US20180050372A9 - Method to recycle plastics, electronics, munitions or propellants using a metal reactant alloy composition - Google Patents

Method to recycle plastics, electronics, munitions or propellants using a metal reactant alloy composition Download PDF

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US20180050372A9
US20180050372A9 US15/155,987 US201615155987A US2018050372A9 US 20180050372 A9 US20180050372 A9 US 20180050372A9 US 201615155987 A US201615155987 A US 201615155987A US 2018050372 A9 US2018050372 A9 US 2018050372A9
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aluminum
molten metal
metal compound
electronics
feed stock
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US10427192B2 (en
US20170326603A1 (en
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Ronald G. Presswood, Jr.
Ian C. Bishop
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Elemental Recycling Inc
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Priority to US16/588,379 priority patent/US10994315B2/en
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    • B09B3/0083
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D19/00Degasification of liquids
    • B01D19/0042Degasification of liquids modifying the liquid flow
    • B01D19/0052Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused
    • B01D19/0057Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused the centrifugal movement being caused by a vortex, e.g. using a cyclone, or by a tangential inlet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/0003Making of sedimentation devices, structural details thereof, e.g. prefabricated parts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/009Heating or cooling mechanisms specially adapted for settling tanks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/26Separation of sediment aided by centrifugal force or centripetal force
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D3/00Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/007Energy recuperation; Heat pumps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D5/00Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B01D5/006Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D5/00Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B01D5/0069Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with degasification or deaeration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02Preparation of oxygen
    • C01B13/0222Preparation of oxygen from organic compounds
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/02Preparation of nitrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/02Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/42Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/14Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot liquids, e.g. molten metals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/57Gasification using molten salts or metals
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01DNON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D15/00Adaptations of machines or engines for special use; Combinations of engines with devices driven thereby
    • F01D15/10Adaptations for driving, or combinations with, electric generators
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01KSTEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K23/00Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
    • F01K23/02Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
    • F01K23/06Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
    • F01K23/064Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle in combination with an industrial process, e.g. chemical, metallurgical
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01KSTEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K7/00Steam engine plants characterised by the use of specific types of engine; Plants or engines characterised by their use of special steam systems, cycles or processes; Control means specially adapted for such systems, cycles or processes; Use of withdrawn or exhaust steam for feed-water heating
    • F01K7/16Steam engine plants characterised by the use of specific types of engine; Plants or engines characterised by their use of special steam systems, cycles or processes; Control means specially adapted for such systems, cycles or processes; Use of withdrawn or exhaust steam for feed-water heating the engines being only of turbine type
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42AMMUNITION; BLASTING
    • F42BEXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B33/00Manufacture of ammunition; Dismantling of ammunition; Apparatus therefor
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42AMMUNITION; BLASTING
    • F42BEXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B33/00Manufacture of ammunition; Dismantling of ammunition; Apparatus therefor
    • F42B33/06Dismantling fuzes, cartridges, projectiles, missiles, rockets or bombs
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02KDYNAMO-ELECTRIC MACHINES
    • H02K7/00Arrangements for handling mechanical energy structurally associated with dynamo-electric machines, e.g. structural association with mechanical driving motors or auxiliary dynamo-electric machines
    • H02K7/18Structural association of electric generators with mechanical driving motors, e.g. with turbines
    • H02K7/1807Rotary generators
    • H02K7/1823Rotary generators structurally associated with turbines or similar engines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02Apparatus characterised by their chemically-resistant properties
    • B01J2219/025Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0263Ceramic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1003Waste materials
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/0946Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05DINDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2220/00Application
    • F05D2220/30Application in turbines
    • F05D2220/31Application in turbines in steam turbines
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05DINDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2220/00Application
    • F05D2220/60Application making use of surplus or waste energy
    • F05D2220/62Application making use of surplus or waste energy with energy recovery turbines

Definitions

  • the present invention relates to a method to recycle plastics, electronics, munitions or propellants and to capture and recover carbon, sulfur, hydrocarbons, and heavy metals from the plastics, electronics, munitions or propellants using a molten aluminum or aluminum alloy bath that may be composed of aluminum, zinc, iron, copper, silicon, and/or calcium alloys.
  • the present invention provides an apparatus for recycling plastics, electronics, munitions or propellants.
  • This can be any type of plastic, such as but not limited to PVC, HDPE, PF, LDPE, ABS, Nylon or other plastics.
  • This can be any consumer electronics such as but not limited to Cell Phones, Portable Electronics Devices, Laptop Computers, Desk Top Computers, Tablets, etc.
  • this can be used to recycle any type of munition or propellant such as, but not limited to, gun power or M6.
  • the process utilizes a molten aluminum or molten aluminum alloy bath.
  • the aluminum can be alloyed with metals that include, but are not limited to zinc, iron, copper, silicon, and calcium.
  • the material is ground and can be dried, and is then introduced into the bath below the surface.
  • the ground material can be forced below the surface using an inert gas such as nitrogen or argon or fed into the bath using a gravity feed. In the process excess heat is generated and can be used to facilitate other processes such as cogeneration of power.
  • the aluminum or aluminum alloy bath reacts to break it down to its elemental parts. These elements are then removed from the bath using a gravimetric process and a gas capture process.
  • the elements removed from the bath can include, but are not limited to, carbon, sulfur, hydrogen, nitrogen, mercury, copper, iron, as well as other rare earth and heavy metals.
  • the process can also produce methane and other hydrocarbons.
  • the elemental materials can be recovered and sold and the hydrocarbons are recovered and sold or burned to facilitate the process.
  • the inert gas is reprocessed and reused.
  • the aluminum or aluminum alloy bath is able to remove oxygen compounds by chemically reacting with them at high temperature.
  • Other compounds such as PVC are broken down as the aluminum or other alloys remove the Chloride to form Aluminum Chloride.
  • the removal of select elements allows the bonds of the organic compounds to be broken, producing volatile organic compounds, as well as elemental compounds.
  • FIG. 1 shows the basic process flow 100 .
  • ground material is introduced below the surface of the molten metal bath 103 using an injection feed system 101 through feed line 102 .
  • the elemental material such as carbon, sulfur and the like, is captured 104 , less dense secondary compounds are removed from the surface of bath 105 , and denser secondary compounds are removed from the bottom of the bath 106 . While this has been described as a method to recycle plastics, electronics, munitions or propellants, use of this method to recycle other organic compounds, such as, but not limited to rubbers, oils and tars are also contemplated.
  • FIG. 1 shows the basic process flow
  • FIG. 2 shows a typical process flow
  • FIG. 3 shows a detailed cross sectional view of the reaction vessel wall
  • FIG. 4 shows a modified flow process incorporating a vortex.
  • the present invention provides a process to recycle plastics, electronics, munitions or propellants.
  • the process utilizes a molten aluminum or molten aluminum alloy bath.
  • the process utilizes a molten aluminum bath as the reactant.
  • the ground feedstock is introduced below the surface of the molten aluminum bath, reacts with the aluminum to decompose the feed stock.
  • elemental carbon, sulfur, copper, iron, and rare earth and heavy metals and molecular hydrogen, nitrogen, methane, and other hydrocarbons are removed from the molten bath.
  • the products can be sold and the nitrogen is either vented to the atmosphere or captured.
  • the process utilizes a molten metal as the primary reactant.
  • the molten metal is aluminum or an aluminum bath.
  • the aluminum can also be alloyed with other elements including, but not limited to, zinc, iron, copper, silicon and calcium. Other metals and metal alloys such as calcium and silicon are also envisioned.
  • the flue gas stream which contains oxygen containing greenhouse gases produced by combustion processes, is passed through the aluminum alloy bath to remove the oxygen-containing gases from the flue gas stream.
  • excess heat is generated and can be used to facilitate other processes such as cogeneration of power.
  • the excess generated by the process is a function of the makeup of the greenhouse gases in the flue gas feed.
  • the process will produce an aluminum salt, in this case aluminum chloride.
  • the present invention also provides a method and apparatus for capturing heavy metals, such as, but not limited to mercury or rare earth metals, which are often found in consumer electronics or munitions.
  • the molten metal bath breaks down the metal compounds as they are introduced into the molten metal bath.
  • the heavy metals settle to the bottom of the reaction vessels and are removed from the reaction vessel. While some aluminum may be entrained in the heavy metals that are removed from the bottom of the reaction vessel, the aluminum can be removed and refined and the heavy metals can be captured.
  • a detailed process flow 200 is shown in FIG. 2 . While the process described discusses processing recycling plastics, electronics, munitions or propellants can be processed using the invention.
  • the ground feed stock is introduced into the treatment process through blower feed line 211 .
  • Blower 210 which may be another type of injector, is used to inject the ground feed stock into reaction vessel 220 through injection line 212 .
  • Injection line 212 introduces the ground feed stock, which is entrained in an inert gas such as nitrogen, below the surface of the molten aluminum compound 226 . Injection line 212 must be sufficiently below the surface of the molten aluminum compound 226 to allow for sufficient mixing.
  • the heavy products of the reaction typically the heavy metals described above will settle out in the reaction vessel.
  • the reaction vessel typically has a sloped bottom, however other designs such conical bottoms and the like can be utilized.
  • Collection lines 223 , 224 , and 225 allow for heavy metals of different densities to be removed. Depending on the size of the process, the heavy products can be continuously removed or a batch removal process can be used.
  • Reaction vessel 220 also includes an aluminum feed line 221 , which is used to supply additional aluminum compound to replace that consumed by the reaction with the ground feed stock. Additional heat may be required during start-up, for example.
  • Heater 227 is provided for this purpose. Heater 227 can be any type heater, including radiative, inductive, and convective. For example, heater 227 would be a microwave heater or a radio frequency heater wherein the frequency is tuned for the metal alloy used.
  • Section A which is shown in more detail in FIG. 3 shows one way the heat can be removed from the process.
  • the reaction vessel 220 is lined with a refractory material 310 , which protects the vessel wall 320 .
  • Cooling plate 330 is attached to the vessel wall 320 and cooling water is circulated in the channels created between the cooling plant 330 and the vessel wall 320 .
  • Insulation 340 surrounds the cooling plate to maximize heat recovery, as well as for safety purposes.
  • the cooling water picks up the heat generated from the process, it can be either sent to a cooling tower or the heat can be recovered and used for other purposes. If the process is used in a facility that needs a hot water source, then the heat recovery system can be designed for this purpose. However, the heat can also be used to generate electricity.
  • a steam turbine electric generation process is represented.
  • the cooling water is introduced thorough cooling feed 228 .
  • the cooling water travels around the reaction vessel 220 , it picks up heat and steam is generated.
  • the steam generated is then sent via steam line 229 to steam turbine 232 .
  • the steam passes through the turbine and as it condenses, turns the turbine blades of turbine 232 .
  • Turbine 232 is coupled to generator 231 .
  • this steam turbine-electric generator process is well known in the art. And any steam turbine-electric generator process could be utilized.
  • the reaction will also produce elemental carbon, elemental sulfur, molecular nitrogen and molecular hydrogen. These will be removed from the reaction vessel using blower 250 . Blower 250 will pull high temperature elemental carbon, elemental sulfur, molecular nitrogen and molecular hydrogen from the reaction vessel 220 through heat exchanger feed line 241 into heat exchanger 240 . Heat exchanger 240 will then cool this material to enable further processing. Any hydrocarbons that are produced may also be condensed in heat exchanger 240 . These liquid hydrocarbons can be collected for further use or sale. Heat exchanger 240 can be any heat exchanger, however in the preferred embodiment, heat exchanger 240 is a forced air heat exchanger, however other heat exchangers, are also envisioned.
  • the process stream then leaves the heat exchanger through line 242 and passes through blower 250 and blower discharge line 252 into two cyclone separators.
  • the first separator 260 separates out carbon from process stream.
  • the carbon is collected though separation line 263 .
  • the remaining process stream proceeds to the second separator 270 , which separates out sulfur from the process stream.
  • the sulfur may be removed using a cold finger as the stream is cooled to less than 444 degrees Celsius.
  • the sulfur is collected through separation line 273 .
  • the remaining process stream which may include gaseous nitrogen and hydrogen, is then separated in cryo unit 280 . In this unit, the gas stream is cooled further and to allow the components to be separated.
  • Nylon 66 (C 12 H 22 N 2 O 2 ) n -->12C+11H 2 +2N+2O 2
  • FIG. 4 illustrates a modified process flow 400 using a vortex entry.
  • the modified process enables recycling of plastics, electronics, munitions or propellants.
  • the ground feed stock is introduced into the treatment process through line fed by a vortex 402 .
  • the vortex 402 is formed within a ceramic bowl 415 by pumping in molten aluminum or aluminum alloy.
  • the molten aluminum or aluminum alloy may be added through a new aluminum input line 404 , or it may be recirculated from the aluminum bath using a pump 406 .
  • the ground feed stock (which may include any of the materials above that need to be recycled) may then be introduced into the ceramic bowl 415 through a gravity feed 405 .
  • the ground feed stock mixes with the molten aluminum or aluminum alloy and the mixture is pulled to the bottom of the bowl from the rotation of the vortex 402 .
  • the bottom of the ceramic bowl 415 may have a connecting line 408 to the aluminum bath, and the mixture of ground feed stock and molten aluminum or aluminum alloy enters the aluminum bath from the connecting line 408 .
  • Other aspects of the modified process flow 400 are similar to that shown with the flow in FIG. 2 .
  • the vortex entry illustrated in FIG. 4 allows for some benefits over other injection systems.
  • the vortex allows better mixing of the ground feed stock with the molten aluminum or aluminum alloy, which allows the recycling reactions to occur more efficiently.
  • the temperature of the mixture has an opportunity to equalize, and the temperature may be relatively close to the temperature of the molten aluminum within the bath. Accordingly, there is less localized cooling, and a more consistent temperature gradient, at the entry injection point when the vortex entry is used.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
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  • Physics & Mathematics (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

This invention relates to a method and apparatus for recycling plastics, electronics, munitions or propellants. In particular, the method comprises reacting a feed stock with a molten aluminum or aluminum alloy bath. The apparatus includes a reaction vessel for carrying out the reaction, as well as other equipment necessary for capturing and removing the reaction products. Further, the process can be used to cogenerate electricity using the excess heat generated by the process.

Description

    PRIORITY
  • This application claims priority to U.S. Provisional Patent Application No. 62/162,648, filed on May 15, 2015, which is incorporated by reference in its entirety herein.
  • FIELD OF THE INVENTION
  • The present invention relates to a method to recycle plastics, electronics, munitions or propellants and to capture and recover carbon, sulfur, hydrocarbons, and heavy metals from the plastics, electronics, munitions or propellants using a molten aluminum or aluminum alloy bath that may be composed of aluminum, zinc, iron, copper, silicon, and/or calcium alloys.
  • BACKGROUND OF THE INVENTION
  • Although a number of methods exist to recycle plastics, electronics, munitions or propellants, these methods are costly and in some cases create a secondary waste that can be more of a problem than the actual initial material itself. Currently, methods of recycling plastics, electronics, munitions or propellants create greenhouse gases such as carbon monoxide or carbon dioxide, as well as, other byproducts such as ammonia and other secondary compounds, which in some cases are more hazardous than the parent material. Further, these processes also produce slag, which currently must be land filled and there is currently no efficient method to recovery heavy metals, such as mercury, or rare earth metals that typically are found in electronics. While these processes work, they require significant energy input or create waste streams that must be disposed of at a cost to the operator and with potential future environmental impact.
  • Thus, there is a need in the art for an improved method to economically recycle plastics, electronics, munitions or propellants while recovering the remaining carbon, sulfur and any rare earth or heavy metals.
  • SUMMARY OF THE INVENTION
  • The present invention provides an apparatus for recycling plastics, electronics, munitions or propellants. This can be any type of plastic, such as but not limited to PVC, HDPE, PF, LDPE, ABS, Nylon or other plastics. This can be any consumer electronics such as but not limited to Cell Phones, Portable Electronics Devices, Laptop Computers, Desk Top Computers, Tablets, etc. As well, this can be used to recycle any type of munition or propellant such as, but not limited to, gun power or M6. The process utilizes a molten aluminum or molten aluminum alloy bath. The aluminum can be alloyed with metals that include, but are not limited to zinc, iron, copper, silicon, and calcium. In all cases the material is ground and can be dried, and is then introduced into the bath below the surface. The ground material can be forced below the surface using an inert gas such as nitrogen or argon or fed into the bath using a gravity feed. In the process excess heat is generated and can be used to facilitate other processes such as cogeneration of power. As the ground material is passed through the bath, the aluminum or aluminum alloy bath reacts to break it down to its elemental parts. These elements are then removed from the bath using a gravimetric process and a gas capture process. The elements removed from the bath can include, but are not limited to, carbon, sulfur, hydrogen, nitrogen, mercury, copper, iron, as well as other rare earth and heavy metals. The process can also produce methane and other hydrocarbons. The elemental materials can be recovered and sold and the hydrocarbons are recovered and sold or burned to facilitate the process. The inert gas is reprocessed and reused.
  • The aluminum or aluminum alloy bath is able to remove oxygen compounds by chemically reacting with them at high temperature. Other compounds such as PVC are broken down as the aluminum or other alloys remove the Chloride to form Aluminum Chloride. The removal of select elements allows the bonds of the organic compounds to be broken, producing volatile organic compounds, as well as elemental compounds.
  • This process has been evaluated in laboratory tests using select plastics and consumer electronics. The ground plastics and consumer electronics was passed through molten aluminum. The flue gas produced and the final alloy mass was analyzed using scanning electron microscope (SEM). The review of the SEM images showed the presence of element carbon, sulfur and aluminum salts. The only items that did not break down were the S-Glass, the silicon, and silica glass.
  • FIG. 1 shows the basic process flow 100. In the basic process, ground material is introduced below the surface of the molten metal bath 103 using an injection feed system 101 through feed line 102. The elemental material, such as carbon, sulfur and the like, is captured 104, less dense secondary compounds are removed from the surface of bath 105, and denser secondary compounds are removed from the bottom of the bath 106. While this has been described as a method to recycle plastics, electronics, munitions or propellants, use of this method to recycle other organic compounds, such as, but not limited to rubbers, oils and tars are also contemplated.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying Figures and drawings, in which:
  • FIG. 1 shows the basic process flow;
  • FIG. 2 shows a typical process flow;
  • FIG. 3 shows a detailed cross sectional view of the reaction vessel wall; and
  • FIG. 4 shows a modified flow process incorporating a vortex.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention provides a process to recycle plastics, electronics, munitions or propellants. The process utilizes a molten aluminum or molten aluminum alloy bath. The process utilizes a molten aluminum bath as the reactant. The ground feedstock is introduced below the surface of the molten aluminum bath, reacts with the aluminum to decompose the feed stock. In the process, elemental carbon, sulfur, copper, iron, and rare earth and heavy metals and molecular hydrogen, nitrogen, methane, and other hydrocarbons are removed from the molten bath. The products can be sold and the nitrogen is either vented to the atmosphere or captured.
  • The process utilizes a molten metal as the primary reactant. In the preferred embodiments the molten metal is aluminum or an aluminum bath. The aluminum can also be alloyed with other elements including, but not limited to, zinc, iron, copper, silicon and calcium. Other metals and metal alloys such as calcium and silicon are also envisioned. The flue gas stream, which contains oxygen containing greenhouse gases produced by combustion processes, is passed through the aluminum alloy bath to remove the oxygen-containing gases from the flue gas stream.
  • In the process, excess heat is generated and can be used to facilitate other processes such as cogeneration of power. The excess generated by the process is a function of the makeup of the greenhouse gases in the flue gas feed.
  • When the feed stock contains other compounds, those compounds can also decomposed or captured. For example, if the feed stock contains inorganic compounds, such as chlorine, the process will produce an aluminum salt, in this case aluminum chloride. The present invention also provides a method and apparatus for capturing heavy metals, such as, but not limited to mercury or rare earth metals, which are often found in consumer electronics or munitions. In the process, the molten metal bath breaks down the metal compounds as they are introduced into the molten metal bath. As additional aluminum is added to the bath, the heavy metals settle to the bottom of the reaction vessels and are removed from the reaction vessel. While some aluminum may be entrained in the heavy metals that are removed from the bottom of the reaction vessel, the aluminum can be removed and refined and the heavy metals can be captured.
  • A detailed process flow 200 is shown in FIG. 2. While the process described discusses processing recycling plastics, electronics, munitions or propellants can be processed using the invention. The ground feed stock is introduced into the treatment process through blower feed line 211. Blower 210, which may be another type of injector, is used to inject the ground feed stock into reaction vessel 220 through injection line 212. Injection line 212 introduces the ground feed stock, which is entrained in an inert gas such as nitrogen, below the surface of the molten aluminum compound 226. Injection line 212 must be sufficiently below the surface of the molten aluminum compound 226 to allow for sufficient mixing. The heavy products of the reaction, typically the heavy metals described above will settle out in the reaction vessel. The reaction vessel typically has a sloped bottom, however other designs such conical bottoms and the like can be utilized. Once the heavy products settle out, they are collected using collection lines 223, 224, and 225. Collection lines 223, 224, and 225 allow for heavy metals of different densities to be removed. Depending on the size of the process, the heavy products can be continuously removed or a batch removal process can be used.
  • Reaction vessel 220 also includes an aluminum feed line 221, which is used to supply additional aluminum compound to replace that consumed by the reaction with the ground feed stock. Additional heat may be required during start-up, for example. Heater 227 is provided for this purpose. Heater 227 can be any type heater, including radiative, inductive, and convective. For example, heater 227 would be a microwave heater or a radio frequency heater wherein the frequency is tuned for the metal alloy used.
  • Thus, the heat generated by the process must be removed. Section A, which is shown in more detail in FIG. 3 shows one way the heat can be removed from the process. The reaction vessel 220 is lined with a refractory material 310, which protects the vessel wall 320. Cooling plate 330 is attached to the vessel wall 320 and cooling water is circulated in the channels created between the cooling plant 330 and the vessel wall 320. Insulation 340 surrounds the cooling plate to maximize heat recovery, as well as for safety purposes. Once the cooling water picks up the heat generated from the process, it can be either sent to a cooling tower or the heat can be recovered and used for other purposes. If the process is used in a facility that needs a hot water source, then the heat recovery system can be designed for this purpose. However, the heat can also be used to generate electricity.
  • Turning back to FIG. 2, a steam turbine electric generation process is represented. In this case, the cooling water is introduced thorough cooling feed 228. As the cooling water travels around the reaction vessel 220, it picks up heat and steam is generated. The steam generated is then sent via steam line 229 to steam turbine 232. The steam passes through the turbine and as it condenses, turns the turbine blades of turbine 232. Turbine 232 is coupled to generator 231. As the turbine turns the rotor of generator 231 though the stator, it generates electricity. While this process is only briefly described, this steam turbine-electric generator process is well known in the art. And any steam turbine-electric generator process could be utilized.
  • Also, as described above, the reaction will also produce elemental carbon, elemental sulfur, molecular nitrogen and molecular hydrogen. These will be removed from the reaction vessel using blower 250. Blower 250 will pull high temperature elemental carbon, elemental sulfur, molecular nitrogen and molecular hydrogen from the reaction vessel 220 through heat exchanger feed line 241 into heat exchanger 240. Heat exchanger 240 will then cool this material to enable further processing. Any hydrocarbons that are produced may also be condensed in heat exchanger 240. These liquid hydrocarbons can be collected for further use or sale. Heat exchanger 240 can be any heat exchanger, however in the preferred embodiment, heat exchanger 240 is a forced air heat exchanger, however other heat exchangers, are also envisioned. The process stream then leaves the heat exchanger through line 242 and passes through blower 250 and blower discharge line 252 into two cyclone separators. The first separator 260 separates out carbon from process stream. The carbon is collected though separation line 263. The remaining process stream proceeds to the second separator 270, which separates out sulfur from the process stream. The sulfur may be removed using a cold finger as the stream is cooled to less than 444 degrees Celsius. The sulfur is collected through separation line 273. The remaining process stream, which may include gaseous nitrogen and hydrogen, is then separated in cryo unit 280. In this unit, the gas stream is cooled further and to allow the components to be separated.
  • Below is a list of possible ground feed stock that may be recycled, and the resulting elemental outputs produced by the reactions within the molten metal bath.
  • Poly Vinyl Chloride: 2(C2H3C1)n-->4C+3H2+2Cl
  • Polypropylene: (C3H6)n-->3C+3H2
  • PET: (C10H8O4)n-->10C+4H2+2O2
  • Polycarbonate: (C16H14O3)n-->16C+7 H2+30O2
  • ABS: (C8H8*C4H6*C3H3N)n-->15C+17/2H2+1N
  • 4-(tert-butyl)styrene (butyl styrene):
      • (CH3)3C6H4CH═CH2-->12C+8H2
  • Nylon 66: (C12H22N2O2)n-->12C+11H2+2N+2O2
  • Dibutyl Phthalate: 3C16H22O4+8Al=48C+33H2+4Al2O3
  • Diphenylamine: 2C12H11N+0Al=24C+22H2+N2
  • Nitrocellulose:
      • 6C6H9(NO2)O5+12Al=36C+27H2+3N2+6Al2O3
      • 2C6H9(NO2)2O5+12Al=12C+9H2+N2+6Al2O3
      • 6C6H9(NO2)3O544Al=36C+27H2+9N2+22Al2O3
  • Dinitrotoluene: 3C7H6N2O4+8Al=21C+9H2+3N2+4Al2O3
  • FIG. 4 illustrates a modified process flow 400 using a vortex entry. As with the process described in FIG. 2, the modified process enables recycling of plastics, electronics, munitions or propellants. Instead of being directly injected into the aluminum bath, the ground feed stock is introduced into the treatment process through line fed by a vortex 402. The vortex 402 is formed within a ceramic bowl 415 by pumping in molten aluminum or aluminum alloy. The molten aluminum or aluminum alloy may be added through a new aluminum input line 404, or it may be recirculated from the aluminum bath using a pump 406. The ground feed stock (which may include any of the materials above that need to be recycled) may then be introduced into the ceramic bowl 415 through a gravity feed 405. The ground feed stock mixes with the molten aluminum or aluminum alloy and the mixture is pulled to the bottom of the bowl from the rotation of the vortex 402. The bottom of the ceramic bowl 415 may have a connecting line 408 to the aluminum bath, and the mixture of ground feed stock and molten aluminum or aluminum alloy enters the aluminum bath from the connecting line 408. Other aspects of the modified process flow 400 are similar to that shown with the flow in FIG. 2.
  • The vortex entry illustrated in FIG. 4 allows for some benefits over other injection systems. The vortex allows better mixing of the ground feed stock with the molten aluminum or aluminum alloy, which allows the recycling reactions to occur more efficiently. Additionally, because the ground feed stock has already mixed with the molten aluminum in the ceramic bowl 415, the temperature of the mixture has an opportunity to equalize, and the temperature may be relatively close to the temperature of the molten aluminum within the bath. Accordingly, there is less localized cooling, and a more consistent temperature gradient, at the entry injection point when the vortex entry is used.
  • As described above, once the feed stock enters the aluminum bath or the vortex, then reactions of the ground feed stock material with the aluminum or aluminum alloy bath will begin. The denser materials will begin to settle while the lighter materials will rise. The lightest materials, such as gas will bubble to the surface, to be recovered there.
  • Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims (11)

What is claimed is:
1. A method of recycling plastics, electronics, munitions or propellants, the method comprising:
injecting a feed stock into a molten metal compound; and
reacting the feed stock with a molten metal compound.
2. The method of claim 1, wherein the molten aluminum compound is aluminum.
3. The method of claim 1, wherein the molten metal compound is an aluminum alloy.
4. The method of claim 3, wherein the molten aluminum compound is an aluminum alloy selected from the group consisting of silicon, magnesium, zinc, copper, iron, and calcium.
5. The method of claim 1, wherein the molten metal compound is silicon.
6. The method of claim 1, wherein the molten metal compound is a silicon alloy.
7. The method of claim 1, wherein injecting a feed stock into a molten metal compound comprises injecting, using a vortex, a feed stock into a molten metal compound.
8. An apparatus for recycling plastics, electronics, munitions or propellants, the apparatus comprising:
a reaction vessel designed to hold a molten metal compound;
a ceramic bowl to force a feed stock stream below the surface of the molten metal compound; and
at least one separator for removing particulate matter from the products.
9. The apparatus of claim 8, wherein the reaction vessel further comprises:
a reaction vessel wall;
a refractory material; and
a cooling plate,
wherein the cooling plate forms a channel for a cooling fluid between the cooling plate and the reaction vessel wall.
10. The apparatus of claim 9 further comprising a steam turbine.
11. The apparatus of claim 10 further comprising an electric generator.
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