapor phase with 35. The method of any preceding or following embodiment/ water or an acid or a base. feature/aspect, wherein said ore or other material, after said 55. The method of any preceding or following embodiment/ liberating, is at least partially converted to calcium silicate, feature/aspect, wherein method further comprises scrubbing calcium aluminosilicate, or both. said cesium salt or rubidium salt or both in vapor phase with 36. The method of any preceding or following embodiment/ water or an acid or a base. feature/aspect, wherein said ore or other material is present 0054 The present invention can include any combination and comprises pollucite. of these various features or embodiments above and/or below 37. The method of any preceding or following embodiment/ as set forth in sentences and/or paragraphs. Any combination feature/aspect, wherein said heating is under pressure. of disclosed features herein is considered part of the present 38. The method of any preceding or following embodiment/ invention and no limitation is intended with respect to com feature/aspect, wherein said heating is under an inert atmo binable features. sphere. 0055 Applicants specifically incorporate the entire con 39. The method of any preceding or following embodiment/ tents of all cited references in this disclosure. Further, when feature/aspect, wherein said heating is in an oxygen-contain an amount, concentration, or other value or parameter is given ing atmosphere. as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as 40. The method of any preceding or following embodiment/ specifically disclosing all ranges formed from any pair of any feature/aspect, wherein said heating is under vacuum. upper range limit or preferred value and any lower range limit 41. The method of any preceding or following embodiment/ or preferred value, regardless of whether ranges are sepa feature/aspect, wherein said heating is under a reductive envi rately disclosed. Where a range of numerical values is recited rOnment. herein, unless otherwise Stated, the range is intended to 42. The method of any preceding or following embodiment/ include the endpoints thereof, and all integers and fractions feature/aspect, wherein said heating is for a period of 5 min within the range. It is not intended that the scope of the utes Or more. invention be limited to the specific values recited when defin 43. The method of any preceding or following embodiment/ ing a range. feature/aspect, wherein said hearing is for a period of from 0056. Other embodiments of the present invention will be about 5 minutes to 100 hours. apparent to those skilled in the art from consideration of the 44. Cesium oxide or rubidium oxide obtained from the present specification and practice of the present invention method of any preceding or following embodiment/feature/ disclosed herein. It is intended that the present specification aspect. and examples be considered as exemplary only with a true 45. The method of any preceding or following embodiment/ scope and spirit of the invention being indicated by the fol feature/aspect, wherein said temperature of said heating is lowing claims and equivalents thereof. from about 1,025°C. to about 3,000° C. 46. The method of any preceding or following embodiment/ 1. A method for recovering at least cesium, rubidium, or feature/aspect, wherein said temperature of said heating is at both from an ore or other material, said method comprising: a temperature Sufficient to volatize said cesium, rubidium, or heating a) said ore or other material, and b) at least one both. reactant together, 47. The method of any preceding or following embodiment/ wherein said heating is at a temperature Sufficient to liber feature/aspect, wherein said ore or other material further ate at least a portion of said cesium, rubidium, or both comprises at least one salt, and wherein said at least one salt from said ore or other material, and reacts with said at least a portion of said cesium, rubidium, or said reactant is an oxide of a metal, or a carbonate of a both to form a cesium salt or a rubidium salt or both. metal, hydroxide of a metal or a hydrate of a metal, that 48. The method of any preceding or following embodiment/ is capable of displacing cesium oxide, rubidium oxide, feature/aspect, wherein at least one salt comprises a chloride. or both from said ore or other material. US 2016/0130682 A1 May 12, 2016

2. The method of claim 1, wherein said reactant is lime, 33. The method of claim 1, further comprising recovering hydrated lime, lime in Solution or calcium carbonate or any cesium or rubidium or both in the form of a gas, wherein said combination thereof. cesium or rubidium or both are in the form of an oxide. 3. The method of claim 1, wherein said reactant is an oxide 34. The method of claim 32, further comprising scrubbing or hydroxide or hydrate or carbonate of calcium. said gas with an aqueous solution or non-aqueous solution. 35. The method of claim 1, wherein said ore or other 4. The method of claim 1, wherein said reactant is an oxide material, after said liberating, is at least partially converted to of strontium, an oxide of barium, an oxide of lithium, or any calcium silicate, calcium aluminosilicate, or both. combination thereof. 36. The method of claim 1, wherein said ore or other 5-10. (canceled) material is present and comprises pollucite. 11. The method of claim 1, wherein said ore or other 37. The method of claim 1, wherein said heating is under material is present as particulates and having an average pressure, under an inert atmosphere, in an oxygen-containing particle size of from about 1 mm to about 15 mm. atmosphere, under vacuum, or under a reductive environ 12-15. (canceled) ment. 16. The method of claim 1, wherein said reactant is present 38-42. (canceled) as particulates and having an average particle size of from 43. The method of claim 1, wherein said hearing is for a about 1 mm to about 15 mm. period of from about 5 minutes to 100 hours. 17. (canceled) 44. Cesium oxide or rubidium oxide obtained from the 18. The method of claim 1, wherein said ore or other method of claim 1. 45. The method of claim 1, wherein said temperature of material and said reactant or both are in particulate form and said heating is from about 1,025° C. to about 3,000° C. each have an average particle size that is within 50% of each 46. The method of claim 1, wherein said temperature of other. said heating is at a temperature Sufficient to Volatize said 19-20. (canceled) cesium, rubidium, or both. 21. The method of claim 1, wherein said ore is present and 47. The method of claim 1, wherein said ore or other Subjected to said heating. material further comprises at least one salt, and wherein said 22. The method of claim 1, wherein said ore is present and at least one salt reacts with said at least a portion of said is cesium-bearing ore or silicate-based ore oraluminosilicate cesium, rubidium, or both to form a cesium salt or a rubidium based ore. salt or both. 23-24. (canceled) 48. The method of claim 47, wherein at least one salt 25. The method of claim 1, wherein said ore or other comprises a chloride or a sulfate. material is in intimate contact with said at least one reactant. 49. (canceled) 26. The method of claim 1, wherein said ore or other 50. The method of claim 1, wherein said method further material and said at least one reactant have a weight ratio of comprises adding at least one salt prior to or during said said ore or other material to said reactant of from about 15:85 heating. to about 85:15. 51. The method of claim 50, wherein said at least one salt 27-28. (canceled) reacts with said at least a portion of said cesium, rubidium, or 29. The method of claim 1, wherein said ore or other both to form a cesium salt or a rubidium salt or both. material and said at least one reactant are mixed together prior 52. The method of claim 47, wherein said cesium salt or to or during said heating. rubidium salt comprises cesium Sulfate, cesium chloride, 30. The method of claim 1, further comprising recovering rubidium sulfate, or rubidium chloride. said cesium or rubidium or both. 53. (canceled) 31. (canceled) 54. The method of claim 47, wherein method further com 32. The method of claim 1, further comprising recovering prises scrubbing said cesium salt or rubidium salt or both in said cesium or rubidium or both in the form of a gas and vapor phase with water or an acid or a base. converting said gas to a liquid solution containing cesium or 55. (canceled) rubidium or both.