Canadian Patents Database / Patent 2885437 Summary

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(12) Patent Application: (11) CA 2885437
(54) English Title: APPARATUS AND METHOD FOR ELECTROCHEMICAL MODIFICATION OF LIQUIDS
(54) French Title: APPAREIL ET PROCEDE POUR MODIFICATION ELECTROCHIMIQUE DE LIQUIDES
(51) International Patent Classification (IPC):
  • B01D 61/46 (2006.01)
  • C22B 3/42 (2006.01)
(72) Inventors :
  • JAMES, PATRICK I. (United States of America)
(73) Owners :
  • BLUE PLANET STRATEGIES, LLC (United States of America)
(71) Applicants :
  • BLUE PLANET STRATEGIES, LLC (United States of America)
(74) Agent: RIDOUT & MAYBEE LLP
(45) Issued:
(22) Filed Date: 2015-03-20
(41) Open to Public Inspection: 2016-09-20
Examination requested: 2018-02-15
(30) Availability of licence: N/A
(30) Language of filing: English

English Abstract


An apparatus for electrochemical modification of
liquid streams employing an electrolytic cell which
includes an anode compartment defined by an anode structure
where oxidation is effected, containing a liquid
electrolyte anolyte, and a cathode compartment defined by a
cathode structure where reduction is effected containing a
liquid electrolyte catholyte. In addition, the
electrolytic cell includes at least one additional
compartment arranged at least partially between the anode
compartment and the cathode compartment and separated from
the anode compartment and the cathode compartment by a
separator structure arranged to supports ionic conduction
of current between the anode structure and the cathode
structure.


Note: Claims are shown in the official language in which they were submitted.

- 22 -
CLAIMS:
1. An apparatus for electrochemical modification of liquid
streams employing at least one electrolytic cell which
comprises:
an anode compartment defined by an anode structure
where oxidation is effected, containing a liquid
electrolyte anolyte;
a cathode compartment defined by a cathode structure
where reduction is effected containing a liquid
electrolyte catholyte:
at least one additional compartment arranged at least
partially between the anode compartment and the
cathode compartment and separated from the anode
compartment and the cathode compartment by a
separator structure arranged to supports ionic
conduction of current between the anode structure and
the cathode structure; and
a system for conducting unidirectional electric
current supported by the electrolytes from the anode
structure through the separator structure and into
the catholyte and to the cathode structure;

- 23 -
wherein, the separator structure incorporates at
least one ion conductive membrane positioned to
contactly separate the anode compartment and the at
least one additional compartment, and arranged to
preferentially conduct a plurality of Hydrogen-like
Cations while impeding transport of at least one
selection of Anions, and at least another ion
conductive membrane positioned to contactly separate
the cathode compartment and the at least one
additional compartment, and arranged to
preferentially conduct at least another selection of
Anions while impeding transport of the plurality of
Hydrogen-like Cations.
2. The apparatus of claim 1 wherein, the cathode
structure comprises conducting cathode particulates forming
a cathode particulates bed and a current feeder device in
at least intermittent contact with said cathode
particulates where the cathode particulates are arranged in
motion and the particulates motion is substantially
independent of a bulk flow of the catholyte.
3. The apparatus of claim 2 wherein, the anode
structure comprises conducting anode particulates forming

- 24 -
an anode particulates bed and a current feeder device in at
least intermittent contact with said anode particulates
where the anode particulates are arranged in motion and the
particulates motion is substantially independent of a bulk
flow of the anolyte.
4. The apparatus of claim 3 comprising a particulate
manipulation system arranged to manipulate particulates
motion such after participating in the target redox
reactions, the anode and the cathode particles are
separated from the respective anolyte and catholyte, and
controllably passed to the cathode compartment and the
anode compartment respectively.
5. The apparatus of claim 1, wherein the at least one
ion conductive membrane positioned to contactly separate
the anode compartment and the at least one additional
compartment incorporates a selective ion conductive
membrane.
6. The apparatus of claim 1, wherein the at least
another ion conductive membrane positioned to contactly
separate the cathode compartment and the at least one
additional compartment incorporates a selective ion
conductive membrane.

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7. The apparatus of claim 5, wherein the at least one
selective ion conductive membrane positioned to contactly
separate the anode compartment and the at least one
additional compartment incorporates a proton selective
Cation conductive membrane.
8. The apparatus of claim 6, wherein the at least
another selective ion conductive membrane positioned to
contactly separate the cathode compartment and the at least
one additional compartment incorporates a sulfate selective
Anion conductive membrane.
9. The apparatus of claim 1, wherein the liquid
electrolyte catholyte comprises Cations and Cation mixtures
selected from the group consisting of Al+3, NH4+, Ba+2, Cd+2,
Ca+2, Cr+2, Cr+3, Co+2, Cu+, Cu+2, H+, H3O+2, Fe+2, Fe+3, Pb+2,
Pb+4, Li+, Mg+2, Mn+2, Ni+2, Hg2+2, Hg+2, K+, Ag+, Sr+2, Na+,
Sn+2, Sn+4, Zn+2.
10. The apparatus of claim 1, wherein the liquid
electrolyte anolyte comprise Anions and Anion mixtures
selected from the group consisting of C2H3O2-/CH3COO-,Br-,
CO3 -2, HCO3-, ClO3-, Cl-,CrO4 -2, CN-, Cr2O7 -2, F-, H-, OH-, ClO-,

- 26 -
IO3 -, I-, NO3-, N -3, NO2-, C2O4 -2, O-2, HC2O4-, O2 -2 , PO4 -3, HPO4 -2,
H2PO4-, SiO3 -2, SO4 -2, HSO4-, S2O3 -2, S -2, HS-, SO3 -2, HSO3-.
11. The apparatus of claim 1, wherein an input into the
anode compartment includes an Acid Rock Drainage or
leachate product.
12. The apparatus of claim 1, wherein an input into the
anode compartment includes a mixture of an Acid Rock
Drainage or leachate product and a raffinate.
13. A method for electrochemical modification of liquid
streams employing at least one electrolytic cell which
comprises:
(a) providing the at least one electrolytic cell
incorporating an anode compartment defined by an
anode structure where oxidation is effected,
containing a liquid electrolyte anolyte;
a cathode compartment defined by a cathode structure
where reduction is effected containing a liquid
electrolyte catholyte:
at least one additional compartment arranged at least
partially between the anode compartment and the
cathode compartment and separated from the anode

- 27 -
compartment and the cathode compartment by a
separator structure arranged to support ionic
conduction of current between the anode structure and
the cathode structure; and
a system for conducting unidirectional electric
current supported by the electrolytes from the anode
structure through the separator structure and into
the catholyte and to the cathode structure;
wherein, the separator structure incorporates at
least one ion conductive membrane positioned to
contactly separate the anode compartment and the at
least one additional compartment, and arranged to
preferentially conduct a plurality of Hydrogen-like
Cations while impeding transport of at least one
selection of Anions, and at least another ion
conductive membrane positioned to contactly separate
the cathode compartment and the at least one
additional compartment, and arranged to
preferentially conduct at least another selection of
Anions while impeding transport of the plurality of
Hydrogen-like Cations;
(b) providing an amount of raw materials and performing
leaching to extract a leachate in a form of a
pregnant leach solution;

- 28 -
(c) performing refining of the pregnant leach solution
to extract desired metals and generate a raffinate;
(d) inputing an Acid Rock Drainage or leachate product
into the cathode compartment and the raffinate into
the at least one additional compartment and conduct
an unidirectional electric current from the anode
structure to the cathode structure;
(e) redirecting an elevated acidity output from the at
least one additional compartment onto the amount of
raw material until predetermined quantities of the
desired metals have been extracted.
14. The method of claim 13, wherein in the step (d) the
input into the cathode compartment represents a mixture of
the Acid Rock Drainage or leachate product and the
raffinate.
15. The method of claim 13, wherein the cathode
structure comprises conducting cathode particulates forming
a cathode particulates bed and a current feeder device in
at least intermittent contact with said cathode
particulates where the cathode particulates are arranged in
motion and the particulates motion is substantially
independent of a bulk flow of the catholyte.

- 29 -
16. The method of claim 13, wherein the anode structure
comprises conducting anode particulates forming an anode
particulates bed and a current feeder device in at least
intermittent contact with said anode particulates where the
anode particulates are arranged in motion and the
particulates motion is substantially independent of a bulk
flow of the anolyte.
17. The method of claim 13, wherein a particulate
manipulation system arranged to manipulate particulates
motion such after participating in the target redox
reactions, the anode and the cathode particles are
separated from the respective anolyte and catholyte, and
controllably passed to the cathode compartment and the
anode compartment respectively.
18. The method of claim 13, wherein the at least one
ion conductive membrane positioned to contactly separate
the anode compartment and the at least one additional
compartment incorporates a selective ion conductive
membrane.
19. The method of claim 13, wherein the at least
another ion conductive membrane positioned to contactly


-30-

separate the cathode compartment and the at least one
additional compartment incorporates a selective ion
conductive membrane.
20. The method of claim 18, wherein the at least one
ion conductive membrane positioned to contactly separate
the anode compartment and the at least one additional
compartment incorporates a proton selective Cation
conductive membrane.
21. The method of claim 19, wherein the at least
another ion conductive membrane positioned to contactly
separate the cathode compartment and the at least one
additional compartment incorporates a sulfate selective
Anion conductive membrane.
22. The method of claim 13, the liquid electrolyte
catholyte comprise Cations and Cation mixtures selected
from the group consisting of Al+3, NH4+, Ba+2, Cd+2, Ca+2,
Cr+2, Cr+3, Co+2, Cu+, Cu+2, H+, H3O+2, Fe+2, Fe+3, Pb+2, Pb+4,
Mg+2, Mn+2, Ni+2, Hg2 +2, Hg+2, K+, Ag+, Sr+2, Na+, Sn+2,
S+4 , Zn+2.
23. The method of claim 13, wherein the liquid
electrolyte anolyte comprise Anions and Anion mixtures


-31-

selected from the group consisting of C2H3O2-/CH3COO-,Br-,
CO3 -2, HCO3-, ClO3-, Cl-, CrO4 -2, CN-, Cr2O7 -2, F-, H-, OH-, ClO-,
IO3-, I-, NO3-, N-3, NO2-, C2O4 -2, O-2, HC2O4-, O2 -2, PO4 -3, HPO4-2,
H2PO4-, SiO3- 2, SO4 -2, HSO4-, S2O3 -2, S-2, HS-, SO3 -2, HSO3-.

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

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1
APPARATUS AND METHOD FOR ELECTROCHEMICAL MODIFICATION OF
LIQUIDS
[0001] This invention was made and reduced to practice
in parts with US government support under National
Institutes of Health (NIH) Small Business Innovation
Research (SBIR) grant 1 R43 ES20096-01 AND Department of
Energy (DOE) Small Business Innovation Research (SBIR)
grant DE-SC0006181. The US government has certain rights
in the invention.
FIELD OF THE INVENTION
[0002] The invention relates to an apparatus and a
method for electrochemical modification of concentrations
of constituents of liquid streams which contain organic
and/or inorganic components. More precisely, the invention
is concerned with an electrolytic cell technology with
potentials to modification of concentrations of the
components.

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BACKGROUND OF THE INVENTION
[0003] Contamination of liquid streams with various
organic and inorganic constituents may represent an
environmental problem affecting environment quality and
represents significant threat to human health and safety.
For example, heavy metals contaminations of aquatic
environments may arise from commercial mining and metal
extraction processes, surfaces modification and protection
processes, or communal and industrial waste sites resulting
from a variety of active or defunct industrial fabrication
and manufacturing activities. Similarly, significant
organic water pollutants, like aliphatic, aromatic, or
halogenated hydrocarbons and phenols may be associated with
oil exploration, extraction and refining, chemicals
production, or large-scale farming and food processing.
[0004] In addition to potentials for significant
environmental damage, affected liquid streams my represent
dilute sources of desirable raw materials like heavy
metals,metal oxides, inorganic salts, and other compounds.
For example, the Berkeley Mine Pit in Butte, Montana alone
represents an estimated 30 billion gallons of acid mine
drainage which at one time contained -180 ppm of copper

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along with other metals which could yield up to 22,000 tons
of pure copper by use of a small treatment facility.
[0005] An economically relevant group of prior art
methods of removal of heavy metal ions from liquid
solutions is based on chemical precipitation. This process
is likely burdened by complexity, high cost, clear
preference for extremely large facilities and high-volume
operations, and efficiency decrease with decrease in
concentration of pollutants. Additional disadvantages may
concern resulting byproduct of precipitated sludge which
may become a concentrated yet mixed contaminant source of
the toxins in the source material. The sludge may mandate
further processing and costly long term disposal as a
highly toxic waste. Many similar disadvantages may burden
alternative heavy ion removal methods that may incorporate:
filtration, ion exchange, foam generation and separation,
reverse osmosis, or combinations of listed processes.
[0006] In contrast, the extraction technologies enabled
by several aspects of the current invention may be adapted
to alleviate at least some of the above considerations.
Additional features of the current invention, for example,
may contribute to the feasibility of modifying prior art
electrowinning technology so that it can be used to

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- 4 -
economically concentrate copper generated in low-grade
process streams instead of simply removing it. In general,
the disclosed embodiments of the copper extraction
technology may prepare a process stream so the customer can
produce new copper from currently inaccessible sources with
existing in-place processing infrastructure, equipment, and
processes.
[0007] The present invention may provide some innovative
features for unlocking this vast and vitally needed
resource. Typical mines contain significant amounts of
their copper in such unviable ores. This invention may
allow the use of this "waste" ore and thereby increase
average heap leach mine output by 25% and thus globally
yield 3 Billion lbs/yr of newly recoverable copper.
[0008] Furthermore, additional features of embodiments
of the current invention may allow for practical metal
recovery from: Acid Rock Drainage (ARD), heavy metal and
radionuclide contaminated sites, and metal contaminated
industrial effluents such as electrowinning, plating plant,
pickling operations, and circuit board manufacture
(etching) discharges.

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[0009] In addition, different embodiments of the current
invention may be applicable and pertinent to commercial and
municipal processes where potential contaminants may be
reprocessed in parallel or in immediate sequence with
processes that may generate such materials to start with.
Even further, methods and apparatus of the current
invention may achieve the above functions in an essentially
integrated manner, frequently using at least one common
treatment loop to simultaneously refine the desired
products, generate materials and compounds that may be
reused in the subsequent performances of the process by the
disclosed apparatus, and generate essentially non-polluting
byproducts.
[0010] Finally, by application of highly integrated
multifunctional devices and processes, the components of
the current invention may achieve desirable results
utilizing optimized quantities of components, raw
materials, ingredients, and required energy; thus
approaching optimized economic results.
SUMMARY OF THE INVENTION
[0011] A method and an apparatus for electrochemical
modification of liquid streams employing an electrolytic

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cell which utilizes an anode compartment defined by an
anode structure where oxidation is effected, containing a
liquid electrolyte anolyte, and a cathode compartment
defined by a cathode structure where reduction is effected
containing a liquid electrolyte catholyte. In addition at
least one additional compartment has been arranged at least
partially between the anode compartment and the cathode
compartment and separated from the anode compartment and
the cathode compartment by a separator structure arranged
to support ionic conduction of current between the anode
structure and the cathode structure. Also, a system for
conducting unidirectional electric current provides a
unidirectional current flow supported by the liquid
electrolytes from the anode structure through the separator
structure and into the catholyte and to the cathode
structure have been provided.
[0012] The
separator structure incorporates at least one
ion conductive membrane positioned to contactly separate
the anode compartment and the at least one additional
compartment, and arranged to conduct a plurality of
Hydrogen-like Cations while impeding transport of at least
one selection of Anions, and at least another selective ion
conductive membrane positioned to contactly separate the
cathode compartment and the at least one additional

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compartment, and arranged to conduct at least another
selection of Anions while impeding transport of the
plurality of Hydrogen-like Cations.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The above and other embodiments, features, and
aspects of the present invention are considered in more
detail in relation to the following description of
embodiments shown in the accompanying drawings, in which:
[0014] FIG. 1. is a schematic view of devices and
processes of some embodiments in accordance with the
current invention.
[0015] FIG. 2. is a schematic view of devices and
processes of different embodiments in accordance with the
current invention.
[0016] FIG. 3. is a schematic view of devices and
processes of other different embodiments in accordance with
the current invention.

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DETAILED DESCRIPTION OF THE INVENTION
[0017] The invention summarized above may be better
understood by referring to the following description, which
should be read in conjunction with the accompanying
drawings. This description of an embodiment, set out below
to enable one to build and use an implementation of the
invention, is not intended to limit the invention, but to
serve as a particular example thereof. Those skilled in the
art should appreciate that they may readily use the
conception and specific embodiments disclosed as a basis
for modifying or designing other methods and systems for
carrying out the same purposes of the present invention.
Those skilled in the art should also realize that such
equivalent assemblies do not depart from the spirit and
scope of the invention in its broadest form. Embodiments
of this instant invention can be of planar, circular, and
concentric tubular or other configurations containing two
or more separate electrolyte compartments as required to
address different application needs.
[0018] One embodiment of the instant invention is
illustrated in Fig. 1.

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[0019] In
specific embodiments of the current invention,
at least one additional compartment 121 may be added
nominally between (at least partially) the cathode and
anode compartments 101 and 131 respectively, and separated
by at least one separator structure 111 arranged to prevent
bulk mixing of the contents of the separated compartments
101, 121, and 131. In some embodiments, the separator
structure 111 may include a pair of ion conductive elements
arranged to allow transport of desired ion species between
the compartments 101, 121, and 131. In one group of
embodiments the separator structure 111 may incorporate ion
conductive membranes 110 and 120 in direct contact with the
contents of the compartments 101 and 121, and compartments
121 and 131 (i.e. contactly separating compartments 101,
121, and 131). The ion conductive membranes may
incorporate ion conductive channels such that specific ions
may be transported between compartments with fluxes
depending on specific embodiment parameters including
applied voltage, ion concentrations, temperature, ion
mobility, and dimensions and surface properties of channels
etc. The parameters may be arranged such that desired
Anions are preferably transported from the cathode
compartment 101 into the at least one additional
compartment 121, while desired Cations may be preferably

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- 10 -
transported from the anode compartment 131 into the at
least one additional compartment 121.
[0020] A
particular combination of the electrical fields
for the cell operation in conjunction with the selective
nature of the separating membranes may allow one to
separate and transfer into the at least one additional
compartment 121 ions of interest so that they may be
concentrated in the added compartment in the manner
comparable to electrodialysis. One feature of such
modified cell may be to gain practical utility for several
industrially important applications.
[0021] In the
Fig. 1 schematically illustrated example,
at least one electrolytic cell 100 having at least three
compartments with at least two separate electrolyte flows
separated by at least two ion conductive membranes 110 and
120 respectively. The at least one cathode compartment 101
input 106 may depend on the specific circumstances of the
application and may include any number of liquid (aqueous
and nonaqueous) streams containing dilute metals of
suitable redox activity. A cathode structure 107 may be
conventional (stationary) assembly or may, in different
embodiments, incorporate a moving bed of conductive

CA 02885437 2015-03-20
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particulates for which numerous compositions may be
appropriate.
[0022] Several metals indicative for some aqueous
solutions of interest as the input 106, may include (but
not be limited by): copper, iron, nickel, cobalt, cadmium,
zinc, indium, gold, platinum, palladium, silver, mercury,
tin, and rhenium. Other metals "M(s)" or metal Cations
"M(+n)"or metal containing ion complexes could be addressed
in applications where one of the goals my be to reduce the
metal's oxidation state (e.g. from +n to +(n-1),
and not necessarily to plate the metal out. The
solutions' pH may be in the range from strongly acidic to
strongly alkaline.
[0023] In particular embodiments, the input 106 may
include Acid Rock Drainage (ARD) containing, for example,
high sulfate acidic solutions including mixtures of dilute
metals, as a result of natural processes attacking exposed
sulfide containing rock (ore). The cathode compartment
output 108 then may have the concentrations of the target
metal ion lowered (this may allow for transformation of the
species from one oxidation state to another without actual
removal of the target metal ion from solution) and the

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sulfate concentration lowered. In another embodiment, the
input 106 may include leachate product.
[0024] Depending upon different embodiments, at least
one anode structure 137 of at least one anode compartment
131 may either utilize a conventional geometrically stabile
DSA electrode or may incorporate moving beds of
particulates, for example, using particulates transferred
to/from the cathode compartment 101.
[0025] At least one additional compartment 121 may be
arranged at least partially between the at least one anode
compartment 131 and the at least one cathode compartment
101, and separated from the anode compartment and the
cathode compartment by the separator structure 111,
incorporating at least two ion conductive membranes 110 and
120, arranged to support ionic conduction of current
between the anode structure 137 and the cathode structure
107, but to restrict transport of selected Anions AN m2 from
the anode compartment 131 into the at least one additional
compartment 121, and to restrict transport of Cations (nli+)
from the at least one cathode compartment 101 into the at
least one additional compartment 131.

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[0026] In some embodiments, the at least one ion
conductive membrane 110 may represent a selective ion
conductive membrane positioned to contactly separate the at
least one cathode compartment 101 and at least one
additional compartment 121 (while being in direct contact
with the liquids contained in the compartments 101 and 121)
and arranged to selectively conduct specific Anions AN-ml or
a composition of Anions as appropriate to the specific
embodiments, while impeding transport of Hydrogen H+ or
Hydrogen-like (e.g. "Haydronium", "Zundel", or "Eigen")
Cations. In contrast, the at least one ion conductive
membrane 120 may represent a selective ion conductive
membrane positioned to contactly separate the at least one
anode compartment 131 and at least one additional
compartment 121 (while being in direct contact with the
liquids contained in the compartments 131 and 121) and
arranged to conduct Hydrogen H+ or Hydrogen-like Cations
while restricting transport of the AN m2 or a composition of
Anions as appropriate to the specific embodiments. As a
result, operations of the cell 100 may result, inter alia,
in gradual increase of concentrations of AN-rril and H+ ions
(and therefore the HmiAN acid)in the at least one additional
compartment 121. Therefore, outputs 129 from the
compartment 121, having elevated acidity, may be used for

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other purposes as the particular groups of embodiments may
mandate or desire.
[0027] One embodiment may include processing of zinc -
where the particulate bed may be transferred into the
anolyte but not in electrical contact with the anode
structure 137. The anode structure may utilize a separate
DSA electrode for oxygen evolution (for example) from water
splitting (H20 4 4H+ + 02 + e-)and the zinc being
spontaneously stripped from the particulate electrode
[using an inert substrate like 316 SS] to generate
concentrated ZnSO4 in the anolyte). The water splitting on
the anode includes generation of protons which may
subsequently be separated from the background supporting
electrolyte (salt) via the proton selective Cation
conductive membrane 120. Membranes selective to other
Cations could be used (for the appropriate embodiments).
[0028] It may be noted that the supporting electrolyte
139 may include a number of common salts or mixtures
thereof. Different embodiments may include (but not be
limited to) all combinations of CA Cations where CA = H+,
Nat, K+, Lit, Cu+2, Ca+2, Mg+2, Mn+2,Ni+2, Fe+2, Fe+3, A1+3, and
NH4, and AN Anions where AN = Acetate, bromide, chloride,
Chlorate, cyanide, hydroxide, hypochlorite, iodate, iodide,

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nitrate, oxalate, perchlorate, phosphate, hydrogen
phosphate, dihydrogen phosphate, bisulfate, and sulfate
plus those shown in the following Table I.
[0029] Table I.
Common Ion Chart
Positive Ions (Cations) Negative Ions (Anions)
Aluminum Al" Acetate C21-L02
/ CH3C00
Ammonium NH4* Bromide Br
Barium Ba " Carbonate COI 2
Cadmium Cd '2 Hydrogen Carbonate Ion /
BicarbonateFIC03
Calcium Ca " Chlorate C103
Chromium (II) Cr +2
Chloride CI
Chromium (III) Cr " Chlorite C102
Cobalt (II) Co *2 Chromate Cr042
Copper (I) Cu ' Cyanide CN
Copper (II) Cu +2 Dichromate Cr,04 2
Hydrogen H ' Fluoride F
Hydronium H30 * Hydride H
Iron (II) Fe +2 Hydroxide OH
Iron (III) Fe'l I lypochlorite CIO
Lead (II) Ph '2 Iodate 103
Lead (IV) Pb" Iodide I
Lithium Li ' Nitrate NO3
Magnesium Mg" Nitride N 3
Manganese (II) Mn +2 Nitrite NO2
Mercury (1) Ilg2 +2 Oxalate
C204 2
Mercury (II) Hg +2 Oxide 0 2
Potassium K ' Hydrogen Oxalate Ion HC204
Silver Ag 4 Perchlorate C104
Strontium Sr" Permanganate Mn04
Sodium Na ''' Peroxide Ion
Tin (II) S1142 Phosphate P043
Tin (IV) Sn -'4 Monohydrogen Phosphate 11P042
Zinc Zn +2 Dihydrogen Phosphate H2PO4
Silicate SiO3 -
Sulfate S042
Hydrogen Sulfate Ion / Bisulfate HSO4
I - mono 5 - penta 9 - nona Thiosul fate S203 2
2 - di 6 - hexa I() - deca Sulfide S 2
3 - tri 7 - hepta Hydrogen Sulfide Ion / Bisultide HS
4 - tetra g - octa Sulfite SO4 2
Hydrogen Sulfite Ion / Bisulfite HS03
[0030] As in the discussion of the above embodiments,
the at least one additional compartment 121 may be
delineated on either side by selective ion conductive

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membranes 110 and 120 which allow selective ionic
conduction. In some embodiments, a simple physical barrier
such as a microporous membrane like DARAMIC available
commercially at least from the Daramic, LLC (a business
unit of Polypore, Inc. with headquarters in Charlotte,
North Carolina USA) could also be used but typically
achieves lower separation efficiency and resultant
concentration differentials than afforded by ion selective
membranes. Typically an Anion selective membrane may be
employed to separate the cathode compartment 101 and the
additional compartment 121. In such an embodiment, a
sulfate selective Anion conductive membrane may be used
(several commercially available). Many commercial
varieties of Anion selective membranes are also available
in alternative, and would be suitable for use herein and in
different embodiments. For the anode compartment 131
/additional compartment 121 separation, a Cation selective
membrane 120 may be used. In some embodiments, a proton
selective membrane like DuPont's Nafion (or NAFION ) may be
used, with a bipolar variant being a possible choice due to
its enhanced suppression of back diffusion of Anions.
Again, many other commercial examples of Cation and proton
selective Cation selective membranes exist and may be
suitable for use herein and in other embodiments. The
emerging polymer membrane based fuel cell industry

CA 02885437 2015-03-20
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represents a market of choice and a motivator for the
future R&D and may be a rich source of new and better
membranes for emerging and yet to emerge embodiments of the
current invention.
[0031] In the embodiments pertinent to the schematics
illustrated in Fig. 1, the outputs 129 may be used in an
extraction procedure wherein, a strong leachant solution
including the output 129 (having e.g. sulfuric acid) may be
passed through raw materials 123 (e.g. crushed ore) to
leach out target metal or metals from the raw materials
123. The resultant leachate 124 (pregnant leach solution
or PLS) may be subsequently processed in a reactor 115 to
remove the dissolved metals. Most of the target metals 116
may be removed, but a residual amount of target metal
remains in a weak solution called raffinate 117. It may be
noted that the leaching procedures may consumes the
leachant (again as acid contained in the output 129) and
fresh makeup leachant (here acid) may need to be added to
the residual raffinate before it is recycled back to leach
more raw materials 123.
[0032] It may be noted that in some embodiments, the
reactor 115 may be based on electrochemical principles and
incorporate electrolytic cells as recited above.

ak 02885437 2015-03-20
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[0033] Regarding embodiments of the current invention
pertinent to the schematic illustration in Fig. 2, where it
may not be desirable to directly input solutions of
interest as the input 106 into the cathode compartment 101,
a portion of the raffinate 206 exiting the reactor 115 may
be inputted into the at least one cathode compartment 101.
The remaining portion of the raffinate 117 may, as before
(e.g. Fig. 1), be directed into the at least one additional
compartment 121 for recycling and further concentration of
the acid ingredients. It may be noted that the residual
metal in the raffinate 117 may not be lost for extraction
and is likely to be reacquired (e.g. plated as metal)
during the subsequent passages through the reactor 115
and/or the cathode compartment 101.
[0034] Furthermore, one may note that Fig. 2-illustrated
embodiments may include addition of further external
components 210 intended to improve devices and operations
acting, for example, as supporting solvents (aqueous or
non-aqueous), detergents, lubricants, emulgators,
coagulats, surfactants, buffers, corrosion inhibitors,
and/or combinations of the above functions.

ak 02885437 2015-03-20
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[0035] Regarding embodiments of the current invention
pertinent to the schematic illustration in Fig. 3, where it
may not be sufficient amount (or flow) of the input 106
(e.g. ADR), the input 106 may vary in time (seasonally or
in response to meteorological conditions), or/and may be
suboptimal to introduce only the input 106 directly into
the at least one cathode compartment 101, the input 106 may
be in-mixed with the portion 306 of the raffinate, in-mixed
directly into the reactor 115, and/or co-applied to the raw
materials 123. It may be noted that, as discussed above
regarding the Fig.2, the metal content in the input 106
exiting through the portion 117 of the raffinate may not be
lost for extraction and is likely to be reacquired (e.g.
plated as metal) during the subsequent passages through the
reactor 115 and/or the cathode compartment 101.
[0036] Processes of controlled removal of products of
electrochemical reactions can be performed continuously
during the operation of the electrolytic cell as customary
in the art of electrochemical disinfection or pollution
removal, or using batch process as customary in art of
conventional electrowinning of metals. Both modes of
operation are in accordance with the present invention.

ak 02885437 2015-03-20
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[0037] The present invention has been described with
references to the exemplary embodiments arranged for
different applications. While specific values,
relationships, materials and components have been set forth
for purposes of describing concepts of the invention, it
will be appreciated by persons skilled in the art that
numerous variations and/or modifications may be made to the
invention as shown in the specific embodiments without
departing from the spirit or scope of the basic concepts
and operating principles of the invention as broadly
described. It should be recognized that, in the light of
the above teachings, those skilled in the art can modify
those specifics without departing from the invention taught
herein. Having now fully set forth the preferred
embodiments and certain modifications of the concept
underlying the present invention, various other embodiments
as well as certain variations and modifications of the
embodiments herein shown and described will obviously occur
to those skilled in the art upon becoming familiar with
such underlying concept. It is intended to include all such
modifications, alternatives and other embodiments insofar
as they come within the scope of the appended claims or
equivalents thereof. It should be understood, therefore,
that the invention may be practiced otherwise than as
specifically set forth herein. Consequently, the present

CA 02885437 2015-03-20
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embodiments are to be considered in all respects as
illustrative and not restrictive.

A single figure which represents the drawing illustrating the invention.

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Title Date
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(22) Filed 2015-03-20
(41) Open to Public Inspection 2016-09-20
Examination Requested 2018-02-15

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Next Payment if small entity fee 2020-03-20 $100.00
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Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Filing $200.00 2015-03-20
Maintenance Fee - Application - New Act 2 2017-03-20 $50.00 2017-02-16
Maintenance Fee - Application - New Act 3 2018-03-20 $50.00 2017-12-19
Request for Examination $400.00 2018-02-15
Extension of Time $200.00 2018-11-28
Maintenance Fee - Application - New Act 4 2019-03-20 $50.00 2019-03-15
Current owners on record shown in alphabetical order.
Current Owners on Record
BLUE PLANET STRATEGIES, LLC
Past owners on record shown in alphabetical order.
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.

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Abstract 2015-03-20 1 19
Description 2015-03-20 21 591
Claims 2015-03-20 10 238
Drawings 2015-03-20 3 52
Representative Drawing 2016-08-23 1 9
Cover Page 2016-10-18 1 39
Prosecution-Amendment 2018-02-15 57 1,414
Description 2018-02-15 27 723
Claims 2018-02-15 10 250
Abstract 2018-02-15 1 19
Prosecution-Amendment 2018-02-19 1 53
Prosecution-Amendment 2018-02-22 6 383
Prosecution-Amendment 2018-05-17 54 1,388
Description 2018-05-17 28 734
Claims 2018-05-17 6 136
Drawings 2018-05-17 3 48
Prosecution-Amendment 2018-05-29 3 209
Correspondence 2018-08-28 1 23
Prosecution-Amendment 2018-08-28 4 268
Correspondence 2018-11-28 1 36
Correspondence 2018-12-04 1 48
Correspondence 2018-12-04 1 50
Prosecution-Amendment 2019-02-27 22 590
Claims 2019-02-27 6 143
Prosecution-Amendment 2019-07-12 5 344