Metal refinement

Information

  • Patent Grant
  • 11319613
  • Patent Number
    11,319,613
  • Date Filed
    Wednesday, August 18, 2021
    3 years ago
  • Date Issued
    Tuesday, May 3, 2022
    2 years ago
  • Inventors
  • Original Assignees
    • Enviro Metals, LLC (Thonotosassa, FL, US)
  • Examiners
    • Swain; Melissa S
Abstract
A method, and systems in which such method may be practiced, allow for the separation of elemental metals from metal alloy. A metal alloy is atomized to form metal alloy particulates. The metal alloy particulates are exposed to an oxidizing agent, such as chlorine gas in the presence of a salt, such as NaCl, an acid, such as HCl, and water. The resulting solution may be filtered to remove particulates, reduced, filtered, reduced, filtered, and so on. In aspects, the method is used to refine gold alloy by oxidation of elemental sponge gold to gold chloride followed by reduction to pure elemental gold.
Description
INTRODUCTION

Precious metals and other compounds are often mixed or melted together to form alloys. For some applications, it is useful to separate the precious metals from the alloy in a refinement process. This precious metal refinement may be used to separate precious metals, such as gold, silver, platinum, palladium, copper, and zinc, from composite alloys.


Current techniques for refining precious metals, however, leave much to be desired. For example, the current gold refinement techniques, such as the Aqua Regia process, the Miller process, and the Wohlwill process use harsh, environmentally damaging chemicals to refine gold, have long batch processing time, and/or are labor-intensive.


The current use of excess chemicals leads to hazardous working conditions and/or negatively impacts the environment. The Aqua Regia process uses a combination of nitric acid and hydrochloric acid to dissolve or separate the metal alloy into its components; the Wholwill process uses a caustic aqueous chloride solution; the Miller process is a pyro-metallurgical process that uses chlorine gas pumped into the molten gold alloy. These chemicals are highly toxic and often result in the production of toxic fumes.


Additionally, current precious metal refinement techniques require long processing times, during which workers may be exposed to these toxic fumes and harsh working conditions. For example, the Aqua Regia process takes eight (8) hours at temperatures around 149° C. A typical Miller processing time is three (3) hours and produces 95% gold. The metal from the Miller process is then put into a Wohlwill cell which is a very slow electrolytic process and requires a tremendous amount of inventory to be tied up in the electrolyte solution.


The use of excess chemicals in these processes erodes machinery and generally prevents such processes from being automated. Thus, it remains desirable to develop systems and methods of precious metal refinement that reduce the use of harsh chemicals and/or automate the tasks.


It is with respect to these and other considerations that the technology provided herein is disclosed. Also, although relatively specific problems have been discussed, it should be understood that the examples and technologies presented herein should not be limited to solving the specific problems identified in the introduction.


SUMMARY

This Summary is provided to introduce a selection of concepts in a simplified form, which concepts are further described below in the Detailed Description. This Summary is not intended to identify key factors or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.


Aspects of the present technology relate to a hydrometallurgical process and apparatuses that use relatively environmentally friendly (e.g., “green chemistry”) reactor technology to refine precious metals and base metals. For example, the technology described herein may be used to refine gold, silver, platinum, palladium, copper, zinc, non-ferrous metals, rare earth metals and other metals from constituent bulk metal alloys. Indeed, the technology described herein may be used to refine gold and other precious metals from scrap jewelry, jewelry sweeps, dory bars, gold ores, and electronic scraps such as phones or computers, to name a few sources. In examples, the technology may be used to dissolve noble metals as well as non-ferrous metals that may exist as a metal chloride. Additionally, as further described herein, aspects of the present technology allow for the recovery of one or more metals aside from the primary metal. For example, platinum recovery, copper as copper oxychloride recovery, or other compounds may be recovered from discharge (e.g., waste) streams of processes used to recover gold from gold alloys.


As further described herein, aspects of the technology exhibit numerous advantages when compared to other precious metal refining methods. For example, under certain conditions, the processing time is reduced by five to ten times than that of other known techniques, chemical usage is reduced by 90% than that of other known techniques, labor is reduced by at least 50% than that of other known techniques, energy needs is decreased 50% than that of other known techniques, and processing space may be reduced to 50% compared to other technologies currently used. Additionally, ambient temperatures of the working environment may be kept at or below 23° C., which may aid in the comfort and safety of precious metal refinement workers. Additionally, for some applications, the present technology may allow for increased purity of the refined metals versus current technology. Additionally, aspects of the technology may use chemicals and techniques that reduce the environmental (e.g., “green chemistry”) impact vis-à-vis other technologies.


One benefit of the technology, for some applications, is that the technology allows for metal tanks, valves, piping, pumps, heat exchangers, sensors, that all may be computerized because of the environment (e.g., temperature, pressure, and chemistries) allows for the use of these metal tanks, valves, piping, pumps, heat exchangers, sensors in electronic communication. The other gold recycling process such as Aqua Regia will oxidize these components relatively quickly. The technology also uses less chemicals, shorter process time and decreased labor intensity along an increased total metal accountability per batch compared to other technologies. The recovery yield may be as much as 99.99% of gold (“Au”), silver (“Ag”, palladium (“Pd”), platinum (“Pt”) and zinc (“Zn”).


In aspects of the technology, a multistage process to refine gold is provided.


Aspects of the technology include a method for refining metal. The method includes providing bulk metal. The bulk metal may comprise one or more elemental metals. The method includes atomizing the bulk metal to form atomized particulate metal alloy, wherein each particulate has a size. The method includes mixing the atomized particulate with a brine solution to form a brine solution suspended with atomized metallic particles. The method also includes mixing the brine solution with an acid to form an acidic brine solution suspended with atomized metallic particles. The method also includes chlorinating the acidic solution suspended with atomized metallic particles to form a chlorinated brine solution with metal-chloride precipitate. The method further includes filtering out the metal-chloride precipitate to form a filtered-chlorinated brine solution. The method also includes reducing the filtered-chlorinated brine solution to form an elemental metal precipitate in a solution. The method also includes filtering out the elemental metal precipitate to form an eluent filtrate. The method also includes reducing the eluent filtrate to form a platinum-group precipitate and solution. The method also includes filtering out the platinum-group precipitate to form a base metal solution. The method also includes reducing the base metal solution to form a base metal precipitate and a water-chloride solution. The method also includes filtering out the base metal precipitate to form a water chloride solution.


In aspects of the technology, the metal chloride precipitate is silver chloride and/or the elemental metal precipitate is gold. The brine solution may comprise 95% water and 5% sodium chloride by weight. The platinum-group precipitate may be ammonium chloroplatinate. The base metal precipitate may be copper oxychloride. The temperature of each of the brine solution chlorinated brine solution, the solution suspended with atomized metallic particles, the chlorinated brine solution with metal-chloride precipitate, the metal-filtrate solution, the filtered-chlorinated brine solution, the eluent filtrate, the platinum-group precipitate and solution, the remaining base metal solution, and the water-chloride solution may be kept below 50° C. The acidic brine solution may comprise 3.5% hydrochloric acid, 4.7% sodium chloride, and 91.8% water by weight.


Aspects of the technology include a method of isolating gold from a gold alloy. The method may comprise: providing a gold alloy comprising gold, silver, platinum, and copper; atomizing the gold alloy to form atomized gold alloy particles; suspending the atomized gold alloy particles in a brine solution, the brine solution comprising sodium chloride and water; precipitating a silver chloride by performing a first stage operation, the first stage operation. The first stage operation may comprise: adding hydrochloric acid to the brine solution to form an acidic brine solution; adding a first surface tension reducer to the acidic brine solution; and bubbling chlorine gas through the acidic brine solution to form a chlorinated brine solution with silver-chloride precipitate. The method may also comprise filtering the silver chloride precipitate in a second stage to form a remaining filtered-chlorinated brine solution; reducing the filtered-chlorinated brine solution in a third stage operation. The third stage operation may comprise: adding a second surface tension reducer to the filtered-chlorinated brine solution: bubbling sulfur dioxide into the filtered-chlorinated brine solution for a period of time to form a metal-filtrate solution, wherein the metal-filtrate comprises elemental gold precipitate; filtering out the elemental gold in a fourth stage operation to form a first filtrate. The method may further comprise treating the first filtrate in a fifth-stage operation. The fifth stage operation may comprise adding ammonium chloride to the first filtrate, adding isopropyl alcohol to the first filtrate, bubbling chlorine through the first filtrate to form a platinum-precipitate solution, wherein the platinum-precipitate solution comprises ammonium chloroplatinate precipitate. The method may further comprise filtering the ammonium chloroplatinate precipitate in a sixth-stage operation to form a base metal solution. The method may further comprise treating a base metal solution in a seventh-stage operation. The seventh-stage operation may comprise adding a base to lower the pH of the base metal solution and cause a base metal compound to precipitate; raising the pH to form a water-chloride solution, wherein the water-chloride solution comprises the base metal precipitate. The method may further comprise filtering the water-chloride solution to collect the base metal precipitate in an eight-stage operation.


In aspects of the technology, the brine solution comprises 5% NaCl in water. The atomized metallic particles may have an average size of 42 microns. Hydrochloric acid (“HCl”) may be added such that the resulting acidic brine solution comprises 10% HCl. The third stage operation may result in at least 99.9% of the gold precipitating out of solution. The period of time may be less than 35 minutes. The first surface tension reliever is isopropyl alcohol. The temperature third-stage operation remains below 52° C.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 illustrates an example system for refining metal.



FIG. 2 illustrates a method for refining metal.



FIG. 3 is a method for atomizing a metal alloy.



FIG. 4 illustrates an example system for oxidizing or reducing metals in solution.



FIG. 5 illustrates a table of example test data for alloy dissolving.



FIG. 6 illustrates a table of example test data for gold precipitation.



FIG. 7 illustrates a table of example test data for platinum group precipitation.



FIG. 8 illustrates a table of example test data for precipitating copper oxychloride.





DETAILED DESCRIPTION

The terminology used in the disclosure herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used in the description of the embodiments of the disclosure and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Also, as used herein, “and/or” refers to and encompasses any and all possible combinations of one or more of the associated listed items. Furthermore, the term “about,” as used herein when referring to a measurable value such as an amount of a compound, amount, dose, time, temperature, and the like, is meant to encompass variations of 20%, 10%, 5%, 1%, 0.5%, or even 0.1% of the specified amount. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Unless otherwise defined, all terms, including technical and scientific terms used in the description, have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.


Aspects of the technology relate to a system to separate relatively pure metal from metal alloys. For example, gold, copper, platinum, palladium, zinc, silver, and other metals may be separated from gold alloys using the system and methods described herein. Additionally, rare earth metals and other non-ferrous metals may be separated from alloys using the systems and methods described herein. For some applications, metals that form chlorides are selected for separation using the techniques described herein.



FIG. 1 illustrates an example system 100 for refining metal. As illustrated, FIG. 1 includes a furnace 101. Furnace 101 may heat an alloy up to a sufficient temperature for melting the alloy. Example alloys include bulk metallic material such as scrap jewelry, jewelry sweeps, dory bars, gold ores, and metal portions of electronic scraps. Where the alloy includes gold, the temperature of the metal alloy may be raised to above 1093° C. In other embodiments, higher temperatures may be obtained where the alloy includes platinum or other metals. Heating of the metal alloy may occur using a variety of known techniques and furnaces, or techniques and furnaces later developed appropriate for heating metal alloys.


A furnace conduit 105 directs flow of molten metal alloy from the furnace 101 to atomization chamber 103. The atomization chamber 103 atomizes the molten metal from the furnace 101. Atomization may occur through a variety of means, such as high-pressure water atomization described below. Examples of high-pressure water atomization are provided with further details herein. In aspects of the technology, the atomization chamber produces a mixture of atomized metallic material in a 5% sodium chloride (“NaCl”)/95% water (“H2O”) solution by weight. In examples, the atomized metallic material has a diameter of about 44 microns (“μm”), about 48 about 52 about 56 about 60 about 64 about 68 about 72 and/or about 75 In some examples, the atomized metallic material is passed through a mesh filter of about 200 mesh, about 230 mesh, about 270 mesh, about 300 mesh, and/or about 325 mesh before proceeding to a metal oxidation reactor system 106. For example, a NaCl/H2O solution may have atomized metallic material suspended in solution, and the solution may first pass through the mesh filter prior to proceeding to the metal oxidation reactor system 106.



FIG. 1 includes a reactor inlet conduit 102. Reactor inlet conduit 102 serves to direct atomized metallic material, suspended in a salt-water solution in examples, produced in the atomization chamber to the metal oxidation reactor system 106. In additional/alternative aspects of the technology, atomized gold metal alloy is derived from other sources, such as gold metal alloy recyclers, and that atomized gold metal alloy is added to metal oxidation reactor system 106 with salt-water solution, in examples. It will be appreciated that the metal oxidation reactor system 106 may be similar to or the same as the reactor system described with reference to FIG. 4. In an example, metal oxidation reactor system 106 receives the atomized metallic material suspended in the water NaCl solution (also referred to herein as a brine solution). In examples, the concentration of salt is about 3%, about 4%, about 5%, about 6%, and about 7% by weight. In examples, metal oxidation reactor system 106 includes one or more vessels in which oxidization of the atomized metallic material may occur.


In examples, the metal oxidation reactor system 106 may include various means (such as inlets to one or more vessels/reactors) to adjust the brine solution. For example, more water or NaCl may be added to reach a targeted salt concentration. Additionally, other reagents may be added. In a particular example, and acid, such as hydrochloric acid is added to form an acidic brine solution. For example, a solution may comprise about 91.8% water, about 4.7% salt, and about 3.5% HCl by weight. Hydrochloric acid may be added using 33% aqueous hydrochloric acid. In other examples the HCl may be about 1.5%, 2.5%, 4.5%, or 5.5% and the NaCl may be about 3%, 6%, 8%, or 10% by weight. Additionally, the atomized metallic material may be agitated during processing by the metal oxidation reactor system 106 using a variety of means, such as a mechanical agitator or mechanical circulation. In examples, an oxidizing reagent is introduced to the oxidation reactor system 106. For example, chlorine gas may be diffused within the water/salt solution using a variety of means, including a Venturi system or bubble diffuser, thus facilitating reaction with the suspended atomized metallic particles disposed within such brine solution. In some applications, this chemical reaction generates HCl that increases the concentration of HCl as the reaction continues. Additionally, other agents, such as quenching agents, surface tension relievers, surfactants, water, and other reagents, may also be introduced in the metal oxidation reactor system 106. Further details regarding one example of a suitable reactor system are provided with reference to FIG. 4.


The metal oxidation reactor system 106 may be used in a batch process. For example, acidic brine solution may be exposed to the oxidizing agent for a predetermined period of time based on the size, mass, and/or composition of the atomized metallic particles in the acidic brine solution. This may allow for the atomized metallic material to oxidize fully or almost fully. The size of the atomized metallic particle may be selected based to reduce processing time. For example, a smaller size such as 40-45 microns may be selected using a mesh screen. The resulting solution, referred to herein in some places as an oxidized brine solution, will include various reduced metal compounds (e.g., chlorinated metals). For some starting materials, the oxidization of the atomized metallic material will form a precipitate metal, such as silver chloride, which may be filtered out of the oxidized brine solution using one or more filters, such as first filter 120.


As illustrated, first filter conduit 118 directs the flow of the oxidized brine solution to a first filter 120. In aspects of the technology, the first filter 120 is sized and shaped to remove one or more precipitate chlorinated metals, such as silver chloride, from the oxidized brine solution. In examples, the first filter is a centrifugal filter or other mechanical filter capable of removing silver chloride precipitate or other precipitate from the oxidized brine solution received from first filter conduit 118.


Silver chloride or other filtrate/sediment may be directed out of the filter using a discharge conduit 112. In aspects of the technology, the filtrations system comprises a centrifugal filtration system and/or cartridge type systems. The remaining filtrate solution may be directed to precipitation reactor system 122 via precipitation reactor conduit 121.


In examples, precipitation reactor system 122 serves as a vessel in which reduction of a chlorinated or oxidized metal may occur. For example, precipitation reactor system 122 may adjust the salt or water in the remaining filtrate by adding more water or NaCl (or other salt) to the filtrate solution to form a filtrate brine solution. Further, the filtrate brine solution may be agitated during processing by the precipitation reactor system 122 using a variety of means, such as a mechanical agitator or pump circulation. In examples, a reducing reagent is introduced to the oxidation reactor system 122. For example, sulfur dioxide gas may be exposed to the filtrate solution using a Venturi system. Additionally, other agents, such as quenching agents, surfactants, surface tension relievers, water, and other reagents may also be introduced in the precipitation reactor 122. Further details regarding one example of a suitable reactor system are provided with reference to FIG. 4. Precipitation of a noble metal, such as gold, may take place as the noble metal is reduced to form an elemental metal precipitate. The resulting precipitate solution may then be transferred to a second filter 132 through a second filter conduit 124.


Elemental metal, such as gold, may be separated from the precipitate solution in a second filter 132. In aspects of the technology, the second filter 132 comprises a centrifugal filtration system and/or cartridge-type systems.


Elemental gold or other precipitate/sediment may be directed out of the second filter 132 using a second discharge conduit 133. The remaining second filtrate solution is directed to secondary precipitation reactor system 136 via secondary precipitation reactor conduit 126 as illustrated.


In examples, secondary precipitation reactor system 136 serves as a vessel in which further reduction of a chlorinated or oxidized metal may occur. For example, secondary precipitation reactor system 136 may adjust the second filtrate solution by adding more water or NaCl (or other salt) to the second filtrate solution. Further, the second filtrate solution may be agitated during processing by the secondary precipitation reactor system 136 using a variety of means, such as a mechanical agitator or pump circulation. In examples, a reagent is introduced to the secondary precipitation reactor system 136. For example, ammonium chloride and/or chlorine gas may be exposed to the second filtrate solution in the secondary precipitation reactor system through a Venturi or other means. Additionally, other agents, such as quenching agents, surface tension relievers, surfactants, water, and other reagents, may also be introduced in the secondary precipitation reactor 136. Further details regarding one example of a suitable reactor system are provided with reference to FIG. 4. Precipitation of other metals or metal composites, such as platinum and palladium, rhodium and ruthenium chloride, may result. The resulting second precipitate solution may then be transferred to a third filter 140 through a third filter conduit 138.


As illustrated, third filter conduit 138 directs the flow of the second precipitate solution to a third filter 140. In aspects of the technology, the third filter 140 is sized and shaped to remove one or more precipitate chlorinated metals, such as ammonium chloroplatinate, from the second precipitate solution. In examples, the third filter 140 is a centrifugal filter or other mechanical filter capable of removing ammonium chloroplatinate precipitate or other precipitate from the second precipitate solution received from third filter conduit 138. Ammonium chloroplatinate or other precipitate/sediment may be directed out of the third filter 140 using a third discharge conduit 141. The remaining liquid forms a third filtrate solution, which may flow to base metal precipitation reactor system 148 via base metal reactor conduit 144.


In examples, base metal precipitation reactor system 148 serves as a vessel in which further reduction of a chlorinated or oxidized metal may occur. For example, base metals such as copper oxychloride, may be precipitated out in base metal precipitator system 148. Further, adjustment of the third filtrate solution may occur by adding more water or NaCl (or other salt) to the third filtrate solution. Additionally, the third filtrate solution may be agitated during processing in the base metal reactor system 148 using a variety of means, such as a mechanical agitator or recirculating pump system. In examples, reducing agents are introduced to the base metal reactor system 148. For example, sodium hydroxide may be added through a Venturi or other means. Additionally, other agents, such as quenching agents, surfactants, surface tension relievers, water, and other reagents such as hydrochloric acid may also be introduced in the base precipitation system 148. Further details regarding one example of a suitable reactor systems are provided with reference to FIG. 4. Precipitation of a base metal, such as copper oxychloride, may result. The resulting forth precipitate solution may then be transferred to a fourth filter 150 through a third filter conduit 152.


As illustrated, fourth filter conduit 152 directs the flow of the fourth precipitate solution to a fourth filter 150. In aspects of the technology, the fourth filter 150 is sized and shaped to remove one or more precipitate chlorinated metals, such as copper oxychloride, zinc chloride, etc., from the second precipitate solution. In examples, the fourth filter 150 is a centrifugal filter or other mechanical filter capable of removing copper oxychloride precipitate or other precipitate from the fourth precipitate solution received. Copper oxychloride or other precipitate/sediment may be directed out of the fourth filter 150 using a fourth discharge conduit 154.


Various scrubbing systems may be in fluidic communication with scrubbing system 107. As illustrated, scrubbing systems 107 are in fluidic communication with first filter 120, second filter 132, third filter 140, and fourth filter 150. The scrubbing systems may scrub the waste gas coming off the systems during a filtering operation, such as the filtering operations described herein. The scrubbing systems 107 may use Cl2 or SO2 gas scrubbers along with ruptured disk valves, pressure relief valves, gas detectors, small fume hoods and emergency alarms or other devices now known or later developed. The scrubber vacuum lines may be connected to all the tanks as well as a fresh air supply. In examples, gases are kept at or near atmospheric pressure for safety reasons. In a particular example, all the gases drawn to the Venturi system (as described further with reference to FIG. 4) are under vacuum. Other safety means may be employed, such as a computerized monitoring system.


It will be appreciated that the conduits 102, 118, 121, 124, 126, 138, 144, and 152 may be any conduit suitable for the transfer of liquid solution containing sediment. For example, pipes, sluices, and channels may be employed.



FIG. 2 is an example method 200 to refine metal. FIG. 2 begins with atomize operation 202, in which a starting bulk metal, such as gold alloy is atomized. In aspects of the technology, the bulk metal may comprise one or more of scrap jewelry, jewelry sweeps, dory bars, gold ores, and electronic scraps. Bulk metal may be atomized using high-pressure water atomization, such as the water pressure atomization described with reference to FIG. 1. Operation 202 results in atomized metallic particles suspended in a solution. In aspects, the solution is a brine solution having about 5% NaCl/95% water solution by weight. In an example, the atomized metallic particles have a size between about 44 μm to 75 μm. In another example, metallic particles are filtered out using a mesh to select for a particular size, such as no greater than 44 μm.


Method 200 then proceeds to oxidization operation 204. At oxidation operation 204, the solution suspended with atomized metallic particles may be pumped into a vessel, such as the oxidation reactor. The oxidation reactor may be part of a metal oxidation reactor system described with references to FIG. 1. The brine solution may be acidified by adding an acid, such as hydrochloric acid to the system to form an acidic brine solution. In an example, an acidic brine solution comprises about 3.5 HCl/4.7% NaCl in water by weight. During operation 204, the solution may be kept between about 5.5° C. and 30° C.


In an example, chlorine gas is used to at least partially oxidize the atomized metallic particles suspended in the acidic brine solution. For example, the micro-bubble mechanism or venturi system may bubble in chlorine gas to the acidic brine solution. As a non-limiting example, an amount of chlorine gas may be bubbled into the acidic brine solution. The amount of chlorine gas may be 75% of the mass of the atomized metal suspended in the acidic brine solution. This forms a chlorinated brine solution.


In aspects of the technology, the micro-bubbled chlorine gas oxidizes the atomized metal. For example, where the atomized metallic particles include a gold alloy comprising gold, palladium, platinum, copper, silver, and zinc, the use of chlorine gas may result in the formation of gold chloride (AuCl3), palladium chloride (PdCl2), platinum chloride (PtCl2), copper chloride (CuCl2 or CuCl) zinc chloride (ZnCl2) and silver chloride (AgCl) as provided by reaction 1 below:




embedded image



where M is a metal, Cl2 is chlorine gas, and MCln represents a metal chloride. Each of the gold chloride, palladium chloride, copper chloride, zinc chloride and platinum chloride may dissolve in solution. Some or all of the silver chloride may not dissolve, and instead form a precipitate. In aspects of the technology, the ratio of water, HCl, NaCl, and atomized metal is controlled to promote the precipitation of silver chloride from solution.


In aspects, the temperature of the chlorinated brine solution is maintained at about 29° C., about 31° C., about 33° C., about 35° C., about 37° C., about 39° C., about 42° C., about 44° C., about 45° C., about 47° C., about 49° C., and about 51° C. during operation 204. In some aspects of the technology, temperature ranging from 5.5-31° C. In aspects of the technology, a surface tension reliever, such as isopropanol, may be added. This may promote the chlorine gas staying in solution, which results in a shorter reaction time for some applications. Operation 204 produces a chlorinated brine solution with metal-chloride precipitate.


Method 200 then proceeds to filter metal-chloride precipitate operation 206. In operation 206, the chlorinated brine solution with metal-chloride precipitate produced in operation 204 is directed towards a filtration system, such as the first filter described with reference to FIG. 1. Metal chloride, such as silver chloride, may be filtered using mechanical means. For example, silver chloride may be filtrated through a centrifugal filter, then a final cartridge (0.5-micron filter), and a rinse water cycle. After filtration, the filtrate containing the gold and other precious metals is transferred to another processing tank for further processing. The silver chloride may be collected for further processing. In aspects of the technology, substantially all the metal precipitate is removed from the chlorinated brine solution. After substantially all the metal precipitate is removed, the remaining filtered-chlorinated brine solution is passed to operation 208.


In operation 208, the remaining filtered-chlorinated brine solution is reduced. In operation 208, one or more of the metal chlorides is reduced using a reducing agent to form an elemental metal precipitate. In aspects of the technology, a precipitation reactor system such as the precipitation reactor system described with reference to FIG. 1 is used. For example, gold chloride may be reduced using sulfur dioxide to produce elemental gold using a precipitation reactor system. A surface tension reducer, such as isopropyl alcohol, may added. In some aspects of the technology, a microbubble diffuser or Venturi system may be used to diffuse sulfur dioxide gas into the filtered-chlorinated brine solution to reduce gold chloride to form sponge gold. During operation 208, the solution may be kept between about 37° C. and 50° C. In some aspects of the technology, the temperature may be kept below 60° C. This results in elemental metal, such as gold, precipitating out of the filtered-chlorinated brine solution to form a metal-filtrate solution. In embodiments where the filtered-chlorinated brine solution includes AuCl3, the following reaction occurs when treated with sulfur dioxide under appropriate conditions:

3SO2+2AuCl3+3H2O→3SO3+6HCl+2Au


Operation 200 then proceeds to filter elemental metal operation 210. In aspects of the technology, and elemental metal, such as gold from a gold-filtrate solution, is filtered. Filtering may occur using a filter similar to or the same as the second filter described with reference to FIG. 1. The elemental metal may be gathered by filtration and washed (rinse). During operation 208, the elemental metal may be washed. For example, a wash may comprise hydrochloric acid, followed by water, then followed by ammonium hydroxide rinse, then deionized water rinse may be added. The eluent filtrate, the first filtrate containing the other precious metals may then be treated in other operations, such as 212.


Method 200 then proceeds to treat eluate filtrate operation 212. Treating eluate filtrate solution may occur using the same or similar systems described above with reference to the secondary precipitation reactor system. In aspects of the technology, the eluent filtrate (or first filtrate) may contain platinum and palladium in solution, which then may be treated to precipitate out the platinum and palladium group metals separately. For example, the eluent filtrate may be saturated with ammonium chloride. Next, chlorine gas may be bubbled into the solution using a microbubble device or Venturi systems. In an example, a surface tension reliever, such as isopropyl alcohol, is added to facilitate the absorption of the chlorine gas into the solution. In examples, during operation 212, the solution may be kept between about 27° C. to 30° C. In some aspects of the technology, the temperature may be kept below 100° C. In aspects of the technology, operation 212 results ammonium chloroplatinate and palladium-compound precipitate to precipitate, and the resulting solution may be further filtered at operation 214.


Method 200 then proceeds to operation 214, where the resulting ammonium chloroplatinate and palladium-compound precipitate and solution are filtered. Filtration may occur using the same or similar systems as those described with reference to the third filter above. For example, cartridge filters may be used. Where cartridge filters are used, the cartridge filters may be washed with saturated solution of ammonium chloride. Operation 216 separates at least a portion of the ammonium chloroplatinate and palladium-compound precipitate from the remaining base metal solution. The ammonium chloroplatinate and palladium-compound precipitate may be gathered and further processed. The base metal solution then proceeds to operation 216.


Method 200 then proceeds to precipitate base metal operation 216. Base metal operation 218 may be performed using the base metal precipitator systems described above. In operation 218, the base metals compounds, such as copper oxychloride and zinc chloride, are precipitated. In examples, base metal operation comprises two parts. A base such as sodium hydroxide is added to raise the pH of the base metal solution. In aspects of the technology, the pH is raised from about 1 to about 13. In aspects, this causes the base metal compound, such as copper oxychloride or Zinc Chloride, to precipitate. In a second stage, an acid such as hydrochloric acid is added to lower the pH to about 7. During operation 216, the solution may be kept between about 27° C. and 49° C. This forms a water-chloride solution. The water-chloride solution may be further processed in operation 218.


Method 200 then proceeds to filter water-chloride solution in operation 218. In aspects of the technology, the water-chloride solution is filtered using a mechanical separator, such as a centrifuge. Indeed, method 200 may be performed using the same or similar filters as those described with reference to the fourth filter above. For example, a copper oxychloride may be filtered out using a computer-controlled centrifugal filter. The resulting filtrate comprises mainly water, in examples. In aspects of the technology, this wastewater may be recycled for use in one or more stages discussed herein or repurposed for other suitable uses.


Method 200 may be described as a batch process. It will be appreciated, however, that method 200 may be performed as a semi-continuous or a continuous process.



FIG. 3 is a method 300 to atomize metal using high-pressure water atomization. Method 300 begins with provide bulk metal operation 302. Bulk metal may come from a variety of sources, such as scrap jewelry, jewelry sweeps, dory bars, gold ores, and electronic scraps. In aspects of the technology, the bulk metal may have a composition as provided in the following table:

















Gold %
Silver %
Copper %
Zinc %
Platinum %
Palladium %




















24.99
10
55
10
Trace
Trace


75
10
10
4.99
Trace
Trace


90
5
4.99
0
Trace
Trace









Method 300 then proceeds to melt bulk metal operation 304. In operation 304, the bulk metal may be heated to substantially melt the bulk metal. For example, an induction furnace may be used to heat the metal up to the melting point of the bulk metal where it is capable of flowing. For example, an induction furnace may heat the bulk metal to a temperature of about 1093° C.


Method 300 then proceeds to atomize operation 306. In operation 306, the molten, free-flowing gold is poured into an atomization chamber. In some examples, the atomization chamber comprises one or more streams of high-pressure water. Those high-pressure streams may be directed at the stream of molten metal, such as gold. In aspects of the technology, the high-pressure water is brine water, comprised of 95% water and 5% NaCl by weight. In some examples, the brine solution may be chilled to about −2° C., filtered, and compressed to a high-pressure (about 5,000 Pounds per square inch, in some aspects of the technology). One or more jets may then spray the chilled brine solution on the molten metal to form fine metal particulate solution.


Method 300 then proceeds to brine operation 308. In brine operation 308, the metal particulate solution may be adjusted with additional salt (such as NaCl), water, and/or and acid. Further, one or more reagents, such as hydrochloric acid, may be added. In a particular example, the solution may be adjusted to target a brine comprising 3.5% HCl/4.7% NaCl in water by weight. This solution may be provided to a metal-oxidation system, such as the metal oxidation system described with reference to FIG. 1.



FIG. 4 illustrates a system 400 for separating metal alloys. As illustrated, FIG. 4 includes a tank 402, a circulation conduit 404 that couples a pump 406, a heat exchanger 418, and a Venturi system 410 to the tank 402 such that each are in fluidic communication.


As illustrated, the tank 402 includes an inlet 412, a side outlet 414, and a bottom inlet/outlet 416 in fluidic communication with the Venturi system 410, pump 406, the heat exchanger 418 via the circulation conduit to circulation conduit 404. Tank inlet 412 may receive various solutions and materials and reagents, such as the HCl, water, brine, or salt, such as NaCl.


A pump 406 may circulate various solutions from the side outlet 414 to the bottom inlet 416 using the circulation conduit 404. The solution may be pumped through a centrifugal pump at 450 gallons per hour.


As illustrated, a heat exchanger 418 and a Venturi 410 are integrated within the circulation conduit 404. The heat exchanger 418 may be a water chiller with feed water of about 5° C. to about 10° C. This may allow a solution passing through the circulation conduit (and/or within the tank 402) to be kept below 38° C.


Proximate to one end 420 of a Venturi 410 is a fluid inlet 422, which is in fluidic communication with a fluid reserve tank 424. The fluid reserve tank 424 may comprise a gas, such as chlorine or sulfur dioxide, or a liquid, such as sodium hydroxide.


The system 400 may additionally include other valves, temperature, pressure, flowrate and other monitors, and other various computerized control systems without departing from the scope of the innovative technologies described herein.


EXAMPLES

In a first example, a metal alloy comprising 50% gold, 7% silver, 36% copper, and 7% zinc was formed from pure elemental metals. The metal alloy was melted by heating the metal in a crucible. The molten metal was poured into an atomizer having high pressure water jets similar to the atomizers described herein. The resulting gold metal alloy powder was passed through a 320 mesh to verify the size of the particles and remove any particles of larger size. The resulting mesh powder was placed into a 900 mL H2O, 100 mL 10% HCl, 50 grams NaCl, 0.5 mL isopropyl alcohol solution. The ratio of mesh powder was 8 oz of mesh powder per liter of the solution. The solution was placed in a reactor system, similar to the reactor system described with reference to FIG. 4. Chlorine gas (Cl2) was pumped into the solution for 50 minutes at a rate of 0.0778 standard cubic feet per minute (scfm) using a Venturi system. At minute 50, a millivolt reading stabilized at 1140, where it did not change for the remaining 10 minutes of the test. This reading indicates that substantially all of the metal was chlorinated.


In a second example, a metal alloy comprising 50% gold, 7% silver, 36% copper, and 7% zinc formed from pure elemental metals via melting. The resulting metal alloy was melted by heating the metal in a crucible. The molten metal was poured into an atomizer having high-pressure water jets similar to the atomizers described herein. The resulting gold metal alloy powder was passed through a 100 to 150 mesh to verify the size of the particles and remove any particles of larger size. The resulting mesh powder was placed into a 900 mL H2O, 100 mL 10% HCl, 50 grams NaCl, 0.5 mL isopropyl alcohol solution. The ratio of mesh powder was 8 oz of mesh powder per liter of the solution. The solution was placed in a reactor system, similar to the reactor system described with reference to FIG. 4. Chlorine gas (Cl2) was pumped into the solution at a rate of 0.0778 standard cubic feet per minute (scfm) using a Venturi system for one hour and five minutes. During that time, a millivolt reading increased from 71 to 467 MV/orp. A millivolt reading read 1117 millivolts at one hour and 10 minutes. This reading indicates that substantially all of the metal was chlorinated.


In a third example, a metal alloy comprising 50% gold, 7% silver, 36% copper, and 7% zinc formed from pure elemental metals via melting. The resulting metal alloy was melted by heating the metal in a crucible. The molten metal was poured into a liquid atomizer having high-pressure water jets similar to the atomizers described herein. The resulting gold metal alloy powder was passed through a 150 to 200 mesh screen to verify the size of the particles and remove any particles of larger size. The resulting mesh powder was placed into a 900 ml H2O, 100 ml HCl, 50 grams NaCl, 0.5 ml isopropyl alcohol solution. The ratio of mesh powder was 8 oz of mesh powder per liter of the solution. The solution was placed in a reactor system, similar to the reactor system described with reference to FIG. 4. A volume of 41.6 cubic feet per minute of Cl2 was pumped into the solution for one hour. During that time, a millivolt reading increased from 330 to 1118 MV/orp, indicating a substantially reacted solution.


Example 2 has seven stages.


Stage 1: Atomization.


Gold alloy (comprising 50% gold, 7% silver, 36% copper, 18% zinc) was heated until it forms a flowing melt. The melted gold alloy was fed into an atomizer through a crucible with a hole (3.175 mm) at the bottom of the crucible leading into a tank with high pressure jets. A 5% NaCl solution (at 7° C.) was sprayed into the atomizer tank at high pressure (5,000 psi). When the melted gold drops into the atomizer tank, the gold solidified and was chopped into a fine powder by the action of the high-pressure 5% NaCl solution being sprayed by the spray jet. The powder was collected by filtration and dried. This atomized material was used for the gold dissolving processing in stage two. This system may be computerized.


Stage 2: Converting Gold Metal Alloy to Metal Chloride.

Au+Ag+Cu+Zn+6Cl2+2H20→AuCl3+AgCl+CuCl2+ZnCl2+2HCl+2ClOH  Chemical Equation


To a reaction vessel (equipped with pump, heat exchanger, and Venturi to draw the chlorine gas into the reactor under vacuum, a thermometer, cooling bath and a millivoltmeter) atomized gold metal alloy (256 g, −320 mesh size) was added. The atomized metal alloy scrap metal comprised 50% gold (128.5 g, 0.652 mole); 7% silver (18 g, 0.167 mole); 36% copper (92 g, 1.448 mole) and 7% Zinc (18 g, 0.275 mole). Hydrochloric acid (33%, 100 mL), water (900 mL), sodium chloride (50 g) and isopropyl alcohol (0.5 mL) was added to the reaction vessel before chlorine gas was added using a Venturi system. At the beginning of the reaction, the temperature was 5.5° C. and a cooling bath temperature was 2° C. while the millivoltmeter had a reading of 230 millivolt. Chlorine gas was added to the reaction vessel under vacuum and at a rate of 0.0778 standard cubic feet per minute (scfm) using a Venturi system. This produced hydrochloric acid during processing. After one minute the chlorine gas flow was 0.0778 scfm, the temperature was 5.5° C. and the voltage was 385 millivolts. The reaction color went from colorless to a very light green during the first 5 minute of chlorine gas addition. The reaction mixture was monitored for 30 minutes. When the voltmeter got to a high of 1,140 millivolts and the temperature was 32° C. after 15 minutes, the reaction was completed. The end temperature was 13° C. The ending color was a very dark green. After the 30 minutes time period, the chlorine gas was turned off and hydrogen peroxide was introduced to mitigate any excess chlorine gas that was in the head space of the reactor. At this stage gold chloride, copper chloride, and zinc chloride where in solution while silver chloride precipitated out of solution. This system may be computerized.


Stage 3: Silver Chloride from Silver Chloride Isolation by Filtration


The dark green solution produced in stage 2 was filtered to collect silver chloride precipitate. The silver chloride precipitate was collected by a filtration process. A Buchner funnel with filter paper (0.2 micron) or polypropylene filter was used in the Buchner funnel for the silver chloride filtration process. Once the silver chloride precipitate was isolated in the Buchner funnel, the silver chloride precipitate was washed with water (3×100 mL distilled water) and then dried to a constant weight. The isolated dried silver chloride weight was 22.32 g which is a silver-colored solid (0.5 microns). Inductive coupled plasma (ICP) analysis indicated that the solid was pure silver chloride. The remaining filtrate and washings were combined into a single solution. The solution was diluted with distilled water to meet 1.5 L for the next processing stage of the gold chloride reduction to gold metal. This system may be computerized.


Stage 4: Gold Isolation.

3SO2+AuCl3+3H2O→3SO3+6HCl+2Au  Chemical Equation


The filtrate produced in stage 3 (1.5 L of solution), which contained the metal chloride (gold chloride, copper chloride, and zinc chloride), was added to a reaction vessel which was equipped with a pump, heat exchanger, a thermometer, cooling bath, a millivoltmeter and a gas Venturi system. The gold chloride solution was heated to 34° C. and hydrochloric acid was added to reach a 3.5% HCl solution by weight. Isopropyl alcohol (1.0 mL) was added to the solution which is at a temperature of about 34° C. Sulfur dioxide gas is added at a rate of 0.0696 standard cubic feet per minute (scfm) for 30 minutes. During the 30 minutes of sulfur dioxide addition, the color of the solution changed from dark green to a brown-gold color. The temperature increases up to 52° C., and the voltage changed from 755 to 395 millivolts and the gold metal precipitated from the solution. Addition of sulfur dioxide was stopped. Elemental gold precipitated out of solution. This system may be computerized.


Stage 5. Filtration.


The resulting gold sponge of stage 4 was isolated using a filtration process. A Buchner funnel was used to filter the gold precipitate. The precipitate filtrate, which was gold sponge, was washed with water (3×300 distilled water) and dried to a constant weight. Inductive coupled plasma (ICP) analysis indicated that the solid was pure gold metal. A total of 128 g (99.6% yield) of gold metal with a purity of 99.9999% as determined by ICP analysis. An in-process sample of the solution was run through the ICP after filtering to determine that we had recovered 100% of the gold. The filtrate and washings were combined and utilized in the next stage for copper and Zinc isolation. This system may be computerized.


Stage 6. Base Metal Precipitation.


To a reaction vessel which is equipped with pump, a heat exchange, a thermometer, a gas venturi system and a millivoltmeter was added the filtrate and washing of stage 5, which comprised a solution (4.0 L) of copper oxychloride (171 g) and zinc chloride (18 g). Sodium hydroxide (80 mL of a 50% solution) was added using the Venturi to increase the pH from 1 to 13. The temperature of the solution was maintained at 37° C. At the high pH level, the copper oxychloride and zinc chloride precipitated over 30 minutes. After the 30 minute time period, it was observed that the precipitation was complete. Next, the pH was decreased from 13 to 7 with hydrochloric acid (50 mL, HCl (33%)) reducing the solution to a 5% NaCl solution (water and sodium chloride). This system may be computerized.


Stage 7. Filtration.


The remaining solution from stage 6 included copper oxychloride. The copper oxychloride was isolated by filtration at pH 7, washed and dried to constant weight. The combined filtrate which is at pH 7 (water) is utilized for stage two processing. A total of 115.92 g of combined copper oxychloride and zinc chloride is isolated. Inductive coupled plasma (ICP) analysis is utilized for analysis. This system may be computerized.


Example 3, Platinum Chloride and Palladium Chloride

In an additional example, to a reaction vessel which is equipped with a pump, a Venturi system to draw the chlorine gas into the reactor under vacuum, a thermometer, cooling bath, a millivoltmeter was add multiple sets of filtrate (3.5 L) from a first filtrate from a gold isolation. The solution comprised platinum (13.1 g, 67.12 mmol) and palladium (13 g, 123.33 mmol) as chlorides. Ammonium chloride (50 g, 0.934 mol) was added to the reaction vessel along with isopropyl alcohol (1.0 mL). Chlorine gas was added using a Venturi system to the reaction vessel under vacuum and at a rate of 0.0056 standard cubic feet per minute (scfm). At 27° C. both the platinum and palladium metals were converted to their respective chloride derivatives.


The ammonium chloroplatinate precipitates immediately at ambient temperature. After 20 to 30 minutes of stirring, the ammonium chloroplatinate was isolated by filtration. To the filtrate containing palladium chloride was added hydrochloric acid (10 mL), which precipitated palladium chloride. In this example, platinum chloride (17.80 g, 66.919 mmol, 99.7%) and palladium chloride (21.85 g, 123.21 mmol, 99.90%) was isolated. Inductive coupled plasma (ICP) analysis is utilized for analysis. This system may be computerized.



FIG. 5 illustrates a table of example test data for dissolving gold alloys in solution using chlorine gas as an oxidizing agent. As illustrated, FIG. 5 illustrates the difference in time it takes for atomized metal alloys of variant sizes to react fully or substantially fully with chlorine gas. As illustrated, FIG. 5 includes six columns. Column 502 indicates the test number. Column 504 indicates the number of minutes the test was run. Column 506 indicates the liters of solution. Column 508 indicates the cubic feet of chlorine gas that was pumped through the vessel during the test period (at a constant rate). Column 510 indicates the temperatures in degrees Fahrenheit during the start middle and end of the test. Column 512 indicates the mesh size range of the atomized metal alloy. For all of the tests one through five, 900 milliliters of water, 100 milliliters of hydrochloric acid at 37% concentration, 50 grams of NaCl, and 0.5 milliliters of isopropyl alcohol was added to a reactor similar or the same as the reactors described above. The atomized gold alloy comprising 50% gold, 7% silver, 36% copper, and 7% zinc was added to the solution. The total weight of the atomized metallic alloy that was added was 256 grams. As indicated in FIG. 5, test one ran for 90 minutes. During that time 6.1 cubic feet of chlorine gas was diffused into the solution. It took 90 minutes for the millivolt reading to indicate that substantially all of the atomized metal in the metal alloy had formed metal chlorides. It will be appreciated that as the size of the atomized particle decreased the speed which the reaction took place increased. The fastest test was test number 5, in which a metal particle size of about 320 mesh was reacted for 30 minutes with 3.85 cubic feet of chlorine gas bubbled through the solution during the test at a constant rate.



FIG. 6 illustrates a table of example test data for gold precipitation. Among other information, FIG. 6 illustrates the varying effects that different temperatures and surface tension relivers have on gold precipitation. FIG. 6 has 10 columns. Column 602 indicates the test number. Column 604 indicates the number of minutes that the test was run. Column 606 indicates the total cubic feet of sulfur dioxide run through a reactor during the test time. Column 608 indicates the starting and ending temperature in degrees Fahrenheit. Column 610 indicates whether polyvinyl alcohol was added during the test. Column 612 indicates whether 1-butanal was added during the test. Column 614 indicates whether 2-methyl/2-butanol was added during the test. Column 616 indicates whether isopropyl alcohol was added during the test. Column 618 indicates the millivolt measurement prior to the start of the test. Column 620 indicates the millivolt reading after the end of the test period.


For all of the tests illustrated in FIG. 6, 2.5 liters of solution was reacted using the reactor similar to or the same as the reactors described above and then was filtered using the techniques described herein to collect elemental gold. The 2.5 liter solution was derived from a gold alloy comprising 70% gold, 20% copper, 5% platinum, and 5% palladium. The gold alloy was atomized and chlorinated by reacting chlorine gas with an acidic brine solution having the atomized material suspended within said solution. A millivolt reader was applied to the solution to monitor when substantially all of the metals had been chlorinated. The techniques/methods applied were similar or the same as the techniques described with respect to operation 208 above. The resulting solution was passed through a filter to remove elemental gold precipitate. It was observed during tests one through six that the gold precipitate stuck to the lining of the reactor at the low temperature. It was further observed that the gold precipitate stuck to the lining during tests 6, 7, 8 and 9 to a lesser extent. Test number 10 there was no sticking. It will be appreciated from a review of FIG. 6 that a temperature range of between 95 degrees Fahrenheit and 122 degrees Fahrenheit allowed for the fastest reaction time at 22 minutes.



FIG. 7 illustrates a table of example test data for platinum group precipitation. FIG. 7 illustrates the effect of changing temperature on precipitation of platinum and palladium, among other things. FIG. 7 has six columns. Column 702 indicates the test number. Column 704 indicates the number of minutes the test was run. Column 706 indicates the number of cubic feet of chlorine gas that was diffused into the solution during the test period, which was at a constant rate. Column 708 indicates the starting temperature and ending temperature in degrees Fahrenheit. Column 710 indicates the number of grams of ammonium chloroplatinate and the corresponding percentage of platinum recovered. Column 712 indicates the number of grams of ammonium chloroplatinate recovered and the corresponding percentage.


For all of the tests provided in FIG. 7, 256 grams of a gold alloy comprising 70% gold, 20% copper, 5% platinum, and 5% palladium was atomized and chlorinated to form an acidic brine solution using techniques similar to or the same as the techniques described with respect to operation 202 and 204 above. The resulting solution was then filtered to remove any precipitate and was reduced to precipitate out and filter the elemental gold using techniques similar to the same as those techniques described with reference to operation 208 and 210. To that resulting filtrate, a total of 3.5 liters was mixed with 50 milliliters of 50% ammonium chloride and one milliliter of isopropyl alcohol. The solution was monitored from a starting pre-precipitation voltage of 800 millivolts to an ending post precipitation millivolt of 650 millivolts. This indicates that the reaction was substantially complete. During the test, the resulting solution was subjected to the indicated cubic feet of chlorine gas as indicated in column 706. It will be appreciated that test #6 completed in the shortest amount of time. Additionally test #6 had the highest percentage of both platinum and palladium recovered, each as a chloride.



FIG. 8 illustrates a table of example test data for precipitating copper oxychloride. FIG. 8 illustrates the effect of varying temperature on the precipitation time of copper oxychloride. FIG. 8 has six columns. Column 802 indicates the test number. Column 804 indicates the number of minutes of the test. Column 806 indicates the starting liters of solution. Column number 808 indicates the starting and ending temperature in degrees Fahrenheit. Column number 810 indicates the total amount of sodium hydroxide in grams at 50% concentration that was added to the solution. Column 812 indicates the total amount of copper oxychloride recovered in grams and as a percentage of the starting copper.


For each of the tests one through six indicated in FIG. 8, the four liter solution comprising an amount of copper chloride to produce a total amount of 176 grams of copper oxychloride at full reaction was provided to a reactor. In each of the tests, 40 grams of sodium hydroxide at a concentration of 50% was added to the starting solution. The starting solution had a pH of around 1 to 0. After the addition of the sodium hydroxide, the pH of the solution was about 13. Once precipitation was substantially complete, as evident by a millivolt reading going from 650 millivolts to 250 millivolts, 50 milliliters of 37% strength hydrochloric acid was added. This lowered the pH to about 7. It will be appreciated that test #1, having a temperature of about 80 degrees Fahrenheit throughout the test, resulted in the fastest precipitation. Additionally, test #1 provided the highest percent recovery of copper as copper oxychloride.


While aspects of the technology were discussed in relation to gold, it will be appreciated that the technologies described herein may be employed to separate metal allows comprising one or more of: all non-ferrous metals and rear earth metals including Aluminum, Magnesium, Titanium, Beryllium, Copper, Zinc, Lead, Tin, Tungsten, Nickel, Molybdenum, Chromium, Gold, Silver, Platinum, palladium, etc.


Further, while various embodiments have been described for purposes of this disclosure, various changes and modifications may be made which are well within the scope of the disclosed methods. Numerous other changes may be made which will readily suggest themselves to those skilled in the art and which are encompassed in the spirit of the disclosure.

Claims
  • 1. A method for refining metal comprising: providing bulk metal, the bulk metal comprising one or more elemental metals;atomizing the bulk metal to form an atomized particulate metal alloy, wherein each atomized particulate has a size;mixing the atomized particulate metal alloy with a brine solution to form a brine solution suspended with atomized metallic particles;mixing the brine solution suspended with atomized metallic particles with an acid to form an acidic brine solution suspended with the atomized metallic particles;chlorinating the acidic solution suspended with atomized metallic particles to form a chlorinated brine solution with a metal-chloride precipitate;filtering out the metal-chloride precipitate to form a filtered-chlorinated brine solution;reducing the filtered-chlorinated brine solution to form an elemental metal precipitate and a first solution;filtering out the elemental metal precipitate to form an eluent filtrate;reducing the eluent filtrate to form a platinum-group precipitate and a second solution;filtering out the platinum-group precipitate to form a base metal solution;reducing the base metal solution to form a base metal precipitate and a water-chloride solution;filtering out the base metal precipitate to form a filtered water-chloride solution.
  • 2. The method of claim 1, wherein the metal chloride precipitate is silver chloride.
  • 3. The method of claim 2, wherein the elemental metal precipitate is gold.
  • 4. The method of claim 1, wherein the brine solution comprises about 5% water about 5% sodium chloride by weight.
  • 5. The method of claim 1, wherein the platinum-group precipitate is ammonium chloroplatinate.
  • 6. The method of claim 1, wherein the base metal precipitate is copper oxychloride.
  • 7. The method of claim 1, wherein the temperature of each of the solution suspended with atomized metallic particles, the chlorinated brine solution with a metal-chloride precipitate, the filtered-chlorinated brine solution, the eluent filtrate, and the filtered water-chloride solution is kept below 50° C.
  • 8. The method of claim 1, wherein the acidic brine solution suspended with atomized metallic particles comprises about 3.5% hydrochloric acid, about 4.7% sodium chloride, and about 91.8% water by weight.
  • 9. A method of isolating gold from a gold alloy, the method comprising: providing a gold alloy comprising gold, silver, platinum, and copper;atomizing the gold alloy to form atomized gold alloy particles;suspending the atomized gold alloy particles in a brine solution, the brine solution comprising sodium chloride and water;precipitating a silver chloride by performing a first stage operation, the first stage operation comprising: adding hydrochloric acid to the brine solution to form an acidic brine solution;adding a first surface tension reducer to the acidic brine solution;bubbling chlorine gas through the acidic brine solution to form a chlorinated brine solution with silver-chloride precipitate;filtering the silver-chloride precipitate in a second stage to form a remaining filtered-chlorinated brine solution;reducing the remaining filtered-chlorinated brine solution in a third stage operation, the third stage operation comprising: adding a second surface tension reducer to the filtered-chlorinated brine solution:bubbling sulfur dioxide into the filtered-chlorinated brine solution to form a metal-filtrate solution, wherein the bubbling sulfur dioxide operation occurs for a period of time, and further wherein the metal-filtrate solution comprises elemental gold precipitate;filtering out the elemental gold in a fourth stage operation to form a first filtrate;treating the first filtrate in a fifth stage operation, the fifth stage operation comprising: adding ammonium chloride to the first filtrate;adding isopropyl alcohol to the first filtrate;bubbling chlorine through the first filtrate to form a platinum-precipitate solution,wherein the platinum-precipitate solution comprises ammonium chloroplatinate precipitate;filtering the ammonium chloroplatinate precipitate in a sixth-stage operation to form a base metal solution;treating a base metal solution in a seventh-stage operation, the seventh-stage operation comprising: adding a base to lower the pH of the base metal solution and cause a base metal compound to precipitate;raising the pH to form a water-chloride solution, wherein the water-chloride solution comprises the base metal precipitate;filtering the water-chloride solution to collect the base metal precipitate in an eight-stage operation.
  • 10. The method of claim 9, wherein the brine solution comprises 5% sodium chloride in water.
  • 11. The method of claim 9, wherein the atomized gold alloy particles have an average size of 42 microns.
  • 12. The method of claim 9, wherein hydrochloric acid is added such that the resulting acidic brine solution comprises 3.5% HCl by weight.
  • 13. The method of claim 9, wherein the third stage operation results in at least 99.9% of the gold precipitating out of solution.
  • 14. The method of claim 13, wherein the period of time of the bubbling of the sulfur dioxide operation is less than 35 minutes.
  • 15. The method of claim 9, wherein the first surface tension reliever is isopropyl alcohol.
  • 16. The method of claim 9, wherein the temperature of the third-stage operation remains below 52° C.
CLAIM OF PRIORITY

This application claims priority to and the benefit of U.S. Provisional Application No. 63/067,275, which was filed on Aug. 18, 2020, and is titled Metal Refinement.

US Referenced Citations (271)
Number Name Date Kind
776131 Gifford et al. Nov 1904 A
961924 Wohlwill Jun 1910 A
2199391 Blaut May 1940 A
3986899 Kole et al. Oct 1976 A
4011077 Kaufman Mar 1977 A
4041126 Baltz et al. Aug 1977 A
4094668 Yannopoulos et al. Jun 1978 A
4124617 Knifton Nov 1978 A
4131454 Piret et al. Dec 1978 A
4163046 Subramanian et al. Jul 1979 A
4172087 Knifton Oct 1979 A
4192723 Laude et al. Mar 1980 A
4231815 Snyder Nov 1980 A
4260139 Oliver et al. Apr 1981 A
4290967 Campbell et al. Sep 1981 A
4319922 MacDonald Mar 1982 A
4319923 Falanga et al. Mar 1982 A
4337091 El-Shazly et al. Jun 1982 A
4353740 Dunn Oct 1982 A
4374876 El-Shazly et al. Feb 1983 A
4378285 Castellanso et al. Mar 1983 A
4389248 Iio et al. Jun 1983 A
4390366 Lea et al. Jun 1983 A
4397686 Winkler et al. Aug 1983 A
4416692 Burch Nov 1983 A
4419325 Prasad Dec 1983 A
4427442 Day Jan 1984 A
4441993 Howald Apr 1984 A
4451639 Prasad May 1984 A
4462879 Castellanos et al. Jul 1984 A
4525254 Feofanov et al. Jun 1985 A
4536597 Pesa Aug 1985 A
4539177 Prasad Sep 1985 A
4557759 McGrew et al. Dec 1985 A
4629807 Knifton Dec 1986 A
4637865 Sergent et al. Jan 1987 A
4639378 Inoue Jan 1987 A
4654145 Demopoulos et al. Mar 1987 A
4655895 Feofanov et al. Apr 1987 A
4662938 Whitney May 1987 A
4670047 Kopatz Jun 1987 A
4670052 Stanley et al. Jun 1987 A
4711660 Kemp et al. Dec 1987 A
4719145 Neely Jan 1988 A
4723998 O'Neil Feb 1988 A
4731110 Kopatz et al. Mar 1988 A
4746379 Rabinkin May 1988 A
4770700 Bertha Sep 1988 A
4822633 Inoue Apr 1989 A
4836982 Brupbacher Jun 1989 A
4857107 Davis Aug 1989 A
4859293 Hirako et al. Aug 1989 A
4888209 Neely Dec 1989 A
4895626 Shor Jan 1990 A
4915905 Kampe et al. Apr 1990 A
4961856 Dalton et al. Oct 1990 A
4970571 Yamakawa et al. Nov 1990 A
5004500 Dunn et al. Apr 1991 A
5009755 Shor Apr 1991 A
5015534 Kampe et al. Apr 1991 A
5045290 Harris et al. Sep 1991 A
5049184 Harner et al. Sep 1991 A
5137700 Sloan Aug 1992 A
5198154 Yokoyama et al. Mar 1993 A
5198273 Ando et al. Mar 1993 A
5232492 Krulik et al. Aug 1993 A
5238662 Dubrovsky et al. Aug 1993 A
5242511 Yokoyama et al. Sep 1993 A
5252522 Dorbath et al. Oct 1993 A
5261945 Alla Nov 1993 A
5354353 Fountain et al. Oct 1994 A
5354359 Wan et al. Oct 1994 A
5372794 Lemaire et al. Dec 1994 A
5393388 Herrmann et al. Feb 1995 A
5405430 Groves et al. Apr 1995 A
5490870 Fountain et al. Feb 1996 A
5506363 Grate et al. Apr 1996 A
5557014 Grate et al. Sep 1996 A
5603750 Sierakowski et al. Feb 1997 A
5614004 Wachi et al. Mar 1997 A
5660619 Wachi et al. Aug 1997 A
5683490 Earley et al. Nov 1997 A
5761779 Maruyama et al. Jun 1998 A
5785736 Thomas et al. Jul 1998 A
5828127 Yamagata et al. Oct 1998 A
5882502 Gomez Mar 1999 A
5908803 Leconte et al. Jun 1999 A
5961833 Green et al. Oct 1999 A
6042894 Goto et al. Mar 2000 A
6045601 Tan Apr 2000 A
6075161 Langguth et al. Jun 2000 A
6090341 Vodrahalli Jul 2000 A
6126720 Okada et al. Oct 2000 A
6162278 Hu Dec 2000 A
6191060 Ofori Feb 2001 B1
6232651 Lee et al. May 2001 B1
6287371 Ota et al. Sep 2001 B1
6337056 Reverso Jan 2002 B1
6355175 Green et al. Mar 2002 B1
6383248 Taylor et al. May 2002 B1
6410241 Sykes et al. Jun 2002 B1
6558448 Hu May 2003 B2
6602319 Murthy et al. Aug 2003 B1
6660059 Ji et al. Dec 2003 B2
6699302 Jones et al. Mar 2004 B1
6736886 Suda et al. May 2004 B2
6740287 Billiet et al. May 2004 B2
6759004 Dwivedi Jul 2004 B1
6770765 Weisbeck et al. Aug 2004 B2
6797409 Ivey Sep 2004 B2
6830823 Kodas Dec 2004 B1
6852425 Hu Feb 2005 B2
6900018 Sykes et al. May 2005 B2
7018833 Sykes et al. Mar 2006 B2
7049098 Sykes et al. May 2006 B2
7066983 Ji et al. Jun 2006 B2
7166796 Nicoloau Jan 2007 B2
7176036 Wang et al. Feb 2007 B2
7205459 Larkins et al. Apr 2007 B1
7468340 Ohya et al. Dec 2008 B2
7473406 Jasra et al. Jan 2009 B2
7524929 Carmeli et al. Apr 2009 B2
7559974 Ji et al. Jul 2009 B2
7655321 Albrecht et al. Feb 2010 B2
7682420 Abe et al. Mar 2010 B2
7682704 Dwivedi Mar 2010 B2
7704298 Ji et al. Apr 2010 B2
7740683 Thorsson et al. Jun 2010 B2
7758916 Schmid et al. Jul 2010 B2
7773131 Kusuda et al. Aug 2010 B2
7776131 Shoji et al. Aug 2010 B2
7927744 Mizutani et al. Apr 2011 B2
8016912 Fekete et al. Sep 2011 B2
8016977 Rasmussen et al. Sep 2011 B2
8017835 Chappell et al. Sep 2011 B2
8034195 Schmid et al. Oct 2011 B2
8039806 Frank et al. Oct 2011 B2
8123980 Kijima et al. Feb 2012 B2
8158281 Ishihara et al. Apr 2012 B2
8173025 Reidhead et al. May 2012 B2
8173026 Rasmussen et al. May 2012 B2
8212005 Carmeli et al. Jul 2012 B2
8329343 Yamaguchi et al. Dec 2012 B2
8348621 Lafont Jan 2013 B2
8450236 Fu et al. Apr 2013 B2
8556237 Yamaguchi et al. Oct 2013 B2
8597399 Ji et al. Dec 2013 B2
8633270 Lochtman et al. Jan 2014 B2
8636920 Kijima et al. Jan 2014 B2
8697399 Huang et al. Apr 2014 B2
8741238 Dreisinger Jun 2014 B2
8779164 Leeuwen et al. Jul 2014 B2
8821613 Ji et al. Sep 2014 B2
8912346 Leeuwen et al. Dec 2014 B2
8932761 Yamaguchi et al. Jan 2015 B2
8974572 Uehara Mar 2015 B2
8986880 Odani et al. Mar 2015 B2
8993166 Mizutani et al. Mar 2015 B2
9016912 Gustafson Apr 2015 B1
9017542 Zhou et al. Apr 2015 B2
9039724 Amplatz et al. May 2015 B2
9039806 Dreisinger et al. May 2015 B2
9115418 Nakamura et al. Aug 2015 B2
9118062 Yamaguchi et al. Aug 2015 B2
9127618 Azevedo et al. Sep 2015 B2
9127619 Lineton et al. Oct 2015 B2
9166221 Yamaguchi et al. Oct 2015 B2
9206492 Lalancette et al. Dec 2015 B2
9209480 Odani et al. Dec 2015 B2
9219218 Ishigami et al. Dec 2015 B2
9339585 Yao et al. May 2016 B2
9382776 Murphree et al. Jul 2016 B2
9431650 Yamaguchi et al. Aug 2016 B2
9499643 Malivemey et al. Nov 2016 B2
9605045 Daniell Mar 2017 B2
9657302 Daniell May 2017 B2
9702028 Otsuka et al. Jul 2017 B2
9732398 Lakshmanan et al. Aug 2017 B2
9735017 Murakami et al. Aug 2017 B2
9742007 Hirose et al. Aug 2017 B2
9742036 Yamaguchi Aug 2017 B2
9799457 Ramello et al. Oct 2017 B2
9844774 Schueth et al. Dec 2017 B2
9881877 Kawabata Jan 2018 B2
9972579 Kawabata May 2018 B1
10065276 Azevedo et al. Sep 2018 B2
10099211 Knott et al. Oct 2018 B2
10136703 Gooch et al. Nov 2018 B2
10174401 Wyatt et al. Jan 2019 B2
10205163 Yamaguchi et al. Feb 2019 B2
10256194 Kawabata Mar 2019 B2
10269727 Kawabata Apr 2019 B2
10292265 Kasuga et al. May 2019 B2
10299376 Nakamura et al. May 2019 B2
10403582 Kawabata Sep 2019 B2
10443139 Mills Oct 2019 B2
10617788 McCoy Apr 2020 B2
10622126 Yamamoto Apr 2020 B2
10665855 Morozumi et al. May 2020 B2
10669608 Lundstrom et al. Jun 2020 B2
10796921 Minami et al. Oct 2020 B2
10836867 Knott Nov 2020 B2
10888973 Franke et al. Jan 2021 B2
11072053 Franke et al. Jul 2021 B2
11072115 Franke et al. Jul 2021 B2
11179781 Lu Nov 2021 B2
20020081739 Brill et al. Jun 2002 A1
20020150940 Sykes et al. Oct 2002 A1
20030018991 Lazzeri et al. Jan 2003 A1
20030083195 Nakamaru et al. May 2003 A1
20030138784 Sykes et al. Jul 2003 A1
20040133019 Dugal et al. Jul 2004 A1
20040138480 Weisbeck et al. Jul 2004 A1
20040197347 Sykes et al. Oct 2004 A1
20040217061 Corzani et al. Nov 2004 A1
20040230083 Weisbeck et al. Nov 2004 A1
20050083785 Shiokawa et al. Apr 2005 A1
20050176264 Lai et al. Aug 2005 A1
20050208125 Politi et al. Sep 2005 A1
20050216959 Brill et al. Sep 2005 A1
20050250008 Mizutani et al. Nov 2005 A1
20060095982 Daniell May 2006 A1
20060123515 Daniell Jun 2006 A1
20060285989 Schade Dec 2006 A1
20070067862 Daniell Mar 2007 A1
20070124830 Daniell May 2007 A1
20070124838 Daniell May 2007 A1
20080081864 Takano Apr 2008 A1
20080143625 Mizushima et al. Jun 2008 A1
20080206651 Kawase et al. Aug 2008 A1
20080220988 Zhou Sep 2008 A1
20080261114 Ishihara Oct 2008 A1
20090047170 Shoji et al. Feb 2009 A1
20090148778 Kawase et al. Jun 2009 A1
20090226819 Ihara et al. Sep 2009 A1
20090285976 Lochtman et al. Nov 2009 A1
20090301891 Locktman et al. Dec 2009 A1
20090321123 Lochtman et al. Dec 2009 A1
20100009094 Lochtman et al. Jan 2010 A1
20100021657 Lochtman et al. Jan 2010 A1
20100075233 Yamaguchi et al. Mar 2010 A1
20100170626 Lochtman et al. Jul 2010 A1
20100176090 Lochtman et al. Jul 2010 A1
20100178584 Hibino et al. Jul 2010 A1
20100223944 Tsujimoto et al. Sep 2010 A1
20100251425 Daniell Sep 2010 A9
20100296987 Hyvarinen et al. Nov 2010 A1
20110064937 Mukoyama et al. Mar 2011 A1
20110083531 Soldenhoff Apr 2011 A1
20110129607 Lee et al. Jun 2011 A1
20120014827 Schade Jan 2012 A1
20120027652 Dreisinger Feb 2012 A1
20120040872 Zhou Feb 2012 A1
20120090825 Yarin et al. Apr 2012 A1
20120118795 Ogram May 2012 A1
20120125670 Kato et al. May 2012 A1
20120231527 Dubois-Calero et al. Sep 2012 A1
20130042912 Kurihara et al. Feb 2013 A1
20140047954 Ji et al. Feb 2014 A1
20140236772 McCoy et al. Aug 2014 A1
20140238191 Otsuka et al. Aug 2014 A1
20150320158 Duffy Nov 2015 A1
20160045841 Kaplan et al. Feb 2016 A1
20160166757 Koyama et al. Jun 2016 A1
20160263653 Kim et al. Sep 2016 A1
20170044644 Goldstein Feb 2017 A1
20170247805 Thus et al. Aug 2017 A1
20180318922 Valls Anglés Nov 2018 A1
20180369970 Azevedo et al. Dec 2018 A1
20190035744 Kawabata Jan 2019 A1
20190048449 Matsunaga et al. Feb 2019 A1
Foreign Referenced Citations (232)
Number Date Country
120941 Sep 1909 CA
395394 Mar 1941 CA
1061573 Sep 1979 CA
1062476 Sep 1979 CA
1197986 Dec 1985 CA
1209523 Aug 1986 CA
1030944 Feb 1989 CN
1070229 Mar 1993 CN
1237644 Dec 1999 CN
1270235 Oct 2000 CN
2443971 Aug 2001 CN
1352310 Jun 2002 CN
1366093 Aug 2002 CN
1450182 Oct 2003 CN
1683573 Oct 2005 CN
1800422 Jul 2006 CN
1821060 Aug 2006 CN
1932052 Mar 2007 CN
101028612 Sep 2007 CN
101029357 Sep 2007 CN
101082084 Dec 2007 CN
101104587 Jan 2008 CN
101255502 Sep 2008 CN
101386930 Mar 2009 CN
101451190 Jun 2009 CN
101451198 Jun 2009 CN
101519731 Sep 2009 CN
101560608 Oct 2009 CN
201330288 Oct 2009 CN
101569889 Nov 2009 CN
101570830 Nov 2009 CN
101660061 Mar 2010 CN
101775501 Jul 2010 CN
101787547 Jul 2010 CN
101793637 Aug 2010 CN
101818250 Sep 2010 CN
101831553 Sep 2010 CN
101850354 Oct 2010 CN
101928838 Dec 2010 CN
201686758 Dec 2010 CN
101942549 Jan 2011 CN
101949005 Jan 2011 CN
101956078 Jan 2011 CN
101974698 Feb 2011 CN
101985691 Mar 2011 CN
102031383 Apr 2011 CN
102031404 Apr 2011 CN
102041393 May 2011 CN
102086029 Jun 2011 CN
102114584 Jul 2011 CN
102134653 Jul 2011 CN
102134654 Jul 2011 CN
102162035 Aug 2011 CN
102218372 Oct 2011 CN
102230083 Nov 2011 CN
102274978 Dec 2011 CN
102392152 Mar 2012 CN
102491287 Jun 2012 CN
102560137 Jul 2012 CN
102560534 Jul 2012 CN
102676837 Sep 2012 CN
102690955 Sep 2012 CN
102703707 Oct 2012 CN
102719675 Oct 2012 CN
102776368 Nov 2012 CN
102923882 Feb 2013 CN
102925705 Feb 2013 CN
102936659 Feb 2013 CN
102978658 Mar 2013 CN
103014760 Apr 2013 CN
103131866 Jun 2013 CN
103194770 Jul 2013 CN
103290223 Sep 2013 CN
103320620 Sep 2013 CN
103342387 Oct 2013 CN
103498052 Jan 2014 CN
103526042 Jan 2014 CN
103649348 Mar 2014 CN
103821009 May 2014 CN
103882240 Jun 2014 CN
103882243 Jun 2014 CN
103931783 Jul 2014 CN
103937988 Jul 2014 CN
104004907 Aug 2014 CN
104018186 Sep 2014 CN
104047024 Sep 2014 CN
104109763 Oct 2014 CN
104308124 Jan 2015 CN
204162762 Feb 2015 CN
104593614 May 2015 CN
104605070 May 2015 CN
104643426 May 2015 CN
104692416 Jun 2015 CN
104789783 Jul 2015 CN
104911364 Sep 2015 CN
104975182 Oct 2015 CN
105112681 Dec 2015 CN
105132708 Dec 2015 CN
105256139 Jan 2016 CN
105621901 Jun 2016 CN
105671315 Jun 2016 CN
105886806 Aug 2016 CN
106119568 Nov 2016 CN
106148723 Nov 2016 CN
106222424 Dec 2016 CN
106222431 Dec 2016 CN
106244822 Dec 2016 CN
106256914 Dec 2016 CN
106298721 Jan 2017 CN
106367609 Feb 2017 CN
106591592 Apr 2017 CN
106676595 May 2017 CN
106702168 May 2017 CN
106868545 Jun 2017 CN
106884093 Jun 2017 CN
107217135 Sep 2017 CN
206521510 Sep 2017 CN
107266229 Oct 2017 CN
107326179 Nov 2017 CN
107457411 Dec 2017 CN
107460324 Dec 2017 CN
107586953 Jan 2018 CN
107805711 Mar 2018 CN
207518241 Jun 2018 CN
207685355 Aug 2018 CN
207845803 Sep 2018 CN
108624759 Oct 2018 CN
3145006 Jun 1982 DE
19852077 Jun 2000 DE
10053450 May 2002 DE
102009021181 Nov 2010 DE
201700012 Jun 2018 EA
118633 Sep 1984 EP
190600146 Dec 1906 GB
190525122 Jan 1907 GB
190600149 Jan 1907 GB
190700530 Oct 1907 GB
190906276 Jul 1909 GB
190914660 Jun 1910 GB
191511818 Feb 1916 GB
161656 Apr 1921 GB
263642 Jan 1927 GB
265036 Feb 1927 GB
435731 Sep 1935 GB
483741 Apr 1938 GB
485089 May 1938 GB
569444 May 1945 GB
578102 Jun 1946 GB
587584 Apr 1947 GB
803261 Oct 1958 GB
910826 Nov 1962 GB
989233 Apr 1965 GB
1055622 Jan 1967 GB
1079013 Aug 1967 GB
1388794 Mar 1975 GB
1449215 Sep 1976 GB
2018828 Oct 1979 GB
176480 Jun 1996 IN
S6067633 Apr 1985 JP
S60208435 Oct 1985 JP
S6137932 Feb 1986 JP
S62185840 Aug 1987 JP
S6324089 Feb 1988 JP
H06306671 Nov 1994 JP
H10326803 Dec 1998 JP
H11222632 Aug 1999 JP
2000178669 Jun 2000 JP
2002030355 Jan 2002 JP
2002275561 Sep 2002 JP
2004018933 Jan 2004 JP
2006057133 Mar 2006 JP
2011058018 Mar 2011 JP
2015218370 Dec 2015 JP
2017171997 Sep 2017 JP
2018150597 Sep 2018 JP
20000037955 Jul 2000 KR
20000049783 Aug 2000 KR
20010054356 Jul 2001 KR
100742513 Jul 2007 KR
10078441 Dec 2007 KR
100784410 Dec 2007 KR
20090123136 Dec 2009 KR
20140087501 Jul 2014 KR
101630087 Jun 2016 KR
20180004862 Jan 2018 KR
101817079 Feb 2018 KR
101844771 Apr 2018 KR
101842107 May 2018 KR
20180073492 Jul 2018 KR
309768 Feb 1997 PL
121919 Jul 2008 RO
125168 Jan 2010 RO
128995 Nov 2013 RO
20130252 Feb 2015 RS
2025516 Dec 1994 RU
94036689 Apr 1997 RU
2164255 Mar 2001 RU
2180008 Feb 2002 RU
2181780 Apr 2002 RU
2003113496 Jan 2005 RU
2003130045 Jul 2005 RU
2291212 Jan 2007 RU
2006128807 Feb 2008 RU
2321648 Apr 2008 RU
2516180 May 2014 RU
2553270 Jun 2015 RU
200912962 Mar 2009 TW
8607046 Dec 1986 WO
2004106560 Dec 2004 WO
2014105867 Jul 2014 WO
2014185817 Nov 2014 WO
2014193929 Dec 2014 WO
2014205184 Dec 2014 WO
2015001023 Jan 2015 WO
2015004018 Jan 2015 WO
2015031984 Mar 2015 WO
2015032253 Mar 2015 WO
2015032282 Mar 2015 WO
2015032809 Mar 2015 WO
2015032997 Mar 2015 WO
2015033850 Mar 2015 WO
2015034151 Mar 2015 WO
2015034231 Mar 2015 WO
2015034260 Mar 2015 WO
2015034715 Mar 2015 WO
2015034834 Mar 2015 WO
2015034852 Mar 2015 WO
2015034990 Mar 2015 WO
2015035116 Mar 2015 WO
2016131445 Aug 2016 WO
200205292 Jul 2003 ZA
4374 Nov 1974 ZM
Non-Patent Literature Citations (1)
Entry
Facebook status update by “Pace Financing and Contractor Services”, Jun. 28, 2018, post has since been removed.
Related Publications (1)
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20220056555 A1 Feb 2022 US
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