Note: Descriptions are shown in the official language in which they were submitted.
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.
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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
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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
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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
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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,
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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.
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[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,
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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.
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[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.
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[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
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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
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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
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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
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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
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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
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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
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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.
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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.
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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.
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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.
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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.
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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.
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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
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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.
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