Patent Application
20180030572
The disclosure relates generally to precious metal recovery from precious metal-containing materials and particularly to gold recovery from gold-containing materials.
The conventional cyanidation/carbon in pulp process has been the main gold extraction method for decades. While cyanidation is effective for leaching gold from some carbonaceous or complex ores, there are serious environmental concerns associated with the use of cyanide in gold leaching processes. Thiosulfate is among the more successful alternative lixiviants for effective leaching of gold. An example of a thiosulfate leaching process for precious metal-containing materials is shown in U.S. Pat. No. 7,544,232.
Some oxide ores may be refractory in nature. They neither yield sufficient gold leaching in a thiosulfate leach system nor are leached as effectively compared to cyanide. Thiosulfate gold extraction from some oxide ores can be minimal. As oxide ores do not contain sulfides (or have very low levels of sulfide), the refractory nature cannot be mitigated in the same manner as for sulfide ores (e.g., by roasting, bio-oxidation or pressure oxidation).
There is a need for a thiosulfate leaching method to address the refractory nature of certain oxide ores in the thiosulfate leach system.
These and other needs are addressed by the various aspects, embodiments, and configurations of the present disclosure. The disclosure is directed generally to pre-treatment of precious metal-containing materials prior to thiosulfate precious metal leaching.
A pre-treatment process can include the steps of:
The precious metal, for example, can be gold.
Whether or not carbon is removed depends on the particle size of the carbon employed. When coarse carbon is employed, the carbon is typically removed before thiosulfate leaching. When fine carbon is employed, the carbon is typically not removed before thiosulfate leaching.
Finely sized carbon can be contacted with the precious metal-containing material either separately after grinding of the material or before and/or during grinding. In the latter case, the carbon particles can be coarsely sized but are ground to a fine size distribution similar to a size distribution of the ground precious metal-containing material.
Prior to leaching in step (c), the precious metal-containing material can be substantially free of contact with thiosulfate. Stated differently, the slurried precious metal-containing material, before and during step (a), typically includes less than 0.005, more typically no more than about 0.0025, and even more typically no more than about 0.001 molar thiosulfate. In some applications, no thiosulfate or other lixiviant is contacted with the precious metal-containing material before or during pre-treatment in step (a).
The precious metal-containing material can be amenable to cyanide leaching (and therefore is not cyanide refractory) but not to thiosulfate leaching (i.e., the material is a thiosulfate refractory precious metal-containing material). In other words, leaching of precious metals from the precious metal-containing material by cyanide can be more effective than precious metal leaching by thiosulfate. Even when leaching of the precious metal-containing material has similar precious metal recoveries using either cyanide or thiosulfate as the lixiviant, the pretreatment process can enhance further precious metal recovery by thiosulfate. The precious metal-containing material may or may not be concentrated. Generally, the precious metal is in a matrix that is predominantly one or more oxides. By way of example, the precious metal-containing material can contain more oxides than sulfides.
The slurry before pretreatment and the pre-treated slurry can each have a pH about pH 3 or higher (and, in some cases, about pH 7 or higher); an oxidation-reduction potential during pretreatment ranging from about 100 to about 600 mV (Ag/AgCl electrode); and/or a rate of contact of a molecular oxygen-containing gas with the slurry during pretreatment of about 0.10 L O2/L slurry/min or higher.
Generally, a weight ratio of the precious metal-bearing material to carbon ranges from about 50:1 to about 1:0.01 but the amount of carbon employed in any application can depend on the carbon particle size. A weight ratio of the precious metal-bearing material to coarsely sized carbon commonly ranges from about 1:5 to about 1:0.01 and more commonly from about 1:3 to about 1:0.5. A weight ratio of the precious metal-bearing material to finely sized carbon commonly ranges from about 1:1 to about 50:1 and more commonly from about 10:1 to about 30:1.
The pre-treatment process can be carried out under ambient conditions (room temperature and atmospheric pressure) in less than 24 hours. Increasing the process temperature can further improve the gold recovery and/or pretreatment kinetics.
The carbon is normally removed from the pre-treated slurry by screening, which generally requires about 95% or more, and even more commonly about 98% or more of the carbon to be retained on the screen while about 90% or more and more commonly about 95% or more of the precious metal-containing material passes through the screen. The relative mean, median, mode, and P80 particle sizes of the carbon and precious metal-containing material are selected to produce at least these levels of separation.
After carbon separation, the discharge slurry from the pre-treatment process, can be directly advanced to thiosulfate leaching. The carbon-depleted slurry can be contacted with thiosulfate in the substantial absence of pH adjustment and/or slurry density adjustment. As an example, a pH of the carbon-depleted slurry is commonly adjusted by no more than about pH 0.1 and the slurry density by no more than about 5%.
The present disclosure can provide a number of advantages depending on the particular configuration. Pre-treating oxide ores in oxygenated water in the presence of activated carbon or other carbon-based materials can improve significantly the gold recovery by thiosulfate leaching. The process can have a low operating cost and provide a straightforward pre-treatment method for oxide ores to be followed by thiosulfate leaching of gold. Attrition, due to mixing of the slurry, is commonly the only cause for carbon loss and may be minimized by proper engineering of the agitators and reactors. The carbon-based material can be recycled and re-used, thereby decreasing operating costs. Inexpensive air (or more expensive oxygen gas) are the only reagents consumed, thereby making the economics of the process very attractive.
These and other advantages will be apparent from the disclosure of the aspects, embodiments, and configurations contained herein.
As used herein, “at least one”, “one or more”, and “and/or” are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions “at least one of A, B and C”, “at least one of A, B, or C”, “one or more of A, B, and C”, “one or more of A, B, or C” and “A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together. When each one of A, B, and C in the above expressions refers to an element, such as X, Y, and Z, or class of elements, such as X1-Xn, Y1-Ym, and Z1-Zo, the phrase is intended to refer to a single element selected from X, Y, and Z, a combination of elements selected from the same class (e.g., X1 and X2) as well as a combination of elements selected from two or more classes (e.g., Y1 and Z0).
The term “a” or “an” entity refers to one or more of that entity. As such, the terms “a” (or “an”), “one or more” and “at least one” can be used interchangeably herein. It is also to be noted that the terms “comprising”, “including”, and “having” can be used interchangeably.
The term “activated carbon” is a form of carbon processed to be riddled with small, low-volume pores that increase the surface area available for adsorption or chemical reactions. Activated carbon can be granular, extruded, bead, impregnated, and/or polymer coated.
The term “carbon” includes a carbon-containing organic material, such as one or more of activated carbon (or activated charcoal or activated coal), coal (e.g., peat, lignite, sub-bituminous coal, bituminous coal, steam coal, anthracite, and graphite), brown coal, coke, hard carbon derived from coconut shells or elemental carbon, a calcined resin, and mixtures thereof.
The term “means” as used herein shall be given its broadest possible interpretation in accordance with 35 U.S.C., Section 112, Paragraph 6. Accordingly, a claim incorporating the term “means” shall cover all structures, materials, or acts set forth herein, and all of the equivalents thereof. Further, the structures, materials or acts and the equivalents thereof shall include all those described in the summary of the invention, brief description of the drawings, detailed description, abstract, and claims themselves.
The term “precious metal” refers to gold and silver.
A “thiosulfate refractory” precious metal-containing material is a material in which at least part of the precious metal-containing material is naturally resistant to recovery by thiosulfate leaching. The recovery of thiosulfate refractory ores can be increased by pretreatment prior to thiosulfate leaching, or by employing cyanide leaching.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
All percentages and ratios are calculated by total composition weight, unless indicated otherwise.
It should be understood that every maximum numerical limitation given throughout this disclosure is deemed to include each and every lower numerical limitation as an alternative, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this disclosure is deemed to include each and every higher numerical limitation as an alternative, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this disclosure is deemed to include each and every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein. By way of example, the phrase from about 2 to about 4 includes the whole number and/or integer ranges from about 2 to about 3, from about 3 to about 4 and each possible range based on real (e.g., irrational and/or rational) numbers, such as from about 2.1 to about 4.9, from about 2.1 to about 3.4, and so on.
The preceding is a simplified summary of the disclosure to provide an understanding of some aspects of the disclosure. This summary is neither an extensive nor exhaustive overview of the disclosure and its various aspects, embodiments, and configurations. It is intended neither to identify key or critical elements of the disclosure nor to delineate the scope of the disclosure but to present selected concepts of the disclosure in a simplified form as an introduction to the more detailed description presented below. As will be appreciated, other aspects, embodiments, and configurations of the disclosure are possible utilizing, alone or in combination, one or more of the features set forth above or described in detail below. Also, while the disclosure is presented in terms of exemplary embodiments, it should be appreciated that individual aspects of the disclosure can be separately claimed.
The accompanying drawing is incorporated into and forms a part of the specification to illustrate several examples of the present disclosure. This drawing, together with the description, explains the principles of the disclosure. The drawing simply illustrates preferred and alternative examples of how the disclosure can be made and used and is not to be construed as limiting the disclosure to only the illustrated and described examples. Further features and advantages will become apparent from the following, more detailed, description of the various aspects, embodiments, and configurations of the disclosure, as illustrated by the drawings referenced below.
The present disclosure provides a process for pre-treating precious metal-bearing materials. The process can be performed prior to thiosulfate leaching and improve the overall precious metal recovery of thiosulfate refractory precious metal-containing materials. The pre-treatment is done by mixing a slurry containing the precious metal-containing material, water, a carbon-based material, and dissolved molecular oxygen (as the oxidizing reagent) for a predetermined residence time.
The precious metal-bearing material can be an oxide ore, concentrate, tailings, leach residue, calcine, and other precious metal-bearing oxide materials. Typical precious metal-bearing oxide ores and concentrates may contain silicates, phosphates, iron oxides, and hydroxides, and relatively low levels of residual sulfides.
In the pre-treatment process, the precious metal-bearing material is mixed, in a stirred tank, vat, or other suitable reactor, with the carbon-based material, such as activated carbon, and water to form the slurry. Molecular oxygen is typically contacted by sparging the slurry. The molecular oxygen can be supplied by a suitable source, such as air, oxygen-enriched air, or industrially-pure oxygen, with ambient air being preferred. The process can be carried out in any water source, whether raw water or relatively clean process water. Other suitable reactors, such as pulse columns, can be any reactor able to adequately mix carbon, the slurried precious metal-containing material, and gas.
Proper reaction conditions can provide relatively high kinetics. Typically, the pre-treatment process is conducted at atmospheric pressure and temperature, though the use of a higher operating temperature (e.g., typically about 35° C. or higher and more typically about 50° C. or higher) can provide improved reaction kinetics. The pH of the slurry is typically about pH 7 or higher, more typically about pH 8 or higher, and even more typically about pH 9 or higher. The oxidation-reduction potential (“ORP”) of the slurry is typically greater than about 100 mV and more typically greater than about 200 mV and typically less than about 750 mV and more typically less than about 500 mV (Ag/AgCl electrode). The rate of sparging of molecular oxygen through the slurry during pre-treatment typically ranges from about 0.05 to about 5 and more typically from about 0.10 to about 2.5 L O2/L slurry/min. The residence time of the slurry in the mixing vessel typically ranges from more than about 1 hour to about 24 hours, depending on the temperature, dissolved oxygen concentration in solution, and the ore type. Ultimately, the pre-treatment conditions, particularly time and temperature of the pretreatment process, carbon-based material dosage, and rate of oxygen addition, are adjusted to optimize precious metal recovery.
The weight ratio of the carbon-based material to the precious metal-bearing material can vary depending on the requirements of the specific ore, the properties of the carbon-based material itself, and the desired level of precious metal recovery. Typically, for coarsely sized carbon the weight ratio of the precious metal-bearing material to the carbon-based material ranges from about 1:3 to about 1:0.01 and more typically from about 1:3 to about 1:0.1. A more typical weight ratio of the precious metal-containing material to the coarsely sized carbon-based material is about 1:0.5. Typically, for finely sized carbon the weight ratio of the precious metal-bearing material to the carbon-based material commonly ranges from about 1:1 to about 50:1 and more commonly from about 10:1 to about 30:1. A more typical weight ratio of the precious metal-containing material to the finely sized carbon-based material is about 20:1. The carbon-based material is generally not consumed in the pre-treatment process and can be recycled and re-used, with make-up for carbon attrition. Oxygen gas is commonly the only reagent consumed though any other oxidant, including ozone and a peroxygen compound such as hydrogen peroxide, may be employed.
The process can be carried out batch-wise or continuously, the latter being preferred.
After pre-treatment is completed, the carbon-based material can be separated by a suitable technique from the pre-treated precious metal-bearing material in the pre-treated slurry. Separation is generally done in applications using coarsely sized carbon particles but not finely sized carbon particles. Coarsely sized carbon particle separation may be done using differences in particle size. To make this effective, a considerable particle size difference between the coarsely sized particles of the carbon-based material and the more finely sized particles of the precious metal-containing material is normally required. Regardless of the separation technique employed, the coarsely sized carbon-based material may be recycled many times to the pre-treatment process.
Unlike operations using coarsely sized carbon particles, operations using finely sized carbon particles generally do not separate the carbon particles from the particles of the pre-treated precious metal-containing material. After precious metal recovery, the finely sized carbon particles are sent to tailings along with the precious metal barren material.
The pre-treated slurry can then be fed directly to the thiosulfate leaching process. No filtration of the slurry before thiosulfate leaching is generally required. Depending on the ore type, the pre-treated slurry commonly has pH greater than about pH 3, more commonly greater than about pH 7, and even more commonly greater than about pH 8. In some cases, no pH adjustment is required before the pre-treated slurry is contacted with the thiosulfate lixiviant to commence leaching. As will be appreciated, thiosulfate leaching is generally performed at a pH of between about pH 7.5 and pH 10.
The method of the present invention is particularly suitable for pre-treatment of gold-bearing oxide ores and concentrates, prior to thiosulfate leaching, to improve the gold recovery of the thiosulfate leaching process. Direct thiosulfate leaching of some gold-bearing ores can result in poor gold recovery, and pre-treatment before the leaching process can provide a substantial increase in gold recovery.
Referring to
In step 116, fresh and/or recycled carbon-based material 128 and an oxidant 198 (e.g., molecular oxygen/air or enriched air) are contacted with the slurry in the mixer unit. The mixer commonly mixes the various slurry constituents at the ambient temperature and atmospheric pressure in an oxygenated condition. The oxidant 108 can be supplied by the use of air, oxygen-enriched air, or pure oxygen and the non-reacted portion of the oxidant gas may be vented as off-gas 112. The residence time of the slurry in the mixer unit depends on the material type and can range from about 1 hr to about 24 hrs.
In one configuration, the carbon-based material is comminuted with the precious metal-bearing material before pretreatment. In that event, a size distribution of the comminuted precious metal-bearing material can be substantially the same as the size distribution of the comminuted carbon.
In optional step 124, most, or all, of the coarsely sized carbon-based material is removed from (e.g., screened out of) the pre-treated slurry 120 to form a carbon-based material-depleted slurry 136. As noted, removing the coarsely sized carbon-based material by screening in the carbon-based material screen unit (not shown) is particularly effective where there is a considerable size difference between the coarsely sized carbon-based material and other solid phases in the pre-treated slurry 120. Screening can typically remove 95% or more of the coarsely sized carbon from the pre-treated slurry. The screened coarsely sized carbon-based material 128 may be directly recycled back to the pre-treatment step 116 and introduced into the mixer unit, typically without requiring further washing or processing. Acid or basic washing can be performed if required or desired.
The carbon-based material depleted slurry 136 or pre-treated slurry 120, as the case may be, is advanced to precious metal recovery step 140 in which the slurry 136 or 120 is contacted with a thiosulfate lixiviant to leach or dissolve most of the precious metal from the precious metal-bearing material. Dissolved precious metals can be recovered by known techniques, such as resin-in-leach, cementation, precipitation, electrolysis, carbon adsorption, and the like, to form a precious metal product 144.
The pulp density of solids (including the precious metal-bearing material and carbon-based material) in the mixer unit may be designed to achieve the required solid pulp density for thiosulfate leaching with or without the removal of the carbon-based material 128. The carbon-based material-depleted slurry 136 can then be fed directly to thiosulfate leaching, without any filtration or water addition being necessary.
The following examples are provided to illustrate certain aspects, embodiments, and configurations of the disclosure and are not to be construed as limitations on the disclosure, as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.
Three different gold-containing oxide ore samples (P80 of 80 μm), were leached with thiosulfate. The leaching was conducted at pH 8, adjusted with calcium hydroxide, for 24 hours at 50° C. using 0.1M calcium thiosulfate, 50 ppm Cu, 0.5-1 L/min air and 20 mL/L resin. No pre-treatment was carried out on the samples.
A second set of the samples were leached using the cyanide carbon-in-leach pretreatment process. Table 2 summarizes the composition of the ores and the gold recovery results by thiosulfate leaching on each sample. The gold recovery of samples A and B is very low and gold recovery from sample C is approximately 71%.
As shown in Table 1, the ores are fairly similar in nature, and besides, oxygen and silicon contain other compounds:
Table 2 shows the gold recovery by thiosulfate leaching and cyanidation.
As is demonstrated above, gold recovery by thiosulfate is in some cases significantly lower than that achieved by cyanidation.
The same three oxide ore samples from Example 1 were pre-treated with activated carbon in oxygenated water at atmospheric temperature and pressure for 24 hrs. The weight ratio of ore to activated carbon was 2:1 in all three of the tests. Overall solid pulp density (inclusive of ore and activated carbon) of the slurry in the pre-treatment process was about 45%, which resulted, after carbon separation, in solid pulp density of 35% in ore-water slurry. The required oxygen gas was supplied by sparging the slurry via industrially-pure oxygen gas with the sparging rate of 0.5 L O2/L slurry/min. The oxidation-reduction potential (“ORP”) of the slurry during pre-treatment was greater than about 100 mV and less than about 500 mV Ag/AgCl. As will be appreciated, the ORP employed depends on the type of ore and the slurry makeup.
The activated carbon was screened out from the pre-treated slurry, and the slurries leached with thiosulfate as described in Example 1. The gold recovery results of the leaching process are presented below in Table 3:
All three samples show a significant increase in gold recovery by thiosulfate leaching, after use of the carbon pretreatment process. Sample A does not achieve the recovery observed with cyanide leaching. Sample B shows a recovery similar to cyanide leaching. Sample C shows a better recovery than with cyanide leaching
The same tests of Example 2 were repeated on the same ores, however, no carbon was added to the pre-treatment process (i.e., ore was mixed in oxygenated water). The final gold recovery from the samples was very similar to those of Example 1. In other words, pre-treatment without the carbon-based material has no beneficial effect on gold recovery by thiosulfate leaching.
Sample B of Example 2 was pre-treated and leached with the identical processes to those of Example 2, except the pre-treatment was conducted for 6 hrs, instead of 24 hrs. Decreasing the pre-treatment duration from 24 hours to 6 hrs decreased the gold recovery from 71.1% to 60.7%.
Various oxygen containing gases, such as pure oxygen gas, air or oxygen-enriched air, may be used for oxygenating. Ore sample A was pretreated in the same manner described in Example 2 with the exception that oxygen was supplied as (i) pure oxygen gas, and (ii) air. Following pretreatment, thiosulfate leaching was performed as described in Example 1. The gold recovery was 86.2% when the pretreatment was performed with oxygen and 81.4% when it performed with air.
Two samples of gold-bearing oxide ore (>95% oxides, <1% Fe, <2% carbon, and 18.5 ppm Au) were pre-treated with activated carbon in oxygenated water at atmospheric pressure for 24 hrs. The weight ratio of ore to activated carbon was 2:1 in all three of the tests. Overall solid pulp density (inclusive of ore and activated carbon) of the pre-treatment process was about 45%, which resulted in solid pulp density of 35% in ore-water slurry, after carbon separation. One sample was pre-treated at 25° C., and the other at 50° C. The obtained gold recoveries after pre-treatment at 25 and 50° C. were 80.8% and 82.2%, respectively. Gold recovery from the ore, without pre-treatment (i.e., direct thiosulfate leaching of the ore), was only 44.7%.
A series of test were conducted on the same ore sample. A baseline test using standard carbon in leach (CIL) cyanidation techniques yielded a gold extraction of 90.1%. Leaching of the same ore using thiosulfate solution (0.1M calcium thiosulfate, 50 ppm Cu, 0.5-1 L/min air and 20 cc/L resin, pH adjusted with calcium hydroxide) yielded a 57.4% gold recovery after twenty four hours leaching.
In tests three through six, the sample was pretreated in 1 litre of water for 6 hours in the presence of coarse activated carbon and/or finely ground activated carbon. The coarse activated carbon was separated from the ore prior to thiosulfate leaching, while the finely ground carbon remained with the ore during leaching. All carbon addition regimens increase the thiosulfate gold extraction above the baseline of 57.4%. The greatest improvement of gold extraction occurs when the ore is pretreated with coarse activated carbon at an ore to carbon ratio of 2:1 (82.9%). High gold extraction (81.8%) also occurs when the sample is pretreated with finely ground carbon at an ore to carbon ratio of 20:1. This indicates that when finely ground carbon is added, a smaller amount of carbon is required to improve the gold recovery. Fine carbon can be added separately or inter-ground with the ore.
A number of variations and modifications of the disclosure can be used. It would be possible to provide for some features of the disclosure without providing others.
For example, while coarsely sized carbon is preferred to avoid the need to continuously add carbon into the slurry and to allow carbon recycle in a continuous mode of operation, finely sized carbon may be used. When using fine carbon, the carbon can not only be introduced in the pretreatment stage but also added into the grinding stage to grind the precious metal-bearing feed material and carbon together to form a combined precious metal-containing and carbon-containing feed to the pretreatment stage. Using fine carbon in this way can reduce the amount of carbon consumed to less than 1 part carbon and 2 parts precious metal-containing feed material. The oxidant can be added during grinding or thereafter to effect pretreatment.
The present disclosure, in various aspects, embodiments, and configurations, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various aspects, embodiments, configurations, subcombinations, and subsets thereof. Those of skill in the art will understand how to make and use the various aspects, aspects, embodiments, and configurations, after understanding the present disclosure. The present disclosure, in various aspects, embodiments, and configurations, includes providing devices and processes in the absence of items not depicted and/or described herein or in various aspects, embodiments, and configurations hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and\or reducing cost of implementation.
The foregoing discussion of the disclosure has been presented for purposes of illustration and description. The foregoing is not intended to limit the disclosure to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the disclosure are grouped together in one or more, aspects, embodiments, and configurations for the purpose of streamlining the disclosure. The features of the aspects, embodiments, and configurations of the disclosure may be combined in alternate aspects, embodiments, and configurations other than those discussed above. This method of disclosure is not to be interpreted as reflecting an intention that the claimed disclosure requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed aspects, embodiments, and configurations. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the disclosure.
Moreover, though the description of the disclosure has included description of one or more aspects, embodiments, or configurations and certain variations and modifications, other variations, combinations, and modifications are within the scope of the disclosure, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative aspects, embodiments, and configurations to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter.
The present application is a continuation application of U.S. application Ser. No. 14/287,889 with a filing date of May 27, 2014, which claims the benefits of U.S. Provisional Application Ser. No. 61/828,558, filed May 29, 2013, both entitled “Method for Pre-Treatment of Gold-Bearing Oxide Ores”, each of which is incorporated herein by this reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61828558 | May 2013 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14287889 | May 2014 | US |
| Child | 15729961 | US |
