WO2011056548A2 - Système de valorisation de déchets par torche d'oxygène et récupération par un acide - Google Patents

Système de valorisation de déchets par torche d'oxygène et récupération par un acide Download PDF

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WO2011056548A2
WO2011056548A2 PCT/US2010/054056 US2010054056W WO2011056548A2 WO 2011056548 A2 WO2011056548 A2 WO 2011056548A2 US 2010054056 W US2010054056 W US 2010054056W WO 2011056548 A2 WO2011056548 A2 WO 2011056548A2
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nitric acid
metal
waste
acid bath
metals
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WO2011056548A3 (fr
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James R. Akridge
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C22B11/042—Recovery of noble metals from waste materials
    • C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/065—Nitric acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • Electronic devices and batteries represent a substantial yearly tonnage of use of metals, metal oxides, plastics, glass, and other materials. Metals of the 3d, 4d, 5d transition series and their oxides are used considerably in these applications.
  • computer monitors can contain lanthanide series oxides used as phosphors coated on the glass surface.
  • Flat panel display devices can contain gold, silver, nickel and platinum in the circuit boards and chips.
  • some electronic devices, such as fluorescent lights, in addition to the phosphor coatings on the interior surface of the glass contain mercury and therefore cannot lawfully be placed in landfill. Mercury can be toxic if it leaches into groundwater or if it contaminates soil, and has value as a raw material if recovered.
  • Common methods to recover metals from primary alkaline and carbon/zinc batteries is to recycle them by either (1) using them as feed in an electric arc furnace, or (2) dissolving them in sulfuric acid to ultimately obtain metal sulfates.
  • Metal sulfates and sulfites themselves are generally not usable and must be converted into metal oxides or carbonates. Thus, sulfates or sulfites must preferably be further processed to be most useful as chemical feed for chemical industries.
  • Electronic devices such as computers, computer terminals, radios, VCR players, DVD players, CD players, and cellular telephones, present a somewhat more complex waste issue (all of such devices, other waste electronic devices and waste batteries are collectively referred to herein as "e- waste") because of the numerous types of devices, the immense physical volume of the devices, the various types of metal used in the various types of devices, and the large volume of each device compared to the amount of metal to be recovered from the device.
  • a known method for recycling electronic devices is disassembly to extract the most valuable metal-containing components, and refurbishing them reuse for those devices that can be recycled in this fashion. When disassembled, the various parts are stripped, sorted into common piles and then each type of scrap is shipped to a recycler specializing in disposing of, or reclaiming, that type of scrap.
  • Non-oxidizing mineral acids such as sulfuric acid, phosphoric acid, and hydrochloric acid are all non-oxidizing mineral acids that can be used to dissolve transition metals. In doing so, they liberate hydrogen from the acid and require the continuous addition of more acid.
  • nitric acid a powerful oxidizing acid
  • dissolution agent for e-waste would have several advantages. First, many, if not all, metal nitrates formed by dissolution of the metals in nitric acid are soluble in the nitric acid. Second, the nitric acid dissolution of metals does not liberate hydrogen (with only few exceptions, and those exceptions do not, or rarely, include 3d, 4d or 5d transition metals or the lanthanide series, which are commonly found in e-waste) and thus does not destroy the acid in the manner described above.
  • a system according to the invention is designed to carry out one or more of the processes set forth herein and optionally includes one or more of a (1) permanganate-based solvent regeneration process and system, (2) zinc generation process and system, (3) Si0 2 particulate generating process, (4) process to grind waste plastic, and (5) process to resolubilize metal oxides and/or metal nitrates and precipitate metal oxides as pigments.
  • the intent of the invention is to create a method to reclaim waste that includes metal, and most preferably e-waste, in a profitable manner.
  • Nonmetallic waste such as phenolic circuit boards, wire insulation bundles, electronic chips, etc.
  • Nonmetallic waste can also optionally be destroyed and/or reclaimed as a clean raw material that can be returned to commercial use through utilization of the invention.
  • the invention can recycle many metals, and optionally other materials, in essentially any type of waste.
  • the process and system of the invention may also incorporate a reclaim and reuse of the nitrous oxide liberated from nitric acid dissolution of components of the waste, thus
  • a process and system according to the invention could be coupled to or include a potassium permanganate manufacturing process/facility.
  • Potassium (or sodium) permanganate may be used for reoxidation of the solvent decomposition products to regenerate nitric acid, as explained further below.
  • the invention uses nitric acid to dissolve most metals (excluding gold and platinum, which can still be reclaimed utilizing the process of the invention) and destroys or cleans nonmetallic components that are placed in the nitric acid bath.
  • the non-soluble but clean material whether it be plastic, glass or any other material not dissolved by the nitric acid can be separated by filtration or other suitable method and reused or disposed.
  • the glass generated by the recycling facility can be further sized, such as by grinding, for use as a road paving material.
  • the metallic nitrates contained in solution in the nitric acid are selectively precipitated as oxides or carbonates by appropriate chemical treatment and can then be sold into commerce as metal oxides, carbonates or nitrates, or be further treated to create elemental metals in some cases.
  • potassium permanganate is typically prepared by extraction of natural Mn0 2 ore (pyrolucite), which is cleaned to remove gangue (mostly Si0 2 ), then ground to a very fine particle size, then reacted in molten KOH in the presence of oxygen and then subject to subsequent electrochemical oxidation to create potassium permanganate:
  • a process and system of the invention could also include or be coupled to a process and system used for manufacturing one or more of zinc phosphate, zinc orthophosphate or other zinc chemicals for the use in water treatment facilities, or in the manufacture of batteries.
  • Zinc phosphates of various types are used for passivation of domestic drinking water delivery piping systems. Zinc also has uses in metallurgy (brass), medical as supplements for dietary use, as calamine (treat skin rash), water pipe treatment, and other commercial applications.
  • Primary alkaline and carbon zinc batteries are about 70% or more by volume of combined manganese oxides (which can be used as the starting materials for preparation of potassium permanganate) and zinc metal and zinc oxides (which can be used as starting material for zinc chemicals for water treatment).
  • Primary alkaline battery cells use about 40% KOH as electrolyte.
  • a permanganate generating process and system and/or a zinc phosphate process and system would make sense because spent alkaline battery cells could provide a low cost and high purity source of raw materials (i.e., zinc oxide and manganese dioxide) for both processes.
  • the use of the output of the permanganate facility which is potassium manganate (the precursor to potassium permanganate) or potassium permanganate, may be used to regenerate (oxidize) the nitrous oxide resulting from the utilization of the nitric acid dissolution of metals (and optionally, non-metals) from waste and most particularly e-waste.
  • the nitrous oxide is oxidized to nitrogen dioxide by permanganate or manganate. This oxidation of nitrous oxide results in the reduction of permanganate or manganate and generation of manganese dioxide as a by-product of the use of manganate or permanganate as the oxidizing compound.
  • Manganese dioxide is the starting material for the manufacturing of potassium permanganate and/or potassium manganate manufacturing process. Therefore, nitrous oxide generated from the action of nitric acid on the e-waste and manganese oxides generated from the regeneration of nitrous oxides could be used as raw materials for the nitric acid and
  • potassium permanganate processes. Alternately, potassium permanganate reduced to potassium
  • manganate by oxidizing NO x is a better starting material for the generation of potassium permanganate through electrolysis of potassium manganate generated from the oxidation of nitrous oxides.
  • Fluorescent lighting tubes of any type can also be recycled with the glass being cleaned for reuse or use in other processes in commerce.
  • the resulting solution contains the metal phosphors (generally metals of the lanthanide series on the Periodic Table), the glass and the mercury.
  • the metals (from the metal phosphors) and mercury can be precipitated and reused and the cleaned glass can be filtered from the nitric acid bath and reused.
  • Figure 1 illustrates a recycling process of the present invention.
  • FIG 2 illustrates another recycling process of the present invention.
  • Figure 3 illustrates another recycling process of the present invention.
  • FIG. 4 illustrates another recycling process of the present invention.
  • Figure 5 illustrates a system for recycling waste according to the invention.
  • Figure 6 illustrates a system for recycling waste according to the invention.
  • Figure 7 illustrates a system for recycling waste according to the invention.
  • This invention can be extended to sodium permanganate by the use of NaOH to increase the pH of the bath.
  • nitric recycle it is desireable to capture the nitrous oxide gas produced when organic material, any metal (the most commonly found in e- waste; copper, silver, lead, iron, gold, platinum, nickel, or tin) react.
  • Nitrous oxide (NOx) is industrially oxidized to NO 2 via the Ostwald process.
  • the Oswald process is normally fed with ammonia (NH 3 ) and uses Pt/Rd catalyst and thermal reaction to generate ultimately NO 2 , which is then dissolved in water to form nitric acid.
  • the Ostwald process is not a generally applicable process for regeneration of nitric acid from nitrous oxides generated from extraction of waste metals reacting with nitric acid.
  • sulfur and sulfur compounds or arsenic
  • the Ostwald catalyst would be poisoned because noble metals used as catalysts (Pt, Rd, Ru, etc. or combinations of these) preferentially react with sulfur and arsenic compounds thus destroying the catalytic action.
  • the catalyst becomes ineffective in the Ostwald process if exposed to sulfur or sulfur containing material (or arsenic compounds). Therefore, though using the Ostwald process for
  • a recycle process according to the invention using the Ostwald process coupled to a nitric acid extraction process would be waste stream specific or at minimum the NOx stream generated by the dissolution action of nitric acid would have to be scrubbed for removal of sulfur (or arsenic) compounds due to the negative effect of sulfur and/or arsenic compounds on the Ostwald catalyst.
  • the Ostwald process would require a substantial installation infrastructure added to the nitric acid process dissolution factory.
  • the invention can also optionally include a permanganate process, either as part of or coupled to a process according to the invention. Such as process is illustrated in Figures 1-3.
  • K 2 Mn0 4 produced from Mn0 2 +KOH+0 2
  • K 2 Mn0 4 is cheaper than KMn0 4 and will oxidize NO to N0 2 ).
  • Mn0 2 is used to make more K 2 Mn0 2
  • the KN0 3 generated from the above equation can be treated with H 2 S0 4 to create more nitric acid and K 2 S0 4 , which can be used as fertilizer:
  • Electrolysis The N0 2 would then be dissolved in water to form nitric acid, which could be returned to the recycling process of the invention.
  • the highest cost processes in the recycle of batteries is the grinding and washing to remove electrolytes and other added compounds so the process can extract the valuable metals and metal oxides contain within.
  • the washed and ground battery scrap is then extracted in nitric acid, dissolving all the metal and metal oxides except undischarged manganese dioxide which is not reacted and falls to the bottom of the leach tank.
  • the undissolved manganese dioxide can be returned to the permanganate process as a starting raw material.
  • manganese nitrates and zinc nitrates contained in the leach solution can be precipitated as manganese dioxide and zinc oxide, which are used in the permanganate and water treatment industries respectively.
  • Sulfuric acid is a non-oxidizing leach acid used in some battery recycling.
  • the issue with non-oxidizing mineral acids is that the metal compounds resulting are sulfides, sulfites, sulfates if sulfuric acid is used or chlorides if hydrochloric acid is used or phosphates if
  • phosphoric acid is used which are metal compounds that are not starting materials for the
  • non-oxidizing mineral acids leave a non-dissolved residue as not all metals are soluble in these mineral acids.
  • Another issue with non-oxidizing mineral acids is that the dissolution of metals using such acids generates hydrogen. The acid is destroyed and cannot be reclaimed so the process continuously must be replenished with more acid and the hydrogen likely goes to waste. The process is not universally useful and it may be preferable financially to landfill rather than use non-oxidizing mineral acids for recycling.
  • the process of the invention avoids all or at least some of the above issues since it forms metal nitrates, which are soluble in nitric acid. Further, hydrogen is not released by nitric acid dissolution of metals (with only exceptions that are non-issues in e- waste). Therefore, the current invention forms metal nitrates and the resulting metal nitrate-containing solution can then be treated, if desired, to precipitate metal oxides and/or carbonates.
  • leach bath can, in many cases be sold as oxides, or can be heat treated to form pure metals.
  • leach bath can, in many cases be sold as oxides, or can be heat treated to form pure metals.
  • mother liquor each refer to a nitric acid bath including one or more metal nitrates
  • AgO can be heated to get silver metal or alternately iron filings can be added to the leach bath and silver metal will precipitate. This is a redox reaction since iron is higher in the electromotive series than silver.
  • CuO can be sold directly or alternately iron filings can be added to the leach solution and copper metal is precipitated as iron is more electromotive than copper.
  • Fe 2 0 3 can be sold directly and would be the first oxide recovered via pH shift of the mother liquor to a pH ⁇ 3 which would cause Fe 2 0 3 to precipitate. Simple filtration would then separate the iron oxides from the solution.
  • Mn0 2 if alkaline or carbon/zinc batteries are recovered precipitates from the bath since Mn0 2 is not dissolved by nitric acid unless it is in contact with a reducing agent such as iron metal or other anode metal. The Mn0 2 would be present if the alkaline or carbon/zinc batteries are not fully discharged.
  • KN0 3 can be used to generate nitric acid by
  • KN0 3 can be sold for fertilizer. Another use is to heat
  • system 2 is a block diagram illustrating four tanks (although any suitable number of tanks can be used). Nitric acid is in tank 1 and scrap is added to tank 1.
  • the solution with dissolved metals can then be moved to different tanks and different metal oxides and/or metal nitrates can be precipitated and/or collected in different tanks. Further, metals that are not dissolved by nitric acid may be dissolved by the addition of other chemicals in tanks 1, 2, 3 and/or 4. Any method or system described herein could be a batch, continuous or semi-batch process.
  • system 3 is basically the same as system 2 except that different waste feeds are placed into different tanks. Since waste feeds are likely not pure in terms of metal content there would likely still be a need to precipitate different metal oxides and metal nitrates in different tanks. Alternatively, a single tank could be used and the different metal oxides and metal nitrates could be precipitated at different times, or potentially at the same time if a convenient sorting method is used thereafter.
  • the process of destruction of the metal containing, metal oxide containing or nonmetal waste material generates nitrous oxides that are collected above the dissolution bath.
  • the nitrous oxide is reoxidized to nitrogen dioxide which is dissolved in water resulting in nitric acid which is used to dissolve more waste material.
  • the manganese oxides generated from the regeneration of nitric acid are returned to the permanganate process for manufacture of additional oxidant for regeneration of nitric acid.
  • potassium permanganate can be reduced to potassium manganate by NOx and then electrolytically reoxidized to the
  • the zinc and manganese oxides are sent to the permanganate process if they are manganese oxides and if zinc oxides are sent to become zinc chemicals used for water treatment facility protection and maintenance.
  • plastic casings for example, those that surround CRT monitors, desktop computers, casing around PC's, DVD's, TV's, and radios
  • the separation will be preferably be mechanical via crushing the devices or otherwise gaining access to the interior and the broken casing will be rejected via magnetic separation or some other manner that does not include hand sorting.
  • the invention preferably utilizes a base to raise the pH in a nitric acid bath (for instance, KOH, NH 3 , ZnO, etc. can all be used to increase pH) to precipitate metals that have been solubilized in the bath.
  • a base for instance, KOH, NH 3 , ZnO, etc. can all be used to increase pH
  • manganese oxides were present in the bath (for example, those present in spent battery cells) they would be recovered and sent for processing and be oxidized to ⁇ 2 ⁇ 0 4 in KOH molten salt in the presence of oxygen in the process making permanganate as end product. Subsequent electrochemical oxidation would produce KMn0 4 (potassium permanganate) from potassium manganate.
  • the zinc compounds would be precipitated as zinc hydroxides. These can be subsequently processed into zinc oxides, zinc phosphates or any other zinc compound desired.
  • the preferred goal would be to utilize the zinc compounds through added processing to manufacture zinc chemicals used in water treatment facilities or for water transport piping protection from bacterial growth. Passivation of water system infrastructure piping requires zinc compounds. There are many other uses for zinc metal and zinc compounds as well.
  • the mother liquor also contains metals from dissolution of electronic components such as silver, lead, tin, nickel, iron, mercury, arsenic, platinum, aluminum, indium, lanthanides such as lanthanum, prasodynium, neodinium, etc.
  • All 3d, 4d, 5d and lanthanide metals and oxides are dissolved in nitric acid and would be present in the mother liquor.
  • the mother liquor is treated by inorganic chemical processes to precipitate in succession the metals as oxides, carbonates or nitrates as desired.
  • iron present is precipitated as ferric oxide by raising the pH to approximately 3. Similar for all the other metals and lanthanides.
  • Some metals may not be separated by choice, for example, the lanthanides, as these can be used in combined form in commerce.
  • Gold and platinum do not dissolve in nitric acid and these may be recovered from the bottom of the dissolution vessel as pure metal in many cases.
  • the reason to treat batteries in a separate tank or process is because the metal values are more concentrated in batteries and the acid strength would have to be different, and the leaching characteristics of oxides (manganese oxides and zinc oxides) are different than for metal like copper, etc.
  • the e-waste enters the breaking/crushing, sorting and concentration facility and is mechanically organized into materials that go directly to recycle in plastics, aluminum metal casing, plated steel casing and so forth to the extent economically feasible. It may be required to first clean the e-waste, and that can be done in any suitable manner, such as by using a wash bath and use the wash water in the nitric recycle so dirty water or waste water is not generated.
  • the concentrated metal-containing e-waste (printed circuit boards, wire bundles, disc drives, crushed monitors, crushed flat panel displays, radio parts, etc.) is ground into pieces preferably not more than a centimeter on any side. This is then fed into the nitric acid bath. Nitric acid is very aggressive and dissolves copper, silver, tin, and finely divided iron, and other metals. Mercury, lead, and the 5d transition metals are not so active and will take longer to dissolve.
  • the nitrous oxides from the primary leach bath will preferably be continuously decanted from the leach bath, nitric acid will be re-added and the leach bath stirred as needed. Stirring can be done via atmospheric air pumped into the bath beneath the liquid from the bottom or any other suitable method.
  • the process and system may be closed with hoods over the leach tank(s) such that the nitrous oxides are captured in a gas handling system.
  • the nitrous oxides could then be lead via a gas-handling system into a reactor bed containing moist basic potassium manganate (or permanganate), where the nitrous oxide is oxidized to nitrogen dioxide.
  • the nitrogen dioxide would then be moved into a water bath where it would dissolve and react with water to form nitric acid.
  • manganese dioxide may be created as a result of the oxidation/reduction of the process. This manganese dioxide may optionally be returned to the permanganate process (if included) for making more
  • the Ostwald process for generation of nitric acid starts with ammonia that is oxidized to nitrogen dioxide using a noble metal-containing catalyst.
  • the production of nitric acid is linked to ammonia production.
  • the Haber Process is used to manufacture ammonia from nitrogen.
  • Ammonia is the raw starting material for the Ostwald Process.
  • the manufacture of nitric acid is nearly always coupled to and on the same site as the manufacture of ammonia process.
  • the Haber process can be used to feed the Ostwald Process for the manufacturing of nitric acid.
  • there is no need to install the Ostwald process with its associated problems of high temperature reaction of oxygen with nitrogen oxides to form nitrogen dioxide over a noble metal catalyst.
  • the presently described process using potassium manganage/potassium permanganate is generally applicable and much simpler.
  • the process of the invention includes or is coupled to a permanganate generation process, one potential benefit is the regeneration of nitric acid from the nitrous oxides collected from the leach bath, wherein the nitric acid is regenerated using the output from the permanganate process. This helps make recycle process environmentally friendly and sustainable because all or most things from the process are reclaimed. Additionally, it should lower the costs for each process.
  • batteries may optionally be included as waste or reclaimed in a separate system using the same process could add further benefits.
  • the increased metal values in batteries helps the recycle process according to the invention obtain more reclaim from the tonnage as batteries have a greater percentage of metal than other e- waste and the zinc and manganese dioxide and manganese oxide reclaimed from battery recycling using the invention optionally goes to a permanganate process as a raw material feed stock.
  • the non-metal waste such as plastic, glass (from CRT's, fluorescent tubes, etc.), Teflon insulation on the copper wires, will be essentially clean of metals.
  • This material can be reused in the appropriate industry or disposed. For example, ground clean glass can be used for the filling of potholes and repaying roads.
  • Au and Pt are not dissolved (unless a solution other than or in addition to nitric acid is used), but fall to the bottom of the leach bath. They can then be collected from the bottom of the tank containing the leach bath or can be solubilized using aqua regia, and later be
  • a process and system according to the invention may be batch, semi-batch or continuous.
  • the metals may be dissolved in one tank and precipitated in another, or different metals could be dissolved in different tanks and/or different metals could be precipitated in different tanks.
  • FIGs. 8- 11 Another exemplary method to convert and reuse nitrogen oxides generated by the use of nitric acid as described herein is by means of an oxygen torch. This is best shown in Figs. 8- 11.
  • the basic principle of the oxygen torch method is to mix NO x with oxygen (0 2 ), which can be supplied in any suitable manner, and then heat the mixture (or preheat the NO x and/or the oxygen) to form N0 2.
  • the N0 2 gas preferably goes to a quench vessel where it is mixed with water to form nitric acid (HN0 3 ), or the N0 2 is re-circulated into the nitric acid bath to form additional nitric acid.
  • FIGS 8 and 9 show block diagrams of an oxygen torch system according to the invention.
  • a nitric acid bath B in a reaction vessel R preferably contains nitric acid that dissolves metals as previously discussed in this application.
  • the nitric acid bath gives off NO x gas.
  • This ⁇ gas is then captured using any suitable means, such as a hood or a casing Rl over or on the vessel R that contains the nitric acid bath B.
  • the NO x gas is preferably preheated to about 500°F (although it can be preheated to any suitable temperature) by preheater 498.
  • the NO x gas is then mixed with oxygen as it enters a reaction zone 500 .
  • the oxygen is supplied as air, enriched air or 0 2 , and is introduced through a conduit C and mixed with the NO x prior to or at the same time as the gases enter reaction zone 500.
  • Reaction zone 500 can be any device that maintains or raises the temperature of the gas enough to preferably convert 90% or more, or 95% or more and most preferably 98% or more of the NO x to N0 2.
  • Reaction zone 500 is preferably an electric oven but can include a natural gas flame or other heating device.
  • Reaction zone 500 is preferably formed of or lined with refractory material because of the high temperatures present.
  • Reaction zone can be at any suitable pressure, but is preferably at atmospheric or slightly less than atmospheric pressure.
  • Figure 9 shows a block diagram, close-up view of the reaction zone 500.
  • a hood or casing Rl is positioned over reaction vessel R in order to capture NOx gas and transfer it through pipe 504.
  • a preheater 506 heats the NOx gas to about 500°F at about one atmosphere pressure. The preheated NO x continues through pipe 504 until it moves into reaction zone 500.
  • oxygen in any suitable form such as 0 2 , air or enriched air, enters reaction zone 500 through a conduit 510.
  • the oxygen preferably enters the reaction zone at ambient temperature and atmospheric pressure although it may be at any suitable temperature and pressure.
  • an igniter 512 which can be any device capable of generating a spark or flame, may be used to ignite the gas and cause it to react.
  • pipe 504 and conduit 500 open into a larger volume reaction zone space 514. This creates a lower pressure in reaction zone 510 to assist in igniting the gas and in moving the gas (utilizing a venturi effect) through reaction zone 500 to quench vessel 520.
  • fans may be used downstream of the reaction vessel 500 (or at any point) to assist in moving the gas.
  • reaction zone 500 The length L and diameter D of reaction zone 500 must be designed such that it is capable of properly converting the volume of NO x it must handle.
  • the gases may move into a quench vessel 520 where they are mixed with water, preferably by the water being sprayed onto the gas through nozzles 522, although the gas can be mixed with water using any suitable method.
  • the water sprayed onto the gas is preferably at ambient temperature and atmospheric pressure although any suitable temperature and pressure would suffice.
  • HNO 3 is formed. Excess water is removed and the HNO 3 can be reused in a process according to the invention.
  • quench vessel 520 if CO is present, it may be converted to C0 2 , and H 2 S would be converted to H 2 S0 4 , and only trace amounts of gas would exit quench vessel 520 (such amounts would not be harmful to the atmosphere). Any vapor or water that exits quench vessel 520 could be quenched again in another vessel and/or be condensed and be drained for further treatment, re-use or disposal.
  • the size and parameters of reaction zone 500 and quench vessel 520 would be selected based upon the amount and composition of the gas entering each, such parameters being known to those skilled in the art.
  • FIGs. 10 and 11 An alternative oxygen torch system is shown in Figs. 10 and 11 that relies on a venturi effect to move the gas through the system.
  • this system is the same as the previously described system except that it has full venturi-effect reaction zone 600 with larger space 614.
  • NO x is again preheated to about 500°F (the preheater is shown in Fig. 11) and the preheated No x is mixed with oxygen in reaction zone 600.
  • reaction zone 600 expands to create a low pressure zone and a venturi effect to pull the gases through the system.
  • reaction zone 600 is the same as reaction zone 500.
  • Igniter 512 may also be used in zone 600.
  • Quench vessel 520 is again preferably utilized.

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  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
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  • Metallurgy (AREA)
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Abstract

L'invention porte sur un procédé et un système pour retirer des métaux à partir de déchets, en particulier de déchets électroniques (ou « e-déchets »). Le procédé comprend d'une manière générale les étapes consistant à dissoudre au moins une partie des métaux provenant des déchets, puis à amener au moins une partie des métaux à précipiter sous la forme d'oxydes métalliques et/ou de nitrates métalliques. Le système peut comprendre de multiples réservoirs ou emplacements pour dissoudre les métaux et/ou faire précipiter les métaux, de préférence sous la forme d'oxydes métalliques ou de nitrates métalliques. Le procédé et le système permettent également de récupérer du gaz pour la régénération d'acide nitrique.
PCT/US2010/054056 2009-10-27 2010-10-26 Système de valorisation de déchets par torche d'oxygène et récupération par un acide Ceased WO2011056548A2 (fr)

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CN104028530A (zh) * 2013-06-27 2014-09-10 中石化上海工程有限公司 废旧电路板的处理方法
WO2018167224A1 (fr) * 2017-03-15 2018-09-20 Umicore Procédé de nitrate pour la fabrication de précurseurs d'hydroxyde de métal de transition
KR20190121857A (ko) * 2017-03-15 2019-10-28 유미코아 전이금속 수산화물 전구체를 제조하기 위한 질산염 공정
US10723624B2 (en) 2017-12-05 2020-07-28 Ascend Performance Materials Operations Llc Process for preparation of nitrogen oxides and nitric acid from nitrous oxide
WO2023283685A1 (fr) * 2021-07-16 2023-01-19 Resource Conservation and Recycling Corporation Pty Ltd Procédé de récupération de valeurs à partir de batteries alcalines

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CN103757284A (zh) * 2013-12-29 2014-04-30 四川师范大学 镍氢废电池正极材料的浸出方法
CN103757415A (zh) * 2013-12-29 2014-04-30 四川师范大学 镍钴锰酸锂废电池正负极混合材料的浸出方法
CN103757235A (zh) * 2013-12-29 2014-04-30 四川师范大学 镍氢废电池正负极混合材料的浸出方法
CN105861836B (zh) * 2015-01-22 2018-11-13 昆明冶金高等专科学校 一种从多金属合金物料中集贵金属的方法
US20210040581A1 (en) * 2016-01-14 2021-02-11 Entegris, Inc. Integrated electronic waste recycling and recovery system and process of using same

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CN104028530A (zh) * 2013-06-27 2014-09-10 中石化上海工程有限公司 废旧电路板的处理方法
WO2018167224A1 (fr) * 2017-03-15 2018-09-20 Umicore Procédé de nitrate pour la fabrication de précurseurs d'hydroxyde de métal de transition
KR20190121857A (ko) * 2017-03-15 2019-10-28 유미코아 전이금속 수산화물 전구체를 제조하기 위한 질산염 공정
JP2020511757A (ja) * 2017-03-15 2020-04-16 ユミコア 遷移金属水酸化物前駆体を製造するための硝酸塩プロセス
KR102136961B1 (ko) 2017-03-15 2020-07-23 유미코아 전이금속 수산화물 전구체를 제조하기 위한 질산염 공정
US11401167B2 (en) 2017-03-15 2022-08-02 Umicore Nitrate process for manufacturing transition metal hydroxide precursors
US10723624B2 (en) 2017-12-05 2020-07-28 Ascend Performance Materials Operations Llc Process for preparation of nitrogen oxides and nitric acid from nitrous oxide
WO2023283685A1 (fr) * 2021-07-16 2023-01-19 Resource Conservation and Recycling Corporation Pty Ltd Procédé de récupération de valeurs à partir de batteries alcalines

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