This invention relates generally to a method and apparatus for processing comminution product into concentrate.
A conventional mineral process plant for base metals porphyry type deposits (i.e. copper sulfide beneficiation) consists of multiple stages of comminution and froth flotation. The comminution stages are required to break the host or matrix rock to expose the crystals or grains of sulfide minerals. This process requires very large amounts of energy—typically 50% or more of the total energy required to produce base metals from their ores. The finer the mineralization of the minerals, the finer the required grind size and therefore the higher the energy requirements. It is recognized that the incremental energy required for given size reduction increases exponentially with size of the particle.
It is also recognized that different kinds of comminution equipment are more efficient than others, depending on the hardness of the ore and range of particle size reduction. For very large particles, such as run-of-mine ore, gyratory crushers are the most efficient. For hard or dry intermediate particles, such as gravels and aggregates, cone crushers and high pressure grinding rolls crushers are more efficient. For wet or soft intermediate particles, semi-autogenous grinding (SAG) or fully-autogenous grinding (AG) mills are more efficient. For finer grinding applications, horizontal ball mills are the equipment of choice. For very fine or ultra-fine grinding, vertical mills, media detritors, Isamills®, and other specially design equipment are the most energy-efficient. All of the above comminution innovations were developed to minimize the power required to achieve a given product particle size assuming some fixed feed particle size.
An alternative method of reducing the power requirement is to increase the product particle size and therefore reduce the amount of comminution work that must be performed. This approach is problematic because it often compromises the recovery in the downstream froth flotation process due to the reduction in liberated surfaces of hydrophobic minerals. For this reason, mineral processing plants try to operate at an economic optimum grind size (particle size), defined as that point at which any incremental recovery benefit for grinding finer is equal to the incremental cost of energy and grinding media required to achieve that grind.
There are many alternative configurations of comminution and flotation circuits.
The above flowsheet, and all current state-of-the-art sulfide beneficiation flowsheets, suffer from several drawbacks, namely:
There is a need in the mining industry to provide a better way to process the comminution product.
The present invention offers a solution to the above limitations of traditional sulfide mineral beneficiation. The nature of the solution stems from the unique ability of the invented process to:
The above qualities allow for a significant reduction in capital cost, operating cost, water requirements, and energy requirements when the invented process is used for sulfide mineral beneficiation.
The selective recirculation circuit can be used in a sulfide beneficiation process as shown in
In an embodiment, the present invention provides a method and apparatus for collecting mineral particles in a feed stream containing slurry and mineral particles, the method and apparatus comprising three stages: a loading stage, a stripping stage and a filtering stage. In the loading stage, the mineral particles in the received feed stream are loaded on barren media to provide loaded media. In the stripping stage, the loaded media is stripped with a stripping solution for separating the mineral particles from the barren media, wherein the barren media is returned to the loading stage for further use and the mineral particles along with the stripping solution are directed to the filtering stage where the stripping solution is recycled back the stripping stage and the mineral particles are directed to concentrates. In the feed stream where the mineral particles comprise recovered particles having exposed hydrophobic faces and unrecovered particles, the loaded media comprises the recovered particles and the unrecovered particles may be discharged along the slurry from the loading stage.
In an embodiment of the present invention, the stripping stage forms a first loop with the loading stage and forms a second loop with the filtering stage. As such, the stripping stage is configured to provide barren media to the loading stage and to receive loaded media from the loading stage via the first loop, while the stripping stage is configured to receive the stripping solution from the filtering stage and to provide the recovered particles to the filtering stage via the second loop.
Thus, the first aspect of the present invention is an apparatus, comprising:
a loading stage configured to receive barren media and a slurry containing mineral particles and to load the barren media with the mineral particles for providing loaded media;
a stripping stage configured to strip the loaded media with a stripping solution into a first portion comprising the barren media and a second portion containing the mineral particles and the stripping solution; and
a filtering stage configured to separate the mineral particles from the stripping solution in the second portion.
According to some embodiments of the present invention, the barren media comprises engineered material having molecules with a functional group configured to attract the mineral particles to the engineered material.
According to some embodiments of the present invention, the engineered material comprises synthetic bubbles and beads having a surface to provide the molecules.
According to some embodiments of the present invention, the synthetic bubbles and beads are made of a hydrophobic material having the molecules.
According to some embodiments of the present invention, the surface of the synthetic bubbles and beads comprises a coating having a hydrophobic chemical selected from the group consisting of poly(dimethysiloxane), hydrophobically-modified ethyl hydroxyethyl cellulose polysiloxanes, alkylsilane and fluoroalkylsilane.
According to some embodiments of the present invention, the surface of the synthetic bubbles and beads comprises a coating made of one or more dimethyl siloxane, dimethyl-terminated polydimethylsiloxane and dimethyl methylhydrogen siloxane.
According to some embodiments of the present invention, the surface of the synthetic bubbles and beads comprises a coating made of a siloxane derivative.
According to some embodiments of the present invention, the stripping stage is arranged to form a first loop with the loading stage, and to form a second loop with the filtering stage.
According to some embodiments of the present invention, the stripping stage configured to provide the first portion containing the barren media to the loading stage and to receive the loaded media via the first loop; and to provide the second portion to the filtering stage and to receive the stripping solution from the filtering stage via the second loop.
According to some embodiments of the present invention, the filtering stage is configured to output concentrates containing the mineral particles.
According to some embodiments of the present invention, the mineral particles comprise recovered particles having exposed hydrophobic surfaces and unrecovered particles, and wherein the loading stage comprises a mixing stage and a screening stage, the mixing stage configured to load the barren media with the recovered particles and the screening stage configured to discharge the unrecovered particles from the loading stage.
According to some embodiments of the present invention, the loading stage comprises a media loading stage and a loaded media recovery stage, the media loading stage configured to load the barren media with mineral particles, the loaded media recovery stage configured to separate the loaded media from the slurry.
According to some embodiments of the present invention, the stripping stage comprises a media stripping stage and a barren media recovery stage, the media stripping stage configured to strip the mineral particles from the loaded media, the barren media recovery stage configured to return the barren particles in the stripping stage to the media loading stage.
According to some embodiments of the present invention, the mineral particles comprise recovered particles and unrecovered particles, the loaded media containing the recovered particles, and wherein the media loading stage comprises an input arranged to receive the slurry and the loaded media recovery stage comprises a first output arranged to discharge the unrecovered particles, and wherein the filtering stage comprises a second output arranged to output the recovered particles.
According to some embodiments of the present invention, the method further comprises a milling stage and a classifying stage, the milling stage configured to mill a first comminution product into a second comminution product, the classifying stage configured to separate coarser particles from finer particles in the second comminution product, and wherein the slurry comprises process water and the coarser particles containing the mineral particles, and wherein the input is arranged to receive the slurry from the classifying stage, and the second output is arranged to return the recovered particles to the milling stage.
According to some embodiments of the present invention, the finer particles in the second comminution product are directed to a further milling stage.
According to some embodiments of the present invention, the finer particles in the second comminution product are further regrinding in the further milling stage into a first reground product and a second reground product having coarse particles than the first reground product, wherein the first reground product is directed to flotation.
According to some embodiments of the present invention, the second reground product also comprises unrecovered particles to be discharged as tails.
According to some embodiments of the present invention, the input is arranged to receive the slurring from a flotation cell.
The second aspect of the present invention is a method for processing a slurry having mineral particles, comprising:
causing barren media to contact with the slurry;
loading the mineral particles on the barren media for providing loaded media in the slurry;
separating the loaded media from the slurry;
stripping the loaded media to obtain mineral particles and barren media; and
discharging the mineral particles in a concentrate stream.
According to some embodiments of the present invention, the causing and loading are carried out in a loading stage and said separating and stripping are carried out in a stripping stage, the method further comprising:
returning the barren media obtaining from said stripping to the loading stage.
According to some embodiments of the present invention, a stripping solution is used in the stripping stage in said stripping, the method further comprising:
receiving mixture of the mineral particles and the stripping solution from the stripping stage;
separating the mineral particles and the stripping solution from the mixture; and
providing the stripping solution to the stripping stage.
According to some embodiments of the present invention, the barren media comprises engineered material having molecules with a functional group configured to attract the mineral particles to the engineered material.
According to some embodiments of the present invention, the engineered material comprises synthetic bubbles and beads having a surface to provide the molecules.
According to some embodiments of the present invention, the synthetic bubbles and beads are made of a hydrophobic material having the molecules.
According to some embodiments of the present invention, the surface of the synthetic bubbles and beads comprises a coating having a hydrophobic chemical selected from the group consisting of poly(dimethysiloxane), hydrophobically-modified ethyl hydroxyethyl cellulose polysiloxanes, alkylsilane and fluoroalkylsilane.
According to some embodiments of the present invention, the surface of the synthetic bubbles and beads comprises a coating made of one or more dimethyl siloxane, dimethyl-terminated polydimethylsiloxane and dimethyl methylhydrogen siloxane.
According to some embodiments of the present invention, the surface of the synthetic bubbles and beads comprises a coating made of a siloxane derivative.
By way of example,
The selective recirculation circuit 80 has many different uses. One of those uses is depicted in
In the above disclosed application, the selective recirculation circuit 80 can be depicted in
The selective recirculation circuit 80 can be used in a coarse particle mineral concentration process as shown in
As seen in
The ball-mill feed 21b is directed to a first milling stage 26. The first milling stage 26 may use one or more ball mills for milling. It should be noted that the ball mills in the first milling stage 26 are no longer operated in closed circuit with hydrocyclones in the second classifying stage 28. The ball mills in the first milling stage 26 are operated in open circuit. This eliminates the high circulating loads (200% to 500% of the fresh feed is recirculated to the mill) that characterize normal ball mill operations, and allows for a reduction of between 65% and 80% of size of the ball milling circuit depending on the cut size selected for the pre-classification step.
The ball mill product 27 is classified in a second classifying stage 28, which uses either a screen or a hydrocyclone operating at a D50 cut size of around 1 mm. The coarse particles 29b from the second classifying stage 28 are directed to a first selective recirculation circuit 80a, wherein recovered coarse particles 29c are returned to the first milling stage 26, while unrecovered particles 29d are directed to tails. This is significantly different from the traditional configuration, in which all of the coarse material is returned to the ball mills. The selective recirculation circuit 80a is optimized for coarse particle recovery (because there is very little detachment). As such only those particles with some exposed hydrophobic faces are contained in the recovered particles 29c to be recycled to the ball mills in the first milling stage 26. The use of the selective recirculation circuit 80a greatly reduces the amount of work that must be done in this comminution step.
The classifier fines 29a—now only 15% to 50% of the original feed but containing perhaps 80% to 95% of the sulfide minerals in the original feed—are then directed to a second milling stage 30 for a secondary grinding step. The second milling stage 30 may consist of vertical mills. Vertical mills are up to 35% more efficient than ball mills for processing fine particles (less than 1 mm); hence, they are a better choice for this fine grinding application. Like the previous grinding step carried out in the first milling stage 26, the vertical mills in the second milling stage 30 are configured with a product classifier in a third classifying stage 32 and another selective recirculation circuit 80b operating in selective recirculation configuration. This allows for the rejection of between 70% and 99% of the remaining material while recovering almost all of the reground sulfide minerals.
The vertical mill product 31 is again treated in a third classifying stage 32. As with the second classifying stage 28, the coarser particles 33b from the third classifying stage 32 are directed to a second selective recirculation circuit 80b, wherein recovered coarse particles 33c are returned to the second milling stage 30, while unrecovered particles 33d are directed to tails. The classifier fines 33a are directed to an optional second flotation stage 34 which may use a flash flotation device—a contact cell or other pneumatic flotation cell—to remove the finest, highest-grade particles 35a from the vertical mill product 31, to be directed to a third milling stage 36. The tails 35b from the second flotation stage 34 are then combined with the tails from the thickening stage 24 and directed to a third selective recirculation circuit 80c for scavenging any remaining sulfide particles. The unrecovered particles 35d from the third selective recirculation circuit 80s are directed to tails, while recovered sulfide particles 35c from the third selective recirculation circuit 80a are combined with the concentrates 23a from the contact cells in the first flotation stage 22 and the finest particles 35a from the second flotation stage 34 and directed to the third milling stage 36, where “polishing mills” are used for the final grinding step. The term “polishing mills” refers to the mills that are operating at very fine grinds—typically 30 to 75 microns—and therefore IsaMills or Stirred Media Detritors (SMD) would be more appropriate for this size range. The final product 37 from the third milling stage 36—containing between 1% and 5% of the original plant feed but perhaps 80% to 95% of the desirable sulfide minerals—is then directed to a third flotation stage 38 to be floated a third and final time. The high grade particles 39a is collected as slurry concentrate, while tails 39b are directed to a fourth selective recirculation circuit 80d. The tails 39d of the fourth selective recirculation circuit 80d are recycled to a prior step (the second flotation stage 34). The recovered particles 39c becomes part of the filtered concentrate.
The benefits of using the first classifying stage 20 and various selective recirculation stages, when compared to a traditional process, include:
It should be noted that the selective recirculation circuit 80 can be used in two different ways in the coarse particle mineral concentration process as depicted in the flowsheet 5: One way is to provide a selective recirculation link between a milling stage and an associated classifying stage. The link is configured to receive coarse particles from the classifying stage and to discard the unrecovered particles as tails so that only the covered coarse particles are returned to the milling stage (see
The incorporation of the selective recirculation circuit 80 in coarse particle mineral concentration can be carried out differently. For example,
As shown in the flowsheet 5′, a first regrinding stage 40 is used to replace the second milling stage 30, the third classifying stage 32 and the intermediate selective recirculation circuit 80b in the flowsheet 5 (
It should be noted that each of the selective recirculation circuits used in the process flow contains barren media and stripping solution. The barren media comprises engineered material having molecules with a functional group configured to attract the mineral particles in feed received in the selective recirculation circuits. The engineered material may comprise synthetic bubbles and beads having a hydrophobic surface to provide the molecules. In an embodiment of the present invention, the synthetic bubbles and beads are made of a naturally hydrophobic material. In another embodiment of the present invention, the surface of the synthetic bubbles and beads comprises a coating having a hydrophobic chemical selected from the group consisting of poly(dimethysiloxane), hydrophobically-modified ethyl hydroxyethyl cellulose polysiloxanes, alkylsilane and fluoroalkylsilane.
In a different embodiment, the surface of the synthetic bubbles and beads comprises a coating made of one or more dimethyl siloxane, dimethyl-terminated polydimethylsiloxane and dimethyl methylhydrogen siloxane. In yet another embodiment, the surface of the synthetic bubbles and beads comprises a coating made of a siloxane derivative.
In an embodiment of the present invention, where mineral particles in the selective recirculation circuit comprise recovered particles having exposed hydrophobic surfaces and unrecovered particles, the loading stage is configured to discharge the unrecovered particles in the tails.
As disclosed above, a selective recirculation circuit 80 has a loading stage and a stripping stage. The loading stage comprises a mixer 82 and a washing screen 84, and the stripping stage comprises a mixer 86 and a washing screen 88. The stripping stage is linked a filter 90. In a different configuration, the mixer 82 is equivalent to a media loading stage and the washing screen 84 is equivalent to a loaded media stage. The mixer 86 is equivalent to a media stripping stage and the washing screen 88 is equivalent to a barren media recovery stage. The filter 90 is equivalent to a filtration stage. As such, the processing stages in the flowsheet 5 (
As shown in
The apparatus for extracting concentrates from the tails provided by a flotation stage as shown in
As shown in
The barren media used in mineral separation as disclosed herein can be synthetic bubbles or beads. The term “loaded media” as disclosed herein refers to synthetic bubbles or beads having mineral particles attached thereto. At least the surface of the synthetic bubbles or beads has a layer of polymer functionalized to attract or attach to the value material or mineral particles in the mixture. The term “polymer bubbles or beads”, and the term “synthetic bubbles or beads” are used interchangeably. The term “polymer” in this specification means a large molecule made of many units of the same or similar structure linked together. The unit can be a monomer or an oligomer which forms the basis of, for example, polyamides (nylon), polyesters, polyurethanes, phenol-formaldehyde, urea-formaldehyde, melamine-formaldehyde, polyacetal, polyethylene, polyisobutylene, polyacrylonitrile, poly(vinyl chloride), polystyrene, poly(methyl methacrylates), poly(vinyl acetate), poly(vinylidene chloride), polyisoprene, polybutadiene, polyacrylates, poly(carbonate), phenolic resin, polydimethylsiloxane and other organic or inorganic polymers. The list is not necessarily exhaustive. Thus, the synthetic material can be hard or rigid like plastic or soft and flexible like an elastomer. While the physical properties of the synthetic beads can vary, the surface of the synthetic beads is chemically functionalized to provide a plurality of functional groups to attract or attach to mineral particles. (By way of example, the term “functional group” may be understood to be a group of atoms responsible for the characteristic reactions of a particular compound, including those define the structure of a family of compounds and determine its properties.)
For aiding a person of ordinary skill in the art in understanding various embodiments of the present invention,
In some embodiments of the present invention, a synthetic bead has a solid-phase body made of a synthetic material, such as polymer. The polymer can be rigid or elastomeric. An elastomeric polymer can be polyisoprene or polybutadiene, for example. The synthetic bead 170 has a bead body 180 having a surface comprising a plurality of molecules with one or more functional groups for attracting mineral particles to the surface. A polymer having a functional group to collect mineral particles is referred to as a functionalized polymer. In one embodiment, the entire interior part 182 of the synthetic bead 180 is made of the same functionalized material, as shown in
According to a different embodiment of the present invention, the synthetic bead 170 can be a porous block or take the form of a sponge or foam with multiple segregated gas filled chambers. The combination of air and the synthetic beads or bubbles 170 can be added to traditional naturally aspirated flotation cell.
It should be understood that the term “bead” does not limit the shape of the synthetic bead of the present invention to be spherical, as shown in
It should also be understood that the surface of a synthetic bead, according to the present invention, is not limited to an overall smooth surface as shown in
It should also be noted that the synthetic beads of the present invention can be realized by a different way to achieve the same goal. Namely, it is possible to use a different means to attract the mineral particles to the surface of the synthetic beads. For example, the surface of the polymer beads, shells can be functionalized with a hydrophobic chemical molecule or compound. Alternatively, the surface of beads made of glass, ceramic and metal can be coated with hydrophobic chemical molecules or compounds. Using the coating of glass beads as an example, polysiloxanates can be used to functionalize the glass beads in order to make the synthetic beads. In the pulp slurry, xanthate and hydroxamate collectors can also be added therein for collecting the mineral particles and making the mineral particles hydrophobic. When the synthetic beads are used to collect the mineral particles in the pulp slurry having a pH value around 8-9, it is possible to release the mineral particles on the enriched synthetic beads from the surface of the synthetic beads in an acidic solution, such as a sulfuric acid solution. It is also possible to release the mineral particles carrying with the enriched synthetic beads by sonic agitation, such as ultrasonic waves.
The multiplicity of hollow objects, bodies, elements or structures may include hollow cylinders or spheres, as well as capillary tubes, or some combination thereof. The scope of the invention is not intended to be limited to the type, kind or geometric shape of the hollow object, body, element or structure or the uniformity of the mixture of the same. Each hollow object, body, element or structure may be configured with a dimension so as not to absorb liquid, including water, including where the dimension is in a range of about 20-30 microns. Each hollow object, body, element or structure may be made of glass or a glass-like material, as well as some other suitable material either now known or later developed in the future.
By way of example, the multiplicity of hollow objects, bodies, elements or structures that are received in the mixture may include a number in a range of multiple thousands of bubbles or beads per cubic foot of mixture, although the scope of the invention is not intended to be limited per se to the specific number of bubbles. For instance, a mixture of about three thousand cubic feet may include multiple millions of bubbles or beads, e.g., having a size of about 1 millimeter, in three thousand cubic feet of the mixture.
The multiplicity of hollow objects, bodies, elements or structures may be configured with chemicals applied to prevent migration of liquid into respective cavities, unfilled spaces or holes before the wet concrete mixture cures, including where the chemicals are hydrophobic chemicals.
The one or more bubbles may take the form of a small quantity of gas, including air, that is trapped or maintained in the cavities, unfilled spaces, or holes of the multiplicity of hollow objects, bodies, elements or structures.
The scope of the invention is intended to include the synthetic bubbles or beads shown herein being made from a polymer or polymer-based material, or a silica or silica-based, or a glass or glass-based material.
It should be understood that the sized-based bead or bubble, weight-based bead or bubble, magnetic-based bead or bubble as described in conjunction with
A mineral particle 171 in the slurry, after combined with one or more collector molecules 173, becomes a wetted mineral particle 172. The collector molecule 173 has a functional group 178 attached to the mineral particle 171 and a hydrophobic end or molecular segment 176. The hydrophobic end or molecular segment 176 is attracted to the hydrophobic molecules 179 on the polymer surface 174.
The selective recirculation circuit 80 of the present invention has been shown as a block diagram in
This application is related to a family of applications, including at least the following:
This application is related to a family of nine PCT applications, which were all concurrently filed on 25 May 2012, as follows:
PCT application no. PCT/US12/39528 (Atty docket no. 712-002.356-1), entitled “Flotation separation using lightweight synthetic bubbles and beads;”
PCT application no. PCT/US12/39524 (Atty docket no. 712-002.359-1), entitled “Mineral separation using functionalized polymer membranes;”
PCT application no. PCT/US12/39540 (Atty docket no. 712-002.359-2), entitled “Mineral separation using sized, weighted and magnetized beads;”
PCT application no. PCT/US12/39576 (Atty docket no. 712-002.382), entitled “Synthetic bubbles/beads functionalized with molecules for attracting or attaching to mineral particles of interest;”
PCT application no. PCT/US12/39591 (Atty docket no. 712-002.383), entitled “Method and system for releasing mineral from synthetic bubbles and beads;” PCT application no. PCT/US12/39596 (Atty docket no. 712-002.384), entitled “Synthetic bubbles and beads having hydrophobic surface;”
PCT application no. PCT/US12/39631 (712-2.385//CCS-0092), entitled “Mineral separation using functionalized filters and membranes;
PCT application no. PCT/US12/39655 (Atty docket no. 712-002.386), entitled “Mineral recovery in tailings using functionalized polymers;” and
PCT application no. PCT/US12/39658 (Atty docket no. 712-002.387), entitled “Techniques for transporting synthetic beads or bubbles In a flotation cell or column,”
all of which are incorporated by reference in their entirety.
This application also related to PCT application no. PCT/US13/28303 (Atty docket no. 712-002.377-1/CCS-0081/82), filed 28 Feb. 2013, entitled “Method and system for flotation separation in a magnetically controllable and steerable foam,” which is also hereby incorporated by reference in its entirety.
This application also related to PCT application no. PCT/US13/42202 (Atty docket no. 712-002.389-1/CCS-0086), filed 22 May 2013, entitled “Charged engineered polymer beads/bubbles functionalized with molecules for attracting and attaching to mineral particles of interest for flotation separation,” which is also hereby incorporated by reference in its entirety.
This application also related to PCT application no. PCT/US14/37823 (Atty docket no. 712-002.395-1/CCS-0123), filed 13 May 2014, entitled “Polymer surfaces having siloxane functional group,” which claims benefit to U.S. patent application Ser. No. 14/890,477, filed 11 Nov. 2014, which is also hereby incorporated by reference in its entirety.
This application also related to PCT application no. PCT/US13/73855 (Atty docket no. 712-002.396-1/CCS-0110), filed 9 Dec. 2013, entitled “Techniques for agglomerating mature fine tailing by injecting a polymer in a process flow,” which is also hereby incorporated by reference in its entirety.
This application also related to PCT application no. PCT/US15/33485 (Atty docket no. 712-002.415-1/CCS-0144), filed 1 Jun. 2015, entitled “Mineral recovery using hydrophobic polymer surfaces,” which is also hereby incorporated by reference in its entirety.
This application also related to PCT application no. PCT/US15/66390 (Atty docket no. 712-002.417-1/CCS-0133), filed 17 Dec. 2015, entitled “Transportable modular system for enhanced mineral recovery from tailings lines and deposits,” which is also hereby incorporated by reference in its entirety.
It should be further appreciated that any of the features, characteristics, alternatives or modifications described regarding a particular embodiment herein may also be applied, used, or incorporated with any other embodiment described herein. In addition, it is contemplated that, while the embodiments described herein are useful for homogeneous flows, the embodiments described herein can also be used for dispersive flows having dispersive properties (e.g., stratified flow).
Although the invention has been described and illustrated with respect to exemplary embodiments thereof, the foregoing and various other additions and omissions may be made therein and thereto without departing from the spirit and scope of the present invention.
This application claims benefit to provisional patent application Ser. No. 62/242,545, filed 16 Oct. 2015, which is hereby incorporated by reference in its entirety.
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/US16/57322 | 10/17/2016 | WO | 00 |
Number | Date | Country | |
---|---|---|---|
62242545 | Oct 2015 | US |