US20150183009A1 - Composition for treating an excavation activity - Google Patents
Composition for treating an excavation activity Download PDFInfo
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- US20150183009A1 US20150183009A1 US14/658,795 US201514658795A US2015183009A1 US 20150183009 A1 US20150183009 A1 US 20150183009A1 US 201514658795 A US201514658795 A US 201514658795A US 2015183009 A1 US2015183009 A1 US 2015183009A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- B09B3/0016—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/605—Compositions for stimulating production by acting on the underground formation containing biocides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
- C09K8/94—Foams
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
- E21B33/138—Plastering the borehole wall; Injecting into the formation
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F15/00—Methods or devices for placing filling-up materials in underground workings
- E21F15/005—Methods or devices for placing filling-up materials in underground workings characterised by the kind or composition of the backfilling material
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F15/00—Methods or devices for placing filling-up materials in underground workings
- E21F15/08—Filling-up hydraulically or pneumatically
Definitions
- the present invention generally involves a composition for treating an excavation activity.
- the composition may be used to treat byproducts and conditions associated with excavation activities to reduce acid rock drainage and/or recover valuable resources.
- excavation activities encompass not only conventional mining operations to locate and recover natural resources below the surface of the earth, but also any other operations that disrupt large areas of the natural surface and/or contour of land.
- excavation activities encompass not only conventional mining operations to locate and recover natural resources below the surface of the earth, but also any other operations that disrupt large areas of the natural surface and/or contour of land.
- highway construction and other large commercial developments often produce the same byproducts and conditions as conventional mining operations and constitute excavation activities within the scope of the present inventions.
- FIG. 1 provides an exemplary drawing of an excavation activity 10 to illustrate various byproducts and conditions that may lead to the generation of various forms of environmentally harmful water pollution.
- the byproducts may include, for example, various forms of mineral processing waste, such as overburden 12 , slag, gangue, and buried pyrite-bearing rock 14 .
- the conditions may include, for example, the excavation site itself, draining adits, tunnels 16 , abandoned pits 18 , and mines.
- rain water 20 , runoff 22 , and other sources of water may pass over and through various portions of the excavation activity 10 and interact and react with the byproducts and conditions to produce undesirable water pollution 24 .
- the undesirable water pollution 24 generally gravity drains through the excavation activity 10 until it reaches an impermeable barrier, such as a natural or man-made liner 26 , which eventually guides the water pollution to an outfall, such as a stream or underground well or ground water infiltration/recharge zone.
- an impermeable barrier such as a natural or man-made liner 26 , which eventually guides the water pollution to an outfall, such as a stream or underground well or ground water infiltration/recharge zone.
- the water pollution 24 produced by excavation activities may be generically referred to as acid rock drainage (ARD) or acid mine drainage (AMD), and will hereinafter be collectively referred to as ARD.
- ARD acid rock drainage
- AMD acid mine drainage
- the combination of water, bacteria, and sulfide minerals exposed to air by excavation activities produces sulfuric acid, sulfates, iron and other metals in the ARD.
- sulfuric acid, sulfates, iron and other metals in the ARD For example, the following four generally-accepted chemical reactions describe the oxidation of sulfide minerals (represented by FeS 2 as a proxy for all reactive sulfide minerals) that produces ARD:
- the elementary chemical ingredients required for the formation of ARD are air, water, and sulfide materials.
- bacteria can facilitate the formation of ARD.
- the production of ARD may be predicted by a number of standard tests, including acid-base accounting tests, humidity cell tests, and column leach tests. For example, in a pH environment of less than approximately 4.5, naturally-occurring bacteria, such as acidithiobacillus ferro-oxidans and related microbes, may act as a catalyst and accelerate reactions 1, 2, and 4 above, lowering the pH even further.
- Hydrogen ions (H + ) and ferric iron ions (Fe +3 ) may also accelerate the oxidation of other metal sulfides that may be present, releasing additional metals such as copper, lead, zinc, cadmium, mercury, and manganese into the ARD.
- An effective method for reducing and/or preventing ARD is to remove and/or isolate one or more of the elementary ingredients—air, water, sulfide materials, and/or bacteria—required for ARD production.
- a generally accepted system and method for treating byproducts and conditions associated with an excavation activity is to disperse one or more active ingredients or reagents over the excavation site to react with one or more of the elementary ingredients.
- the byproducts and conditions associated with excavation activities are often buried, widely dispersed, and otherwise inaccessible to direct application of the active ingredients, requiring a combination of closely-spaced boreholes, gravity, and voluminous amounts of water to transport the active ingredients to the affected areas to be treated.
- One embodiment of the present invention is a composition for treating an excavation activity that includes a reagent suspended in foam to form a reagent-foam mixture.
- the reagent is selected to react with at least one of sulfides or bacteria in waste rock or tailings materials to reduce acid rock drainage.
- the reagent includes at least one of limestone, dolomite, sodium bicarbonate, steel slag, fly ash, or sodium hydroxide.
- Another embodiment of the present invention is a composition for treating an excavation activity that includes a reagent suspended in foam to form a reagent-foam mixture.
- the reagent is selected to react with at least one of sulfides or bacteria in waste rock or tailings materials to reduce acid rock drainage.
- the reagent includes at least one of milk, sodium thiocyanate, bio-solids, sawdust, paper, or composted animal manure.
- the present invention may also include a composition for treating an excavation activity that includes a reagent suspended in foam to form a reagent-foam mixture.
- the reagent is selected to react with at least one of sulfides or bacteria in waste rock or tailings materials to reduce acid rock drainage.
- the reagent includes at least one of iron, copper, manganese oxide, zeolite minerals, peat, activated carbon, or organic resins.
- FIG. 1 is a simplified cross-section drawing of an exemplary excavation activity
- FIG. 2 is a simplified block diagram of a system for treating an excavation activity according to one embodiment of the present invention
- FIG. 3 is a simplified cross-section drawing of the excavation activity shown in FIG. 1 being treated according to one embodiment of the present invention
- FIG. 4 is a simplified cross-section drawing of an excavation deposit being treated according to an embodiment of the present invention.
- FIG. 5 is a simplified cross-section drawing of an excavation pit being treated according to an embodiment of the present invention.
- Various embodiments of the present invention provide a system and method for transporting and applying various gaseous, liquid, and/or solid active ingredients or reagents through natural or man-made porous and permeable media to treat an excavation activity to reduce and/or prevent water pollution, namely acid rock drainage (ARD), and/or facilitate valuable resource recovery.
- a stable foam slurry may be used to transport and apply the gaseous, liquid, and/or solid active ingredients or reagents.
- the system and method may be used at or with an excavation activity, including zones adjacent to the excavation activity and/or excavation deposits, to reduce and/or prevent the spread of ARD.
- FIG. 2 provides a simplified block diagram of a system 30 for treating an excavation activity 32 according to one embodiment of the present invention.
- the excavation activity 32 may encompass byproducts and conditions associated with conventional mining operations as well as any other operations that disrupt large areas of the natural surface and/or contour of land.
- the byproducts and conditions may comprise porous and permeable materials, such as broken or fractured geological rock formations, ore, ore concentrates, coal, mine tailings, mine waste, slag, sand, or soil.
- Metallurgical processes, natural chemical changes such as oxidation, and/or biological activity may act on the porous and permeable materials to produce ARD, as previously described.
- the byproducts and conditions may contain valuable constituents, such as gold, silver, the platinum group metals, uranium, copper, lead, zinc, or any element that could economically be recovered from ore either found in place or excavated from the ground and subjected to conventional metallurgical processes for economic recovery.
- the system 30 generally includes a distribution network 34 in fluid communication with the excavation activity 32 .
- the distribution network 34 may be proximate to or remote from the excavation activity 32 and may comprise any suitable system for conveying or transporting a fluid to the excavation activity 32 .
- the distribution network 34 may comprise a piping system 36 and one or more pumps 38 or blowers that provide fluid communication between one or more supply tanks and the excavation activity 32 .
- the piping system 36 may connect, for example, one or more of a surfactant tank 40 , a liquid reagent tank 42 , a compressor 44 , and/or a solid reagent tank 46 to the excavation activity 32 .
- the various tanks may supply one or more active ingredients or reagents to the excavation activity 32 to remove and/or isolate one or more of the elementary ingredients—air, water, sulfide materials, and/or bacteria—required for ARD production.
- the surfactant tank 40 may supply a foaming agent 48 to the distribution network 34 to create a stable foam media for transporting or conveying one or more active ingredients or reagents to the excavation activity 32 .
- foam includes any two-phase fluid comprised of a liquid and a gas partitioned by a surfactant (e.g., soap) into bubbles.
- the foaming agent 48 may comprise, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, natural surfactants derived from animal proteins, and/or combinations thereof.
- the actual foaming agent 48 and the active ingredients it carries will be customized for each application based on the objective of the application, the chemical makeup, physical condition, and microbiological suites present, and the degree of saturation of the polluting or resource-grade materials. It should be understood by one of ordinary skill in the art that various surfactants are contemplated within the scope of the present invention, and the present invention is not limited to any particular surfactant unless specifically recited in the claims.
- the liquid reagent tank 42 , compressor 44 , and/or solid reagent tank 46 may supply one or more active ingredients or reagents to mix with the foaming agent 48 , with the actual active ingredients or reagents selected to react with one or more of the elementary ingredients—air, water, sulfide materials, and/or bacteria—required for ARD production.
- the liquid reagent tank 42 if present, may supply one or more liquid active ingredients or reagents 50 selected to react with one or more of the elementary ingredients.
- the liquid reagent tank 42 may supply a liquid bactericide selected to react with bacteria at the excavation activity 32 to reduce and/or prevent the production of ARD.
- Possible bactericides include, for example, sodium lauryl sulfate, waste milk or other dairy by-products, bi-polar lipids, and/or sodium thiocyanate.
- the liquid reagent tank 42 may supply solutions, such as sodium hydroxide and/or hydrated lime solutions, selected to adjust the pH at the excavation activity 32 .
- the liquid reagent tank 42 may supply solutions, such as sodium cyanide, thiourea, sodium hypochlorite, and/or hydrogen peroxide, selected to dissolve or leach precious metals from the excavation activity 32 .
- the liquid reagent tank 42 may supply solutions selected to coat the excavation activity 32 and isolate the excavation minerals from air and/or water.
- a solution of dissolved potassium permanganate has been shown to coat particulate mine waste materials with a layer of manganese dioxide and thus isolate pyrite-bearing rocks from air and water to prevent the production of ARD.
- solutions of dissolved phosphate have been shown to complex with dissolved iron and starve bio-oxidation of pyrite through disruption of the kinetics of equations 2, 3, and 4 previously discussed.
- the compressor 44 may similarly supply one or more gaseous active ingredients or reagents 52 selected to react with one or more of the elementary ingredients.
- the compressor 44 may supply carbon dioxide, nitrogen, or other inert gases that can displace oxygen proximate to the byproducts and conditions associated with the excavation activity 32 , thereby interfering with or preventing one or more of the chemical reactions known to produce ARD.
- the compressor 44 may supply hydrogen sulfide which, in addition to displacing oxygen, may also immobilize heavy metals present in solution at the excavation activity 32 .
- the solid reagent tank 46 may similarly supply one or more solid active ingredients or reagents 54 selected to react with one or more of the elementary ingredients.
- solid active ingredients or reagents 54 selected to react with one or more of the elementary ingredients.
- limestone, dolomite, cement kiln dust, steel slag, sodium bicarbonate, fly ash, and various pozzolanic materials may provide acid-neutralizing alkalinity to sulfide-bearing rock materials prone to produce ARD.
- slow-release bactericides may be used to suppress pyrite oxidizing bacteria
- organic materials such as cellulose, wood, and paper, bio-solids, and/or animal and vegetable proteins may be used to suppress pyrite oxidation.
- Processed peat, natural peat, zeolite minerals, manganese oxides, and similar man-made products such as resins may be added to adsorb heavy metals.
- Additional solid active ingredients or reagents within the scope of the present invention may include zero valent iron, nano-scale iron, powdered iron oxy-hydroxides, and powdered copper which have the ability to chemically alter or detoxify dissolved pollutants.
- the various liquid, gaseous, and/or solid active ingredients or reagents 50 , 52 , 54 are mixed or added to the foaming agent 48 to form a reagent-foam composition or mixture 56 .
- a foam tube 58 and/or a mixer 60 may be included in the distribution network 34 , as needed, to homogeneously mix or prepare the reagent-foam mixture 56 .
- the actual active ingredient or reagent mixed with the foaming agent 48 will depend on the actual conditions at the excavation activity 32 .
- Table I below identifies various active ingredients or reagents that may be selected to react with one or more of the elementary ingredients—air, water, sulfide materials, and/or bacteria—required for ARD production:
- Table II identifies various active ingredients or reagents that may be selected to react with one or more heavy metals or other pollutants to facilitate recovery, detoxification, and or immobilization:
- the reagent-foam composition or mixture 56 may be dispersed over the excavation activity 32 using standard grouting technology such as packers, specialized grout casing, or foam-retaining bulkheads for large underground mine voids, as desired.
- standard grouting technology such as packers, specialized grout casing, or foam-retaining bulkheads for large underground mine voids, as desired.
- the reagent-foam mixture 56 expands omni-directionally (upward, downward, and circumferentially) as an advancing front that coats and saturates the porous and permeable materials present at the excavation activity 32 .
- the grout tubing or packers may be repositioned as needed to allow the injection point(s) to be varied to disperse the reagent-foam mixture 56 in the desired zone.
- the foaming agent 48 effectively penetrates porous and permeable materials commonly found at excavation activities 32 , leaving a coating on the materials when the foam dissipates.
- the exothermic reactions associated with the oxidation of sulfides frequently results in warm, dry zones that will quickly dissipate the moisture from the foam, precipitating a higher concentration of active ingredients or reagents at that particular location that suppress additional chemical or bacterial oxidation.
- the precipitated active ingredients or reagents do not obstruct or otherwise clog the porous and permeable materials, allowing for subsequent applications over time without a loss of effectiveness.
- foaming agent 48 provides superior transport and deposition characteristics compared to conventional liquid dispersal techniques, while requiring substantially less water.
- the system 30 may further include a liner 62 and/or a collection network 64 in fluid communication with the excavation activity 32 .
- the liner 62 may comprise a natural or man-made surface beneath at least a portion of the excavation activity 32 that provides a barrier for any water draining from the excavation activity 32 .
- the collection network 64 may comprise perforated drainage pipes that collect and channel water draining from the excavation activity 32 to a collection point 66 for additional processing and disposal.
- FIGS. 3-5 provide simplified drawings of various excavation activities being treated according to embodiments of the present invention.
- FIG. 3 shows the use of multiple injection ports 68 to distribute and disperse the reagent-foam mixture 56 into a buried excavation deposit 70 .
- the omni-directional expansion of the reagent-foam mixture 56 through the excavation deposit 70 allows for complete coverage of the excavation deposit 70 using fewer injection ports 68 , with a corresponding reduction in water consumption.
- the omni-directional expansion of the reagent-foam mixture 56 allows the system 30 to treat a surface excavation deposit 72 from the bottom.
- FIG. 5 shows use of the system 30 to economically treat localized or isolated excavation activities such as fractures 74 or other shallow geological disturbances in an excavation pit 76 .
- the distribution network 34 may facilitate precise application of the reagent-foam mixture 56 , thereby reducing the consumption of water and active ingredients in the process.
- An excavation activity comprises a twenty acre excavation deposit containing a pollution generating pyrite-bearing rock zone that has been delineated through borehole and geophysical data.
- the excavation deposit has a total volume of approximately 3.2 million cubic yards, of which approximately one-third or 1.1 million cubic yards is void space.
- Approximately 25% of the excavation deposit volume i.e., approximately 806,000 cubic yards) contains the pollution generating pyrite-bearing rock, with approximately 266,000 cubic yards of voids in this pollution-generating zone.
- the designed distribution network includes a commercial air compressor with a capacity of 100 cubic feet per minute and a standard pressure of 100 pounds per square inch, a pump with a capacity from 5 to 20 gallons per minute, tanks, and other conventional foam-generating equipment connected generally as shown in FIG. 2 .
- the designed piping system includes 4-inch diameter pipe installed in a plurality of boreholes drilled into the approximate geometric centroids of the pyrite-bearing rock zones. The annulus between the pipe and the surrounding pyrite-bearing rock zones is filled with sand or concrete.
- the active ingredients or reagents for this application are selected to provide an anti-bacterial action, acidic pH neutralizing actions, and oxygen depletion actions.
- the selected anti-bacterial reagents include sodium lauryl sulfate (which is also the foaming agent); waste milk (nutrient for beneficial bacteria to out-compete pyrite-oxidizing bacteria); and bio-solids (bacterial inoculum).
- the selected acidic pH neutralizing reagent is finely crushed limestone powder having a grain size from approximately 20 mesh (0.84 mm) to approximately 200 mesh (0.074 mm).
- the selected oxygen-depleting reagent is a fine-grained sawdust waste product having a nominal diameter of approximately 20 mesh (0.84 mm). Hypothetical laboratory testing and/or field trials indicate the following ratios of the foaming agent and active ingredients or reagents produce the desired reagent-foam mixture:
- the resulting reagent-foam mixture contains about 3.85% solids by volume or about 10,238 cubic yards of solid active ingredients for the entire treatment outlined in this example.
- An excavation activity comprises a 200 acre abandoned open pit mine site that exposes a fractured, pyrite-bearing rock zone that has been delineated through borehole, geochemical data, and geologic interpretation.
- the fracture zone is a combination of natural geological conditions and over-break from blasting activity in creating the excavation.
- the zone of intense fracturing extends at least 100 feet into the excavation wall rock and through the floor of each bench, as shown in FIG. 5 .
- the fractures constitute less than 1% of the total rock mass volume. Every linear foot of excavation bench includes an estimated 150 cubic yards of rock, of which 1.5 cubic yards are void space. There are 2 miles of bench in the pyrite-rock exposure, resulting in 15,840 cubic yards of fracture that requires treatment in this pollution-generating zone.
- the designed distribution network includes a commercial air compressor with a capacity of 100 cubic feet per minute and a standard pressure of 100 pounds per square inch, a pump with a capacity from 5 to 20 gallons per minute, tanks, and other conventional foam-generating equipment connected generally as shown in FIG. 2 .
- the designed piping system includes 2-inch diameter pipe installed in a plurality of boreholes drilled into the pyrite-bearing fractured rock zones. The annulus between the pipe and the surrounding pyrite-bearing rock zones is filled with cementitious grout to seal the pipe into the rock mass.
- the active ingredients or reagents for this application are selected to provide an anti-bacterial action and acidic pH neutralizing actions.
- the anti-bacterial ingredients include sodium lauryl sulfate (which is also the foaming agent); waste milk (nutrient for beneficial bacteria to out-compete the pyrite oxidizing bacteria); and bio-solids (bacterial inoculum).
- the selected acidic pH neutralizing reagent is finely crushed limestone powder having a grain size from approximately 200 mesh (0.074 mm) to approximately 400 mesh (0.037 mm) and a solution of sodium hydroxide having a pH of 12.0. This reagent-foam mixture was selected to allow the placement of particulate limestone in larger fractures and the injection of liquid active ingredients in zones of small fractures.
- the sodium hydroxide provides immediate pH reduction, and the limestone provides long-term pH control. Hypothetical laboratory testing and/or field trials indicate the following ratios of the foaming agent and active ingredients or reagents produce the desired reagent-foam mixture:
- the resulting reagent-foam mixture contains about 0.93% solids by volume or about 3,640 cubic yards of solid active ingredients for the entire treatment outlined in this example.
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Abstract
Description
- The present application is a Divisional of U.S. patent application entitled “System and Method for Treating an Excavation Activity”, Ser. No. 13/211,074 filed on Aug. 16, 2011, all of which is hereby incorporated herein by reference in its entirety for all purposes. Any disclaimer that may have occurred during prosecution of the above-referenced application is hereby expressly rescinded.
- The present invention generally involves a composition for treating an excavation activity. In particular embodiments of the present invention, the composition may be used to treat byproducts and conditions associated with excavation activities to reduce acid rock drainage and/or recover valuable resources.
- Byproducts and conditions associated with excavation activities are known to lead to the generation of various forms of environmentally harmful pollution. As used herein, excavation activities encompass not only conventional mining operations to locate and recover natural resources below the surface of the earth, but also any other operations that disrupt large areas of the natural surface and/or contour of land. For example, highway construction and other large commercial developments often produce the same byproducts and conditions as conventional mining operations and constitute excavation activities within the scope of the present inventions.
-
FIG. 1 provides an exemplary drawing of anexcavation activity 10 to illustrate various byproducts and conditions that may lead to the generation of various forms of environmentally harmful water pollution. The byproducts may include, for example, various forms of mineral processing waste, such as overburden 12, slag, gangue, and buried pyrite-bearingrock 14. The conditions may include, for example, the excavation site itself, draining adits,tunnels 16,abandoned pits 18, and mines. As shown inFIG. 1 ,rain water 20,runoff 22, and other sources of water may pass over and through various portions of theexcavation activity 10 and interact and react with the byproducts and conditions to produceundesirable water pollution 24. Theundesirable water pollution 24 generally gravity drains through theexcavation activity 10 until it reaches an impermeable barrier, such as a natural or man-madeliner 26, which eventually guides the water pollution to an outfall, such as a stream or underground well or ground water infiltration/recharge zone. - The
water pollution 24 produced by excavation activities may be generically referred to as acid rock drainage (ARD) or acid mine drainage (AMD), and will hereinafter be collectively referred to as ARD. The combination of water, bacteria, and sulfide minerals exposed to air by excavation activities produces sulfuric acid, sulfates, iron and other metals in the ARD. For example, the following four generally-accepted chemical reactions describe the oxidation of sulfide minerals (represented by FeS2 as a proxy for all reactive sulfide minerals) that produces ARD: -
FeS2+7/2O2+H2O→Fe2++2SO4 2−+2H+ 1. -
Fe2++¼O2+H+→Fe3++½H2O 2. -
Fe3++3H2O→Fe(OH)3+3H+ 3. -
FeS2+14Fe3++8H2O→15Fe2++2SO4 2−+16H+ 4. - As shown by the preceding equations, the elementary chemical ingredients required for the formation of ARD are air, water, and sulfide materials. As described below, bacteria can facilitate the formation of ARD. Once each elementary ingredient is present, the production of ARD may be predicted by a number of standard tests, including acid-base accounting tests, humidity cell tests, and column leach tests. For example, in a pH environment of less than approximately 4.5, naturally-occurring bacteria, such as acidithiobacillus ferro-oxidans and related microbes, may act as a catalyst and accelerate reactions 1, 2, and 4 above, lowering the pH even further. Hydrogen ions (H+) and ferric iron ions (Fe+3) may also accelerate the oxidation of other metal sulfides that may be present, releasing additional metals such as copper, lead, zinc, cadmium, mercury, and manganese into the ARD.
- An effective method for reducing and/or preventing ARD is to remove and/or isolate one or more of the elementary ingredients—air, water, sulfide materials, and/or bacteria—required for ARD production. For example, a generally accepted system and method for treating byproducts and conditions associated with an excavation activity is to disperse one or more active ingredients or reagents over the excavation site to react with one or more of the elementary ingredients. As shown in
FIG. 1 , however, the byproducts and conditions associated with excavation activities are often buried, widely dispersed, and otherwise inaccessible to direct application of the active ingredients, requiring a combination of closely-spaced boreholes, gravity, and voluminous amounts of water to transport the active ingredients to the affected areas to be treated. Although effective at reducing or preventing ARD for the areas actually reached, the water-dispersed active ingredients often fail to reach all of the byproducts and conditions requiring treatment before passing through the excavation site. Therefore, an improved system and method for reliably dispersing active ingredients to treat excavation activities would be useful. - Aspects and advantages of the invention are set forth below in the following description, or may be obvious from the description, or may be learned through practice of the invention.
- One embodiment of the present invention is a composition for treating an excavation activity that includes a reagent suspended in foam to form a reagent-foam mixture. The reagent is selected to react with at least one of sulfides or bacteria in waste rock or tailings materials to reduce acid rock drainage. The reagent includes at least one of limestone, dolomite, sodium bicarbonate, steel slag, fly ash, or sodium hydroxide.
- Another embodiment of the present invention is a composition for treating an excavation activity that includes a reagent suspended in foam to form a reagent-foam mixture. The reagent is selected to react with at least one of sulfides or bacteria in waste rock or tailings materials to reduce acid rock drainage. The reagent includes at least one of milk, sodium thiocyanate, bio-solids, sawdust, paper, or composted animal manure.
- The present invention may also include a composition for treating an excavation activity that includes a reagent suspended in foam to form a reagent-foam mixture. The reagent is selected to react with at least one of sulfides or bacteria in waste rock or tailings materials to reduce acid rock drainage. The reagent includes at least one of iron, copper, manganese oxide, zeolite minerals, peat, activated carbon, or organic resins.
- Those of ordinary skill in the art will better appreciate the features and aspects of such embodiments, and others, upon review of the specification.
- A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:
-
FIG. 1 is a simplified cross-section drawing of an exemplary excavation activity; -
FIG. 2 is a simplified block diagram of a system for treating an excavation activity according to one embodiment of the present invention; -
FIG. 3 is a simplified cross-section drawing of the excavation activity shown inFIG. 1 being treated according to one embodiment of the present invention; -
FIG. 4 is a simplified cross-section drawing of an excavation deposit being treated according to an embodiment of the present invention; and -
FIG. 5 is a simplified cross-section drawing of an excavation pit being treated according to an embodiment of the present invention. - Reference will now be made in detail to present embodiments of the invention, one or more examples of which are illustrated in the accompanying drawings. The detailed description uses numerical and letter designations to refer to features in the drawings. Like or similar designations in the drawings and description have been used to refer to like or similar parts of the invention.
- Each example is provided by way of explanation of the invention, not limitation of the invention. In fact, it will be apparent to those skilled in the art that modifications and variations can be made in the present invention without departing from the scope or spirit thereof. For instance, features illustrated or described as part of one embodiment may be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents.
- Various embodiments of the present invention provide a system and method for transporting and applying various gaseous, liquid, and/or solid active ingredients or reagents through natural or man-made porous and permeable media to treat an excavation activity to reduce and/or prevent water pollution, namely acid rock drainage (ARD), and/or facilitate valuable resource recovery. A stable foam slurry may be used to transport and apply the gaseous, liquid, and/or solid active ingredients or reagents. In particular embodiments, the system and method may be used at or with an excavation activity, including zones adjacent to the excavation activity and/or excavation deposits, to reduce and/or prevent the spread of ARD. Although described generally in the context of treating and/or preventing acid rock drainage associated with mining activities, one of ordinary skill in the art will appreciate that embodiments of the present invention may be readily adapted to treat virtually any excavation or mineral processing activity to reduce and/or prevent the spread of undesirable contamination.
-
FIG. 2 provides a simplified block diagram of asystem 30 for treating anexcavation activity 32 according to one embodiment of the present invention. As previously described, theexcavation activity 32 may encompass byproducts and conditions associated with conventional mining operations as well as any other operations that disrupt large areas of the natural surface and/or contour of land. The byproducts and conditions may comprise porous and permeable materials, such as broken or fractured geological rock formations, ore, ore concentrates, coal, mine tailings, mine waste, slag, sand, or soil. Metallurgical processes, natural chemical changes such as oxidation, and/or biological activity may act on the porous and permeable materials to produce ARD, as previously described. Alternately, or in addition, the byproducts and conditions may contain valuable constituents, such as gold, silver, the platinum group metals, uranium, copper, lead, zinc, or any element that could economically be recovered from ore either found in place or excavated from the ground and subjected to conventional metallurgical processes for economic recovery. - As shown, the
system 30 generally includes adistribution network 34 in fluid communication with theexcavation activity 32. Thedistribution network 34 may be proximate to or remote from theexcavation activity 32 and may comprise any suitable system for conveying or transporting a fluid to theexcavation activity 32. For example, as shown inFIG. 2 , thedistribution network 34 may comprise apiping system 36 and one ormore pumps 38 or blowers that provide fluid communication between one or more supply tanks and theexcavation activity 32. Thepiping system 36 may connect, for example, one or more of asurfactant tank 40, aliquid reagent tank 42, acompressor 44, and/or asolid reagent tank 46 to theexcavation activity 32. In this manner, the various tanks may supply one or more active ingredients or reagents to theexcavation activity 32 to remove and/or isolate one or more of the elementary ingredients—air, water, sulfide materials, and/or bacteria—required for ARD production. - The
surfactant tank 40 may supply afoaming agent 48 to thedistribution network 34 to create a stable foam media for transporting or conveying one or more active ingredients or reagents to theexcavation activity 32. As used herein, “foam” includes any two-phase fluid comprised of a liquid and a gas partitioned by a surfactant (e.g., soap) into bubbles. The foamingagent 48 may comprise, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, natural surfactants derived from animal proteins, and/or combinations thereof. Theactual foaming agent 48 and the active ingredients it carries will be customized for each application based on the objective of the application, the chemical makeup, physical condition, and microbiological suites present, and the degree of saturation of the polluting or resource-grade materials. It should be understood by one of ordinary skill in the art that various surfactants are contemplated within the scope of the present invention, and the present invention is not limited to any particular surfactant unless specifically recited in the claims. - The
liquid reagent tank 42,compressor 44, and/orsolid reagent tank 46 may supply one or more active ingredients or reagents to mix with the foamingagent 48, with the actual active ingredients or reagents selected to react with one or more of the elementary ingredients—air, water, sulfide materials, and/or bacteria—required for ARD production. For example, theliquid reagent tank 42, if present, may supply one or more liquid active ingredients orreagents 50 selected to react with one or more of the elementary ingredients. Theliquid reagent tank 42 may supply a liquid bactericide selected to react with bacteria at theexcavation activity 32 to reduce and/or prevent the production of ARD. Possible bactericides include, for example, sodium lauryl sulfate, waste milk or other dairy by-products, bi-polar lipids, and/or sodium thiocyanate. Alternately or in addition, theliquid reagent tank 42 may supply solutions, such as sodium hydroxide and/or hydrated lime solutions, selected to adjust the pH at theexcavation activity 32. In still further embodiments, theliquid reagent tank 42 may supply solutions, such as sodium cyanide, thiourea, sodium hypochlorite, and/or hydrogen peroxide, selected to dissolve or leach precious metals from theexcavation activity 32. By way of further example, theliquid reagent tank 42 may supply solutions selected to coat theexcavation activity 32 and isolate the excavation minerals from air and/or water. For example, a solution of dissolved potassium permanganate has been shown to coat particulate mine waste materials with a layer of manganese dioxide and thus isolate pyrite-bearing rocks from air and water to prevent the production of ARD. Similarly, solutions of dissolved phosphate have been shown to complex with dissolved iron and starve bio-oxidation of pyrite through disruption of the kinetics of equations 2, 3, and 4 previously discussed. - The
compressor 44, if present, may similarly supply one or more gaseous active ingredients orreagents 52 selected to react with one or more of the elementary ingredients. For example, thecompressor 44 may supply carbon dioxide, nitrogen, or other inert gases that can displace oxygen proximate to the byproducts and conditions associated with theexcavation activity 32, thereby interfering with or preventing one or more of the chemical reactions known to produce ARD. Alternately or in addition, thecompressor 44 may supply hydrogen sulfide which, in addition to displacing oxygen, may also immobilize heavy metals present in solution at theexcavation activity 32. - The
solid reagent tank 46, if present, may similarly supply one or more solid active ingredients orreagents 54 selected to react with one or more of the elementary ingredients. For example, limestone, dolomite, cement kiln dust, steel slag, sodium bicarbonate, fly ash, and various pozzolanic materials may provide acid-neutralizing alkalinity to sulfide-bearing rock materials prone to produce ARD. Alternately, or in addition, slow-release bactericides may be used to suppress pyrite oxidizing bacteria, and/or organic materials, such as cellulose, wood, and paper, bio-solids, and/or animal and vegetable proteins may be used to suppress pyrite oxidation. Processed peat, natural peat, zeolite minerals, manganese oxides, and similar man-made products such as resins may be added to adsorb heavy metals. Additional solid active ingredients or reagents within the scope of the present invention may include zero valent iron, nano-scale iron, powdered iron oxy-hydroxides, and powdered copper which have the ability to chemically alter or detoxify dissolved pollutants. - As shown in
FIG. 2 , the various liquid, gaseous, and/or solid active ingredients or 50, 52, 54 are mixed or added to thereagents foaming agent 48 to form a reagent-foam composition ormixture 56. For example, afoam tube 58 and/or amixer 60 may be included in thedistribution network 34, as needed, to homogeneously mix or prepare the reagent-foam mixture 56. The actual active ingredient or reagent mixed with the foamingagent 48 will depend on the actual conditions at theexcavation activity 32. For example, Table I below identifies various active ingredients or reagents that may be selected to react with one or more of the elementary ingredients—air, water, sulfide materials, and/or bacteria—required for ARD production: -
TABLE I Elementary Ingredient Reagent Anticipated Reaction Air Fresh or composted wood chips, Consumes oxygen by sawdust, or cellulose organic decay Mushroom compost Animal & vegetable protein Bio-solids Paper products Nitrogen Displaces air/oxygen Carbon Dioxide Hydrogen Sulfide Displaces air & forms metal sulfides Water Potassium permanganate Coats reactive solutions surfaces to render Keeco Mix (micro-silicate them impermeable encapsulation material) Paint (latex or oil-based) or other water-resistant coating material Sulfides Limestone Neutralize acidity Dolomite Kiln dust Sodium bicarbonate Fly ash Flue gas desulfurization Coal combustion by-products Pozzolanic materials (cement) Steel slag Lime solution Sodium hydroxide solution Ammonia solution Bacteria Sodium lauryl sulfate solution Bactericide Sodium lauryl sulfate Milk Bi-polar lipids Phosphate solution Sodium thiocyanate solution Composted animal manure Inoculate polluting Municipal sewage bio-solids materials with beneficial Natural soils from wetlands bacteria Keeco Mix (micro-silicate encapsulation material) - Alternately, or in addition, Table II below identifies various active ingredients or reagents that may be selected to react with one or more heavy metals or other pollutants to facilitate recovery, detoxification, and or immobilization:
-
TABLE II Pollutant Reagent Anticipated Reaction Heavy Metals (e.g., Zero Valent Iron Adsorb dissolved Cd, Hg, Pb) or Nano-scale iron metals to the reagent Base Metals (e.g., Iron oxy-hydroxide Cu, Zn, Fe) powder Copper powder Manganese oxide minerals Peat (processed & natural) Zeolite minerals Organic resins Activated carbon Dissolved and/or Zero Valent Iron Convert toxic dissolved volatile organic Nano-scale iron organic carbon compounds compounds to harmless compounds Sodium cyanide Bleach (sodium Detoxify cyanide leach solutions hypochlorite solution) in gold mining Hydrogen peroxide solution Sulfur dioxide Sodium cyanide Sodium cyanide Leach gold or silver leach solution from ore Buffered carbonate Sodium bicarbonate Leach uranium solution from ore Thiourea leach H2NCSNH2, an Leach gold or silver solution organic compound from ore soluble in water Sulfuric acid H2SO4 Leach copper or uranium leach solution from ore - As shown in
FIG. 2 , the reagent-foam composition ormixture 56 may be dispersed over theexcavation activity 32 using standard grouting technology such as packers, specialized grout casing, or foam-retaining bulkheads for large underground mine voids, as desired. At the point of introduction, the reagent-foam mixture 56 expands omni-directionally (upward, downward, and circumferentially) as an advancing front that coats and saturates the porous and permeable materials present at theexcavation activity 32. The grout tubing or packers may be repositioned as needed to allow the injection point(s) to be varied to disperse the reagent-foam mixture 56 in the desired zone. - Preliminary tests have shown that the foaming
agent 48 effectively penetrates porous and permeable materials commonly found atexcavation activities 32, leaving a coating on the materials when the foam dissipates. For example, the exothermic reactions associated with the oxidation of sulfides frequently results in warm, dry zones that will quickly dissipate the moisture from the foam, precipitating a higher concentration of active ingredients or reagents at that particular location that suppress additional chemical or bacterial oxidation. In addition, the precipitated active ingredients or reagents do not obstruct or otherwise clog the porous and permeable materials, allowing for subsequent applications over time without a loss of effectiveness. As a result, multiple reagents may be applied in sequence, if desired, using the same injection point ordistribution network 34. These and other benefits indicate that the foamingagent 48 provides superior transport and deposition characteristics compared to conventional liquid dispersal techniques, while requiring substantially less water. - As further shown in
FIG. 2 , thesystem 30 may further include aliner 62 and/or acollection network 64 in fluid communication with theexcavation activity 32. Theliner 62 may comprise a natural or man-made surface beneath at least a portion of theexcavation activity 32 that provides a barrier for any water draining from theexcavation activity 32. Alternately, or in addition, thecollection network 64 may comprise perforated drainage pipes that collect and channel water draining from theexcavation activity 32 to acollection point 66 for additional processing and disposal. -
FIGS. 3-5 provide simplified drawings of various excavation activities being treated according to embodiments of the present invention. For example,FIG. 3 shows the use ofmultiple injection ports 68 to distribute and disperse the reagent-foam mixture 56 into a buriedexcavation deposit 70. The omni-directional expansion of the reagent-foam mixture 56 through theexcavation deposit 70 allows for complete coverage of theexcavation deposit 70 usingfewer injection ports 68, with a corresponding reduction in water consumption. As shown inFIG. 4 , the omni-directional expansion of the reagent-foam mixture 56 allows thesystem 30 to treat asurface excavation deposit 72 from the bottom. Expansion of the injected reagent-foam mixture 56 beneath theexcavation deposit 72 causes upward dispersal and distribution of the selected active ingredients or reagents. Finally,FIG. 5 shows use of thesystem 30 to economically treat localized or isolated excavation activities such asfractures 74 or other shallow geological disturbances in anexcavation pit 76. As shown, thedistribution network 34 may facilitate precise application of the reagent-foam mixture 56, thereby reducing the consumption of water and active ingredients in the process. - One of ordinary skill in the art can readily determine with minimal experimentation preferred combinations and ratios of the various foaming agents and active ingredients or reagents depending on the particular excavation activity. Based on the enhanced distribution and dispersal characteristics of the foaming
agent 48 compared to conventional distribution and dispersal methods, it is anticipated that the fractional percentage of active ingredients or reagents in the reagent-foam mixture will be substantially less than needed in conventional methods. For example, it is anticipated that the active ingredients or reagents, particularly the solid active ingredients or reagents, will comprise less than 10%, and in some embodiments less than 5%, 2%, or 1%, by volume of the reagent-foam mixture, resulting in substantial savings. Nonetheless, the following hypothetical examples are provided for illustration and not limitation of the present invention. - An excavation activity comprises a twenty acre excavation deposit containing a pollution generating pyrite-bearing rock zone that has been delineated through borehole and geophysical data. The excavation deposit has a total volume of approximately 3.2 million cubic yards, of which approximately one-third or 1.1 million cubic yards is void space. Approximately 25% of the excavation deposit volume (i.e., approximately 806,000 cubic yards) contains the pollution generating pyrite-bearing rock, with approximately 266,000 cubic yards of voids in this pollution-generating zone.
- The designed distribution network includes a commercial air compressor with a capacity of 100 cubic feet per minute and a standard pressure of 100 pounds per square inch, a pump with a capacity from 5 to 20 gallons per minute, tanks, and other conventional foam-generating equipment connected generally as shown in
FIG. 2 . The designed piping system includes 4-inch diameter pipe installed in a plurality of boreholes drilled into the approximate geometric centroids of the pyrite-bearing rock zones. The annulus between the pipe and the surrounding pyrite-bearing rock zones is filled with sand or concrete. - The active ingredients or reagents for this application are selected to provide an anti-bacterial action, acidic pH neutralizing actions, and oxygen depletion actions. The selected anti-bacterial reagents include sodium lauryl sulfate (which is also the foaming agent); waste milk (nutrient for beneficial bacteria to out-compete pyrite-oxidizing bacteria); and bio-solids (bacterial inoculum). The selected acidic pH neutralizing reagent is finely crushed limestone powder having a grain size from approximately 20 mesh (0.84 mm) to approximately 200 mesh (0.074 mm). The selected oxygen-depleting reagent is a fine-grained sawdust waste product having a nominal diameter of approximately 20 mesh (0.84 mm). Hypothetical laboratory testing and/or field trials indicate the following ratios of the foaming agent and active ingredients or reagents produce the desired reagent-foam mixture:
-
Volume in 1 cubic Component yard of mixture Percent by Volume Water 3.20 cubic feet 11.9% Waste milk 0.17 cubic feet 0.6% Bio-solids 0.15 cubic feet 0.6% Crushed limestone 0.80 cubic feet 3.0% Sawdust 0.05 cubic feet 0.2% Surfactant (SLS) 0.21 cubic feet 0.8% Gas (air) 22.42 cubic feet 83.0% Totals 27.0 cubic feet 100% - The resulting reagent-foam mixture contains about 3.85% solids by volume or about 10,238 cubic yards of solid active ingredients for the entire treatment outlined in this example.
- An excavation activity comprises a 200 acre abandoned open pit mine site that exposes a fractured, pyrite-bearing rock zone that has been delineated through borehole, geochemical data, and geologic interpretation. The fracture zone is a combination of natural geological conditions and over-break from blasting activity in creating the excavation. The zone of intense fracturing extends at least 100 feet into the excavation wall rock and through the floor of each bench, as shown in
FIG. 5 . The fractures constitute less than 1% of the total rock mass volume. Every linear foot of excavation bench includes an estimated 150 cubic yards of rock, of which 1.5 cubic yards are void space. There are 2 miles of bench in the pyrite-rock exposure, resulting in 15,840 cubic yards of fracture that requires treatment in this pollution-generating zone. - The designed distribution network includes a commercial air compressor with a capacity of 100 cubic feet per minute and a standard pressure of 100 pounds per square inch, a pump with a capacity from 5 to 20 gallons per minute, tanks, and other conventional foam-generating equipment connected generally as shown in
FIG. 2 . The designed piping system includes 2-inch diameter pipe installed in a plurality of boreholes drilled into the pyrite-bearing fractured rock zones. The annulus between the pipe and the surrounding pyrite-bearing rock zones is filled with cementitious grout to seal the pipe into the rock mass. - The active ingredients or reagents for this application are selected to provide an anti-bacterial action and acidic pH neutralizing actions. The anti-bacterial ingredients include sodium lauryl sulfate (which is also the foaming agent); waste milk (nutrient for beneficial bacteria to out-compete the pyrite oxidizing bacteria); and bio-solids (bacterial inoculum). The selected acidic pH neutralizing reagent is finely crushed limestone powder having a grain size from approximately 200 mesh (0.074 mm) to approximately 400 mesh (0.037 mm) and a solution of sodium hydroxide having a pH of 12.0. This reagent-foam mixture was selected to allow the placement of particulate limestone in larger fractures and the injection of liquid active ingredients in zones of small fractures. The sodium hydroxide provides immediate pH reduction, and the limestone provides long-term pH control. Hypothetical laboratory testing and/or field trials indicate the following ratios of the foaming agent and active ingredients or reagents produce the desired reagent-foam mixture:
-
Volume in 1 cubic Component yard of mixture Percent by Volume Water 2.53 cubic feet 9.4% Waste milk 0.84 cubic feet 3.1% Bio-solids 0.0125 cubic feet 0.05% Crushed limestone 0.24 cubic feet 0.9% Sodium Hydroxide 0.0125 cubic feet 0.05% Surfactant (SLS) 0.21 cubic feet 0.8% Gas (air) 23.17 cubic feet 85.8% Totals 27.0 cubic feet 100% - The resulting reagent-foam mixture contains about 0.93% solids by volume or about 3,640 cubic yards of solid active ingredients for the entire treatment outlined in this example.
- This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other and examples are intended to be within the scope of the claims if they include structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
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- 2011-12-07 MX MX2014001796A patent/MX2014001796A/en unknown
- 2011-12-07 PE PE2014000213A patent/PE20141912A1/en active IP Right Grant
- 2011-12-07 AP AP2014007500A patent/AP2014007500A0/en unknown
- 2011-12-07 CA CA2845211A patent/CA2845211C/en active Active
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- 2011-12-07 EA EA201490468A patent/EA201490468A1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105057314A (en) * | 2015-08-23 | 2015-11-18 | 长春黄金研究院 | In-situ bioremediation processing method for cyanide-contained tailing slag |
| CN107570524A (en) * | 2017-09-08 | 2018-01-12 | 芜湖市中瓷环保材料技术有限责任公司 | The processing method of copper tailing |
Also Published As
| Publication number | Publication date |
|---|---|
| PE20141912A1 (en) | 2014-12-01 |
| CA2845211A1 (en) | 2013-02-21 |
| MX2014001796A (en) | 2014-07-30 |
| CL2014000377A1 (en) | 2014-10-10 |
| US8985902B2 (en) | 2015-03-24 |
| US20130045052A1 (en) | 2013-02-21 |
| CO6970579A2 (en) | 2014-06-13 |
| EA201490468A1 (en) | 2014-07-30 |
| WO2013025233A1 (en) | 2013-02-21 |
| AU2011374961A1 (en) | 2014-03-06 |
| CA2845211C (en) | 2019-01-08 |
| AP2014007500A0 (en) | 2014-03-31 |
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