CA2967308C

CA2967308C - Methods for recovering cesium or rubidium values from ore or other materials

Info

Publication number: CA2967308C
Application number: CA2967308A
Authority: CA
Inventors: Bart F. Bakke
Original assignee: Cabot Corp
Current assignee: Cabot Corp
Priority date: 2014-11-12
Filing date: 2015-09-30
Publication date: 2020-09-22
Anticipated expiration: 2035-09-30
Also published as: WO2016076957A1; BR112017010016A2; BR112017010016B1; SE1750567A1; CN107109517A; AU2015347280A1; US20160130682A1; CA2967308A1; DE112015005125T5; AU2015347280B2; CN107109517B; SE542168C2

Abstract

A method to liberate and recover cesium, rubidium, or both from ore or other material is described. The method involves 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 of the cesium or rubidium or both from the ore. Cesium or rubidium or both resulting from the method are further described.

Description

METHODS FOR RECOVERING CESIUM OR RUBIDIUM VALUES
FROM ORE OR OTHER MATERIALS
BACKGROUND OF THE INVENTION
[0001]

[0002] The present invention relates to liberating and/or recovering at least one metallic element from ore. More particularly, the present invention relates to methods for recovering cesium, rubidium, or both from ore or other material.

[0003] Cesium salts, such as cesium formate, are increasingly being discovered as useful components or additives for a variety of industrial applications, such as in the hydrocarbon recovery areas. However, deposits of "primary" ore, that is, ore that contains high amounts of cesium with insignificant amounts of undesirable impurities, are rare, and operators have long sought techniques to enhance recovery of cesium and/or rubidium from known deposits of ore, such as primary ore and secondary ore, or other materials containing cesium and/or rubidium. It would be highly desirable to develop methods that work well no matter what the cesium and/or rubidium content is in the ore. In other words, it would be useful to have methods that work well with primary ore and/or secondary ore, or other materials containing cesium and/or rubidium.

[0004] However, cesium-containing secondary ore, while available, presents major problems with regard to recovering the cesium from such ore. For instance, the expense of recovering significant amounts of cesium from low yield ore can be quite time consuming and expensive based on known methods. These same problems also can exist with rubidium containing ore or ore containing cesium and rubidium.

[0005] Accordingly, there is a need in the industry to develop methods for recovering the highly sought and valued minerals bearing cesium, rubidium, or both, from ore, such as primary and/or secondary ore (also referred to as cesium-containing secondary ore) or other materials.

SUMMARY OF THE PRESENT INVENTION

[0006] A
feature of the present invention is to provide a method to effectively recover cesium, rubidium, or both, from all types of cesium bearing ore and/or rubidium ore, whether high yield bearing ore or low yielding bearing ore.

[0007] A
further feature of the present invention is to provide methods to utilize the cesium, rubidium, or both, recovered from ore in the production of cesium-containing fluids, such as cesium formate and the like.

[0008]
Additional features and advantages of the present invention will be set forth in part in the description that follows, and in part will be apparent from the description, or may be learned by practice of the present invention. The features and other advantages of the present invention will be realized and attained by means of the elements and combinations particularly pointed out in the description.
[0008a] Still another feature of the present invention is to provide a method for recovering at least cesium, rubidium, or both from an ore, said method comprising:
heating, in an oxygen-containing environment, a mixture comprising a) said ore, and b) at least one reactant, liberating, cesium oxide or rubidium oxide or both, from said mixture, in the form of a gas, and scrubbing said gas with an aqueous solution or non-aqueous solution wherein said reactant is an oxide of a metal, or a carbonate of a metal, hydroxide of a metal or a hydrate of a metal, that displaces cesium oxide, rubidium oxide, or both from said ore.

[0009] To achieve these and other advantages, and in accordance with the purposes of the present invention, as embodied and broadly described herein, the present invention relates to methods to recover cesium, rubidium, or both from ore and/or other materials containing cesium and/or rubidium. The method involves heating ore or other material containing at least cesium, rubidium, or both with at least one reactant. The 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 of displacing cesium oxide, rubidium oxide, or both from the ore or other material. The heating is at a - 2a -temperature sufficient to liberate at least a portion of the cesium, rubidium, or both from the ore or other material. For instance, this temperature can be 1,000 C or higher.
Examples of the reactant include, but are not limited to, lime, hydrated lime, lime in solution, or calcium carbonate, or any combinations thereof.

[0010] The present invention further relates to cesium oxide or rubidium oxide or both obtained from any of the methods of the present invention.

[0011] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide a further explanation of the present invention, as claimed.

[0012] The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate some of the features of the present invention and together with the description, serve to explain the principles of the present invention. The descriptions are not intended to limit the scope or the spirit of the invention.
BRIEF DESCRIPTION OF DRAWINGS

[0013] Fig. 1 is a flow diagram showing one process of the present invention for recovering cesium, rubidium, or both, from ore.

[0014] Fig. 2 is a flow diagram showing a further process of the present invention for recovering cesium, rubidium, or both.
DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0015] The present invention relates to methods for recovering at least cesium, rubidium, or both from ore or other material containing cesium and/or rubidium. The present invention also relates to cesium oxide or rubidium oxide obtained from these methods.

[0016] In more detail, the cesium and/or rubidium can be of any form in the ore or other material containing the cesium and/or rubidium. For instance, the cesium can be present in any ore or other material as a cesium oxide. The rubidium can be present in any ore or other material as rubidium oxide. Preferably, the ore includes cesium, such as pollucite (a cesium aluminosilicate ore) with the preferred formula of CsAlSi206. In many cases, the cesium aluminosilicates also include rubidium. The ore can be a high-assay ore or a low-assay ore. A
low-assay ore, also considered a secondary ore, can comprise 25 wt% Cs20 or less based on the overall weight of the ore.

[0017] The ore (overall) can be or include 20 wt% Cs20 or less, 15 wt% Cs20 or less, 10 wt% Cs20 or less, from 1 wt% to 15 wt% Cs20, from 1 wt% to 10 wt% Cs20, from 0.25 wt%
to 5 wt% Cs20, less than 1 wt% Cs20 or about 0.1 wt% Cs20 or more or other low amounts of cesium containing ore, or other amounts within or outside of any one of these ranges based on the total wt% of the ore. The Rb20 can be present in these same amounts alone or with the C s20

[0018] The ore (overall) can be or include 20 wt% Cs20 or more, 25 wt% Cs20 or more, 35 wt% Cs20 or mores, from 20 wt% to 35 wt% Cs20, from 21 wt% to 35 wt% Cs20, from 25 wt% to 35 wt% Cs20 or more or other higher amounts of cesium containing ore, or other amounts within or outside of any one of these ranges based on the total wt% of the ore. The Rb20 can be present in these same amounts alone or with the Cs20.

[0019] The ore can include, comprise, consist essentially of, or consist of pollucite, nanpingite, carnallite, rhodozite, pezzottaite, rubicline, borate ramanite, beryls, voloshonite, cesstibtantite, avogadrite, margaritasite, kupletskite, nalivkinite, petalite, spodumene, lepidolite, biotite, mica, muscovite, feldspar, microcline, Li-muscovite, lithiophilite, amblygonite, illite, cookeite, albite, analcime, squi, amphiboles, lithian mica, amphibolite, lithiophospahe, apatite and/or londonite, or any combinations thereof. The ore can comprise, consist essentially of, or consist of pollucite, an aluminosilicate mineral having the general formula (Cs>Na)[AlSi20611-120. The ore can have at least 1 wt% pollucite based on the weight of the ore, or from 1 to 5 wt% pollucite based on the weight of the ore, or at least 3 wt% pollucite based on the weight of the ore. Other amounts are from 1 wt% to 40 wt% or from 1 wt% to 35 wt%, or from 1 wt% to 30 wt%, or from 1 wt% to 25 wt% pollucite based on the weight of the ore.

[0020] The ore or other material containing at least cesium and/or rubidium can be in any shape or size. Preferably, the ore or other material is in the form of particulates, powder, or a plurality of particles. The ore or other material can be of a size of -200 mesh or smaller. For instance, at least 50% by weight (or at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, from 50 wt% to 100 wt %) of the ore or other material can be present as a powder or particulates having a mesh of -200 mesh.

[0021] The ore or other material can be present as particulates or powder and have an average particle size of from about 1 mm to about 15 min. For instance, the average particle size can be from about 2 mm to about 12 mm.

[0022] If the ore or other material containing at least cesium and/or rubidium is recovered as large pieces, such as over 15 mm in size, this ore or other material can be reduced to particulates (for instance, to the sizes mentioned above) by crushing, milling, or other techniques.

[0023] With regard to the crusher, any crusher can be used that can reduce large rocks into smaller rocks or individual pieces. Examples of crushers that can be used include, but are not limited to, a jaw crusher, a gyratory crusher, a cone crusher, an impact crusher, such as a horizontal shaft impactor, hammer mill, or vertical shaft impactor. Other examples of crushers that can be used include compound crushers and mineral sizers. As an option, a rock breaker can be used before crushing to reduce oversized material too large for a crusher. Also, more than one crusher can be used and/or more than one type of crusher can be used in order to obtain desirable sizes and processing speeds.

[0024] In an optional crushing step, preferably, the ore can be crushed to obtain crushed ore that is or includes powder or particles or particulates, where at least 50% by weight (e.g., or least 60% or at least 70% or at least 80%, or at least 90%, or at least 95% or 100% by weight) of the crushed ore has a size capable of passing through a mesh/screen of 200 mesh, or passing through a mesh/screen of 175 mesh, or passing through a mesh/screen of 150 mesh, or passing through a mesh/screen of 125 mesh, or passing through a mesh/screen of -200 mesh, but not passing through +100 mesh (all U.S. mesh sizes).

[0025] In lieu of ore, examples of "other material" that contain at least cesium and/or rubidium that can be subjected to the methods of the present invention include, but are not limited to, tailings, and recycled material.

[0026] Regarding the at least one reactant that is heated with the ore or other material containing cesium and/or rubidium, as indicated, this reactant can be one or more reactants.
The reactant can be an oxide of a metal, or a carbonate of a metal, or a hydroxide of a metal, or a hydrate of a metal. The reactant is capable of displacing cesium oxide, rubidium oxide, or both from the ore or other material. Examples of the reactant include, but are not limited to, lime, hydrated lime, lime in solution, or calcium carbonate or any combination thereof. The reactant can be an oxide and/or hydrate and/or hydroxide and/or carbonate of calcium. The reactant can be an oxide of strontium, an oxide of barium, an oxide of lithium, or any combination thereof. The reactant can be an oxide and/or hydrate and/or hydroxide and/or carbonate of strontium, and/or can be an oxide and/or hydrate and/or hydroxide and/or carbonate of barium, and/or can be an oxide and/or hydrate and/or hydroxide and/or carbonate of lithium. The reactant is not magnesium oxide.

[0027] The reactants can be present as a powder or particulates or particles or in other forms. The reactant can be present as particulates or particles having a size of -200 mesh or smaller. For instance, at least 50% by weight (e.g., or at least 60%, or at 70%, or at least 80%, or at least 90%, or at least 95%, or at least 100% by weight) of the reactant can have a size of -200 mesh. The reactant can be present as particulates having an average particle size of from about 1 mm to about 15 mm, or from about 2 mm to about 12 mm.

[0028] Since the at least one reactant and the ore or other material containing the cesium and/or rubidium are heated together, it is advantageous that the ore or other material and the reactant have similar or the same particle sizes. For instance, the ore or other material and the reactant can each have a particle size (e.g., average particle size) that is within 50% of each other or within 25% of each other, or within 10% of each other, or within 5%
of each other.

[0029] For the heating of the reactant with the ore or other material containing the cesium and/or rubidium, preferably the ore or other material is in intimate contact with the reactant.
This can be achieved by mixing the ore or other material with the reactant so that the reactant is substantially uniformly distributed throughout the ore or other material.
Alternatively, the reactant can be non-uniformly distributed throughout the ore or other material.

[0030] The ore or other material and the at least one reactant can be used in various weight ratios. Preferably, the ore or other material and the at least one reactant have a weight ratio of ore or other material : reactant of from about 15:85 to about 85:15 or, for instance, from about 5:95 to about 95:5 or from about 40:60 to about 60:40.

[0031] The ore or other material and the reactant(s) can be mixed together prior to and/or during the heating step. Any mixer can be used to accomplish the mixing of the two, such as an auger, mixer, blender, and the like.

[0032] Regarding the heating step, the heating is generally at a temperature of 1,000 C or higher. The temperature is a reference to the average temperature achieved by the ore or other material. The temperature can be from about 1,000 C to about 3,000 C or more, for instance, from about 1,025 C to about 1,750 C, or from about 1,000 C to about 2,000 C, or from about 1,025 C to about 3,000 C, or the temperature of the heating can be at a temperature sufficient to volatize said cesium, rubidium, or both, that is present in the ore or other material, and this can be temperatures as stated here or above 3,000 C.

[0033] The heating can be accomplished in any apparatus or device typically used to heat minerals or ore. For instance, the heating can occur in a furnace (e.g., rotary furnace) or in an oven and the like.

[0034] The heating that is used in the present invention can be a single step heating process or staged heating or have multiple heating steps. The heating temperature can be achieved by ramping up the temperature. For instance, the ramping of the temperature to the desired temperature to achieve liberation can be ramped up at least 1 C per minute, at least 5 C per minute, at least 10 C per minute, or at least 15 C per minute, or more.

[0035] The heating can be done under pressure or under an inert atmosphere or in an oxygen-containing atmosphere, or under vacuum or under a reductive environment (such as in a bed of carbon).

[0036] The heating can be for a period of 5 minutes or more, such as from about 5 minutes to 100 hours or more. Generally, the heating occurs until the available amount (or portion thereof) of cesium and/or rubidium is liberated from the ore or other material. Generally, the process can liberate at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99% by weight, or 100 wt% of all available cesium and/or rubidium present in the ore or other material.

[0037] During the heating process, the cesium and/or rubidium can be liberated, for instance, in the form of a gas. The gas can be typically a cesium oxide and/or rubidium oxide.
The cesium or rubidium or both, in the form of a gas, can be recovered using various techniques. For instance, the cesium and/or rubidium gas can be recovered by scrubbing the gas with an aqueous solution or non-aqueous solution. The scrubbing of the gas can be done with water or a salt solution or other solution. The recovery of the cesium oxide or rubidium oxide from the gas formed can be done by subjecting the gas to condensation temperatures, for instance, spraying the gas with water or other aqueous or non-aqueous solutions.

[0038] In the present invention, the ore or other material, after the cesium and/or rubidium are liberated, can be at least partially converted to calcium silicate, calcium aluminosilicate, or both, when calcium is used as one of the reactants or as all of the reactant.

[0039] With the present invention, the reaction efficiency of liberating cesium and/or rubidium values from the ore or other material can be to a yield that is near complete extraction of the cesium oxide and/or rubidium oxide values that are present in the ore or minerals or other materials.
[00401 Figure 1 sets forth a block diagram showing the various steps of the methods of the present invention including optional steps. The blocks or rectangles defined by dashed lines are optional steps. Referring to Figure 1, cesium bearing or ore material and/or rubidium bearing or ore material is obtained (10) and optionally subjected to crushing or milling to reduce the size of the material (12) preferably to the particle sizes mentioned herein. Then, the material is introduced into an oven or furnace or other heating device (14) and a reactant (16) is also introduced. As indicated, optionally the reactant and cesium/rubidium bearing material can be mixed prior to being introduced into the furnace, or can be mixed in the furnace.
Further, the reactant and/or cesium/bearing material can be introduced as batches, continuously, semi-continuously, and the like. Heat (18) is then introduced to the material and then cesium and/or rubidium are liberated or displaced (20) such as cesium oxide and/or rubidium oxide. As an option, the cesium oxide/rubidium can be liberated as a gas. The cesium/rubidium is separated from the remaining ore/material (22). The remaining ore/material can be discarded, or returned to the process (10 and/or 14) and/or for further processing. The liberated cesium and/or rubidium (24) can then be converted to a liquid or subjected to condensation (28) and then converted to cesium and/or rubidium salts or other products such as cesium formate, cesium hydroxide, cesium sulfate (32), and the like. Similar rubidium materials can be formed from rubidium when rubidium is the source material.
100411 As an option, the ore/material can contain one or more salts. The one or more salts can be naturally part of the ore/material (present in the starting ore/material).
In the alternative, or in addition, the one or more salts can be added to the ore/material before and/or during the process of the present invention. The presence of one or more salts can permit a further reaction between the liberated cesium, rubidium, or both, and the salt, and this can form cesium salts and/or rubidium salts, such as but not limited to, cesium sulfate and/or rubidium sulfate. The adding of one or more salts can be done prior to liberating of the cesium, rubidium or both from the ore or other material, and/or can be done during the liberating of the cesium, rubidium or both, and/or can be done after the liberating of the cesium, rubidium, or both. Preferably, the one or more salts are added before or during the liberating of the cesium, rubidium, or both. For instance, as the ore or other material is heated with at least one reactant, the cesium and/or rubidium begin to decompose and eventually are liberated. If one or more salts are present, the cesium and/or rubidium being release from the ore or other material will then react with the one or more salts. The cesium and/or rubidium, for instance, can begin to decompose and be available to react with any salt present at temperature of about 1080 C to 1090 C and higher. The reaction of the cesium and/or rubidium from the ore or other material generally reacts completely and quickly at temperatures of 1100 C or higher.
Generally, if a salt(s) is present, it will not react until the cesium and/or rubidium is decomposed or liberated from the ore or other material (e.g., when the cesium and/or rubidium is present as an oxide), or, otherwise rendered available for further reaction with a salt.
Generally, the reaction of the salt with cesium and/or rubidium is best conducted when the salt reaction is advanced to and beyond temperatures that where liquid phase diffusion is promoted, or enabled, and/or, up to such temperatures that promote the vapor phase release of the comprised cesium and/or rubidium inventory (e.g., when the inventory of cesium and/or rubidium is in the vapor phase and the salt is in the vapor phase).
[0042] As an option, beforehand, water can be added to the ore or other material to leach any salt present in the ore or other material and as an option, the ore or other material can be heated to concentrate the salt solution that was formed from the leaching. For instance, the salt solution can be concentrated to 30% to 50% by weight in solution or more.
[0043] The salt that can be naturally present or added (to the ore or other material) can be, for instance, a sulfate salt, like a sulfate salt from Group I or Ha or Ilb of the Periodic Table of the Elements, such as, for example, Li, Na, K, Rb, Cs, Mg, Ca, Sr, and/or Ba sulfates. The salt can be a metal chloride salt (Li, Na, K, Rb, Cs, Mg, Ca, Sr, and/or Ba chloride). The salt used can be in any shape or size. Preferably, the salt is in a faun that is capable of being in intimate contact with the liberated cesium and/or rubidium. The salt can be in powder form, wherein at least 80 wt% of the powder is about -200 mesh. To react the liberated cesium and/or rubidium with the salt, the two reactants can be mixed together. If added, the weight ratio of salt to liberated cesium and/or rubidium is from 30%. to about 85% by weight liberated cesium or rubidium to 15% to about 70% by weight salt. The mixture of salt and liberated cesium and/or rubidium can be subjected to heat and up to temperature of from 500 C to 3,000 C or higher.
This can be done by rotary kiln, or heating device or furnace. The heating time can be from minutes to hours (e.g., 10 minutes to 10 hours or more). The cesium and/or rubidium salt formed from this second reaction can then be subjected to evaporation techniques to concentrate the cesium salt and/or rubidium salt (e.g., cesium sulfate) so as to precipitate out the cesium salt and/or rubidium salt for easier recovery.
[0044] Once the starting material is suitably decomposed, 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, and/or, the cesium salt and/or rubidium salt, which can be in the vapor phase, can be scrubbed or otherwise contacted with water to form a salt solution, which can then be concentrated as a salt solution by heating to remove or evaporate some of the water. Or as an option, the cesium and/or rubidium values, 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 cesium and/or rubidium values, liberated as a vapor phase can be scrubbed or otherwise contacted with a base.
[0045] Figure 2 further sets forth a block diagram showing the various steps of the methods of the present invention including optional steps involving the presence and/or addition of salts to the process. The blocks or rectangles defined by dashed lines are optional steps. Referring to Figure 2, cesium bearing or ore material and/or rubidium bearing or ore material is obtained (10) and optionally subjected to crushing or milling to reduce the size of the material (12) preferably to the particle sizes mentioned herein. Then, the material is introduced into an oven or furnace or other heating device (14) and a reactant (16) is also introduced. One or more salts (36) can be introduced at any point or multiple points in the process as 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) can be present as part of the ore or material (10). As indicated, optionally the reactant and cesium/rubidium bearing material can be mixed prior to being introduced into the furnace, or can be mixed in the furnace. Further, the reactant and/or cesium/bearing material can be introduced as batches, continuously, semi-continuously, and the like. Heat (18) is then introduced to the material and then cesium and/or rubidium (e.g., cesium oxide and/or rubidium oxide) are liberated or displaced (20). As an option, cesium oxide/rubidium can be liberated as a gas. Then, the cesium and/or rubidium (20) reacts with the salt(s) (38) to form cesium salt(s) and/or rubidium salt(s). The cesium salt(s) and/or rubidium salt(s) can be formed in the vapor phase. The cesium salt and/or rubidium material is separated from the remaining ore/material (22). The remaining ore/material can be discarded, or returned to the process (10 and/or 14) and/or for further processing. The cesium salt(s) and/or rubidium salt(s) can be recovered (48).
The cesium salt(s) and/or rubidium salt(s) can be scrubbed with water or acid or an organic liquid (40) to obtain a solution (42) (e.g., a salt solution, a salt of the acid solution, an cesium and/or rubidium organic solution). The solution can be subjected to evaporation or other techniques to concentrate the solution (44). Similar rubidium materials can be formed from rubidium when rubidium is the source material.
[0046] As an option, the method can maintain a slight CO presence (e.g., 1 wt% or less, such as 500 ppm or less in the solution, based on wt of solution), which can be advantageous to facilitate the recovery of the cesium and/or rubidium.
[0047] The type of reactions that can be achieved with various cesium-containing minerals are provided below. However, it is to be appreciated that while Pollucite is the mineral portrayed in the exemplary reaction shown below, other cesium-bearing minerals or ores can be used. Further, while calcium oxide is used as the preferred reactant, again, it is to be appreciated that other reactants can be used.
Reaction #1 (Larnite):
Cs20 A1203 4S102 + 8 CaO
>1150 C
p=== Ca2 Al2 Si07 +3 Ca2 SiO4 + Cs20 1\
Lightly Gehlenite Larnite Sintered Reaction #2 (Rankinite):
Cs20 A1203 4S102 + 61/2 CaO
>1150 C
Ca2 Al2 Si07+ 11/2 Ca3 Si2 07+ CS20 Lightly Gehlcnite Rankinite Sintered Reaction #3 (VVoIlastonite):
Cs20 A1203 4S102 + 5 CaO
>1150 C Ca 2 Al2 Si07+ 3 Ca SiO3 + Cs20 Lightly Gehlenite Wollastonite Sintered [0048] As an option, the recovered Cs20 can then be processed for a variety of uses. For instance, the Cs20 can be used to form cesium compounds, such as cesium formate. For instance, the Cs20 can be recovered and subjected to further recovery processes by reacting the Cs20 with at least one salt, where the salt is capable of recovering at least one metallic element, such as cesium, to form a reaction product that includes at least one metallic element. For instance, the salt can be a sulfate salt. Details of this further processing step can be found in U.S. Patent No.
7,323,150. By using this process, the cesium can be converted to a precursor salt, such as cesium sulfate, from which other cesium salts are produced. Other methodology similarly can produce alternative cesium salts from precursors like cesium hydroxide and cesium carbonate. As described, for instance, in U.S. Patent No. 7,759,273, the cesium can be formed into a cesium formate which subsequently can then be converted to a different cesium metal salt. Another process to form cesium salts is described in U.S. Patent No. 6,652,820. This method involves forming a cesium salt by reacting cesium sulfate with lime to form cesium hydroxide which can then be converted to a cesium salt, such as cesium formate. As stated, the cesium compounds can be very desirable as drilling fluids or other fluids used for hydrocarbon recovery, such as completion fluids, packer fluids, and the like.
[0049] The processes described in U.S. Patent No. 6,015,535 can also be used to form desirable cesium compounds, such as cesium formate. The various formulations and compositions described in the following patents can be used with the cesium or cesium compounds recovered by the processes of the present invention: U.S. Patent No.
7,407,008;
7,273,832; 7,211,550; 7,056,868; 6,818,595; 6,656,989; and 6,423,802.
[0050] The present invention includes the following aspects/embodiments/features in any order and/or in any combination:
1. A method for recovering at least cesium, rubidium, or both from an ore or other material, said method comprising:
heating a) said ore or other material, and b) at least one reactant together, wherein said heating is at a temperature sufficient to liberate at least a portion of said cesium, rubidium, or both from said ore or other material, and said reactant is an oxide of a metal, or a carbonate of a metal, hydroxide of a metal or a hydrate of a metal, that is capable of displacing cesium oxide, rubidium oxide, or both from said ore or other material.
2. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is lime, hydrated lime, lime in solution or calcium carbonate or any combination thereof 3. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is an oxide or hydroxide or hydrate or carbonate of calcium.

4. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is an oxide of strontium, an oxide of barium, an oxide of lithium, or any combination thereof.
5. The method of any preceding or following embodiment/feature/aspect, wherein said temperature of said heating is 1,000 C or higher.
6. The method of any preceding or following embodiment/feature/aspect, wherein said temperature of said heating is from about 1,000 C to about 2,000 C.
7. The method of any preceding or following embodiment/feature/aspect, wherein said temperature of said heating is from about 1,025 C to about 1,750 C.
8. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material is present as particulates.
9. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material is present as particulates in a size of about -200 mesh or smaller.
10. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material is present as particulates having at least 50% by weight of -200 mesh.
11. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material is present as particulates and having an average particle size of from about 1 mm to about 15 mm.
12. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material is present as particulates and having an average particle size of from about 2 mm to about 12 mm.
13. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is present as particulates.

14. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is present as particulates and having a size of about -200 mesh or smaller.
15. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is present as particulates and having at least 50% by weight of -200 mesh.
16. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is present as particulates and having an average particle size of from about 1 mm to about 15 mm.
17. The method of any preceding or following embodiment/feature/aspect, wherein said reactant is present as particulates and having an average particle size of from about 2 mm to about 12 mm.
18. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material and said reactant or both are in particulate form and each have an average particle size that is within 50% of each other.
19. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material and said reactant or both are in particulate form and each have an average particle size that is within 25% of each other.
20. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material and said reactant or both are in particulate form and each have an average particle size that is within 10% of each other.
21. The method of any preceding or following embodiment/feature/aspect, wherein said ore is present and subjected to said heating.
22. The method of any preceding or following embodiment/feature/aspect, wherein said ore is present and is cesium-bearing ore.

23. The method of any preceding or following embodiment/feature/aspect, wherein said ore is present and is silicate-based ore.
24. The method of any preceding or following embodiment/feature/aspect, wherein said ore is present and is a1uminosilicate-based ore.
25. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material is in intimate contact with said at least one reactant.
26. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material and said at least one reactant have a weight ratio of said ore or other material to said reactant of from about 15:85 to about 85:15.
27. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material and said at least one reactant have a weight ratio of said ore or other material to said reactant of from about 5:95 to about 95:5.
28. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material and said at least one reactant have a weight ratio of said ore or other material to said reactant of from about 40:60 to about 60:40.
29. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material and said at least one reactant are mixed together prior to or during said heating.
30. The method of any preceding or following embodiment/feature/aspect, further comprising recovering said cesium or rubidium or both.
31. The method of any preceding or following embodiment/feature/aspect, further comprising recovering cesium or rubidium or both in the form of a gas.

32. The method of any preceding or following embodiment/feature/aspect, further comprising recovering said cesium or rubidium or both in the form of a gas and converting said gas to a liquid solution containing cesium or rubidium or both.
33. The method of any preceding or following embodiment/feature/aspect, further comprising recovering cesium or rubidium or both in the form of a gas, wherein said cesium or rubidium or both are in the form of an oxide.
34. The method of any preceding or following embodiment/feature/aspect, further comprising scrubbing said gas with an aqueous solution or non-aqueous solution.
35. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material, after said liberating, is at least partially converted to calcium silicate, calcium aluminosilicate, or both.
36. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material is present and comprises pollucite.
37. The method of any preceding or following embodiment/feature/aspect, wherein said heating is under pressure.
38. The method of any preceding or following embodiment/feature/aspect, wherein said heating is under an inert atmosphere.
39. The method of any preceding or following embodiment/feature/aspect, wherein said heating is in an oxygen-containing atmosphere.

40. The method of any preceding or following embodiment/feature/aspect, wherein said heating is under vacuum.

41. The method of any preceding or following embodiment/feature/aspect, wherein said heating is under a reductive environment.

42. The method of any preceding or following embodiment/feature/aspect, wherein said heating is for a period of 5 minutes or more.

43. The method of any preceding or following embodiment/feature/aspect, wherein said hearing is for a period of from about 5 minutes to 100 hours.

44. Cesium oxide or rubidium oxide obtained from the method of any preceding or following embodiment/feature/aspect.

45. The method of any preceding or following embodiment/feature/aspect, wherein said temperature of said heating is from about 1,025 C to about 3,000 C.

46. The method of any preceding or following embodiment/feature/aspect, wherein said temperature of said heating is at a temperature sufficient to volatize said cesium, rubidium, or both.

47. The method of any preceding or following embodiment/feature/aspect, wherein said ore or other material further comprises at least one salt, and wherein said at least one salt reacts with said at least a portion of said cesium, rubidium, or both to form a cesium salt or a rubidium salt or both.

48. The method of any preceding or following embodiment/feature/aspect, wherein at least one salt comprises a chloride.

49. The method of any preceding or following embodiment/feature/aspect, wherein at least one salt comprises a sulfate.

50. The method of any preceding or following embodiment/feature/aspect, wherein said method further comprises adding at least one salt prior to or during said heating.

51. The method of any preceding or following embodiment/feature/aspect, wherein said at least one salt reacts with said at least a portion of said cesium, rubidium, or both to form a cesium salt or a rubidium salt or both.

52. The method of any preceding or following embodiment/feature/aspect, wherein said cesium salt or rubidium salt comprises cesium sulfate, cesium chloride, rubidium sulfate, or rubidium chloride.

53. The method of any preceding or following embodiment/feature/aspect, wherein said cesium salt or rubidium salt comprises cesium sulfate, cesium chloride, rubidium sulfate, or rubidium chloride.

54. The method of any preceding or following embodiment/feature/aspect, wherein method further comprises scrubbing said cesium salt or rubidium salt or both in vapor phase with water or an acid or a base.

55. The method of any preceding or following embodiment/feature/aspect, wherein method further comprises scrubbing said cesium salt or rubidium salt or both in vapor phase with water or an acid or a base.
[0051] The present invention can include any combination of these various features or embodiments above and/or below as set forth in sentences and/or paragraphs.
Any combination of disclosed features herein is considered part of the present invention and no limitation is intended with respect to combinable features.
[0052] Applicants submit that when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defiling a range.
[0053] Other embodiments of the present invention will be apparent to those skilled in the art from consideration of the present specification and practice of the present invention disclosed herein. It is intended that the present specification and examples be considered as exemplary only with a true scope and spirit of the invention being indicated by the following claims and equivalents thereof.

Claims

CLAIMS:

1. A method for recovering at least cesium, rubidium, or both from an ore, said method comprising:
heating, in an oxygen-containing environment, a mixture comprising a) said ore, and b) at least one reactant, liberating, cesium oxide or rubidium oxide or both, from said mixture, in the form of a gas, and scrubbing said gas with an aqueous solution or non-aqueous solution wherein said reactant is an oxide of a metal, or a carbonate of a metal, a hydroxide of a metal or a hydrate of a metal, that displaces cesium oxide, rubidium oxide, or both from said ore.

2. The method of claim 1, wherein said at least one reactant is lime, hydrated lime, lime in solution, or calcium carbonate, or any combination thereof.

3. The method of claim 1, wherein said at least one reactant is an oxide or hydroxide or hydrate or carbonate of calcium.

4. The method of claim 1, wherein said at least one reactant is an oxide of strontium, an oxide of barium, an oxide of lithium, or any combination thereof.

5. The method of any one of claims 1 to 4, wherein said heating is at a temperature of 1,000°
C or higher.

6. The method of any one of claims 1 to 4, wherein said heating is at a temperature from about 1,000° C to about 2,000° C.

7. The method of any one of claims 1 to 4, wherein said heating is at a temperature from about 1,025° C to about 1,750° C.

8. The method of any one of claims 1 to 7, wherein said ore is present as particulates.

9. The method of any one of claims 1 to 7, wherein said ore is present as particulates with a size of about -200 mesh or smaller.

10. The method of any one of claims 1 to 7, wherein said ore is present as particulates and has a size of at least 50% by weight of -200 mesh.

11. The method of any one of claims 1 to 7, wherein said ore is present as particulates and has an average particle size of from about 1 mm to about 15 mm.

12. The method of any one of claims 1 to 7, wherein said ore is present as particulates and has an average particle size of from about 2 mm to about 12 mm.

13. The method of any one of claims 1 to 7, wherein said at least one reactant is present as particulates.

14. The method of any one of claims 1 to 7, wherein said at least one reactant is present as particulates and has a size of about -200 mesh or smaller.

15. The method of any one of claims 1 to 7, wherein said at least one reactant is present as particulates and has a size of at least 50% by weight of -200 mesh.

16. The method of any one of claims 1 to 7, wherein said at least one reactant is present as particulates and has an average particle size of from about 1 mm to about 15 mm.

17. The method of any one of claims 1 to 7, wherein said at least one reactant is present as particulates and has an average particle size of from about 2 mm to about 12 mm.

18. The method of any one of claims 1 to 7, wherein said ore and said at least one reactant are in particulate form and each has an average particle size that is within 50%
of each other.

19. The method of any one of claims 1 to 7, wherein said ore and said at least one reactant are in particulate form and each has an average particle size that is within 25%
of each other.

20. The method of any one of claims 1 to 7, wherein said ore and said at least one reactant are in particulate form and each has an average particle size that is within 10%
of each other.

21. The method of any one of claims 1 to 20, wherein said ore is cesium-bearing ore.

22. The method of any one of claims 1 to 20, wherein said ore is silicate-based ore.

23. The method of any one of claims 1 to 20, wherein said ore is aluminosilicate-based ore.

24. The method of any one of claims 1 to 23, wherein said ore is in intimate contact with said at least one reactant.

25. The method of any one of claims 1 to 24, wherein said ore and said at least one reactant have a weight ratio of said ore to said at least one reactant of from about 15:85 to about 85:15.

26. The method of any one of claims 1 to 24, wherein said ore and said at least one reactant have a weight ratio of said ore to said at least one reactant of from about 5:95 to about 95:5.

27. The method of any one of claims 1 to 24, wherein said ore and said at least one reactant have a weight ratio of said ore to said at least one reactant of from about 40:60 to about 60:40.

28. The method of any one of claims 1 to 27, wherein said ore and said at least one reactant are mixed together prior to or during said heating.

29. The method of any one of claims 1 to 28, further comprising converting said gas to a liquid solution containing cesium oxide or rubidium oxide or both.

30. The method of any one of claims 1 to 29, wherein a portion of said ore , after said liberating, is partially converted to calcium silicate, calcium aluminosilicate, or both.

31. The method of any one of claims 1 to 30, wherein said ore comprises pollucite.

32. The method of any one of claims 1 to 31, wherein said heating is under pressure.

33. The method of any one of claims 1 to 30, wherein said heating is for a period of 5 minutes or more.

34. The method of any one of claims 1 to 30, wherein said heating is for a period of from about 5 minutes to 100 hours.

35. The method of any one of claims 1 to 5, wherein said heating is at from about 1,025° C to about 3,000° C.

36. The method of any one of claims 1 to 35, wherein said ore further comprises at least one salt, and wherein said at least one salt reacts with a portion of said cesium, rubidium, or both to form a cesium salt or a rubidium salt or both.

37. The method of claim 36, wherein said at least one salt is a chloride salt.

38. The method of claim 36, wherein said at least one salt is a sulfate salt.

39. The method of any one of claims 1 to 30, wherein said method further comprises adding at least one salt prior to or during said heating.

40. The method of claim 39, wherein said at least one salt reacts with a portion of said cesium, rubidium, or both to form a cesium salt or a rubidium salt or both.

41. The method of claim 36, wherein said cesium salt or rubidium salt comprises cesium sulfate, cesium chloride, rubidium sulfate, or rubidium chloride.

42. The method of claim 40, wherein said cesium salt or rubidium salt comprises cesium sulfate, cesium chloride, rubidium sulfate, or rubidium chloride.

43. The method of claim 36, wherein said method further comprises scrubbing said cesium salt or rubidium salt or both in vapor phase with water or an acid or a base.

44. The method of claim 40, wherein said method further comprises scrubbing said cesium salt or rubidium salt or both in vapor phase with water or an acid or a base.