US20150360286A1 - Recycling process for recycling granulated metallic materials containing surface impurities - Google Patents

Recycling process for recycling granulated metallic materials containing surface impurities Download PDF

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Publication number
US20150360286A1
US20150360286A1 US14/654,393 US201314654393A US2015360286A1 US 20150360286 A1 US20150360286 A1 US 20150360286A1 US 201314654393 A US201314654393 A US 201314654393A US 2015360286 A1 US2015360286 A1 US 2015360286A1
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Prior art keywords
subprocess
metal
temperature
recycling
granulated
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Abandoned
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US14/654,393
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English (en)
Inventor
Iban Vicario Gomez
Alberto Abuin Arizeta
Francisco Javier Antonanzas Gonzalez
Lourdes Yurramendi Sarasola
Juan Carlos Mugica Iraola
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Fundacion Tecnalia Research and Innovation
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Fundacion Tecnalia Research and Innovation
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Assigned to FUNDACION TECNALIA RESEARCH & INNOVATION reassignment FUNDACION TECNALIA RESEARCH & INNOVATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ABUIN ARIZETA, Alberto, ANTONANZAS GONZALEZ, FRANCISCO JAVIER, MUGICA IRAOLA, JUAN CARLOS, VICARIO GOMEZ, Iban, Yurramendi Sarasola, Lourdes
Publication of US20150360286A1 publication Critical patent/US20150360286A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • B22F1/0085—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F8/00—Manufacture of articles from scrap or waste metal particles
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • C22B7/001—Dry processes
    • 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

Definitions

  • the present invention relates to a metal preparation and recycling process having application in the metallurgical industry and more specifically in the field of metal recovery for recovering metals contained in waste materials, particularly when they have a small particle size.
  • waste materials are characterized in that the metal is contaminated with organic material such as oil, plastic, wood, paint, etc., and they can also contain inorganic impurities.
  • the object of the invention is a process which allows removing the non-metallic components, mainly organic products and various impurities, from waste materials with a high metallic content. Even though the process is applicable to metallic materials of various granulometries and sizes, it is particularly suitable for small metallic particles that are non-recoverable or recoverable with a low yield and/or quality by means of the processes known today.
  • the process is suitable for a large number of metals which include aluminium, copper, magnesium, zinc, etc. and their alloys.
  • Patent U.S. Pat. No. 7,976,611 describes a continuous process for recovering metals in which the organic components are removed by means of direct combustion at high temperatures.
  • the indicated process temperatures are between 400 and 1100° C., preferably from 600 to 900° C. and specifying the maximum preferred temperature in the range of 700-850° C.
  • the addition of oxygen at these temperatures allows removing the organic part by means of oxidation but it has several drawbacks.
  • the treatment temperature is too high for a large number of metals, including Al, Mg, Pb, since they have lower melting temperatures.
  • Patent GB-1,370,071 uses an inclined rotary furnace for recovering chips with adhered organic materials by means of a process which includes moving the chips through a tortuous path with an ascending temperature gradient in an atmosphere with the presence of oxygen. It indicates that the treatment temperature must be sufficient so that it vaporizes or oxidizes the organic contaminants but less than that at which the metal is substantially oxidized. However, the necessary temperature which is furthermore different for each treated metal is not specified. Only the specific temperature for bronze treatment is indicated which at most must be 200° F. lower than the melting temperature. Applied to a good number of metals, this temperature margin generates the above mentioned problems: significant metal oxidation and a high metal volatilization towards the gas outlet.
  • the invention applies a chip compaction system at the output temperature or after a partial cooling, followed optionally by melting the compacted metal in a melting furnace.
  • the chips are compacted at a high temperature but 500° F. lower than the melting temperature of the treated metal.
  • the compaction temperature is much lower than the semi-solid temperature and therefore does not assure that the metal is in a soft enough state so as to allow an optimum metal compaction.
  • this patent is not suitable for working with materials which are large in size and with small concentrations of organic loads.
  • Patent U.S. Pat. No. 3,744,779 presents a continuous process for recovering scrap metals by means of “destructive distillation” of the organic components at temperatures where the metal is relatively unaffected, with heating in the absence of oxygen.
  • the process actually consists of two well differentiated subprocesses. First, the metallic waste is heated in the absence of oxygen, a distillate of volatile organic compounds being produced. When the temperature is high enough and the heavy organic compounds which are still together with the metal are pyrolyzed generating complex mixtures of pyrolytic liquids and gases. The management of the gases released from both subprocesses is very complex: the volatile compounds directly volatized from the waste which will be mixed subsequently with the condensable products generated in the pyrolysis step must first be condensed.
  • incondensable pyrolytic gases which must be continuously removed will be generated at the outlet of the furnace. It is a process that is well adapted to metallic waste contaminated only with volatile organic products, even allowing their recovery, however, it has the complexity typical of pyrolytic processes when it comes to waste with complex mixtures of organic products, particularly when non-volatile, high molecular weight products are present. Furthermore, this process has the disadvantage that the final metal must be processed by means of physical separation once obtained and a salt bath is used for cleaning the metal from carbonaceous waste. The use of salts has a great environmental impact due to the creation of slags that are difficult to recover. On the other hand, it is necessary to melt the recovered metal for obtaining a suitable cleaning.
  • the present invention overcomes the problems mentioned in the processes described above and relates to a recycling process for recycling metals from waste materials which consists of three subprocesses.
  • the organic fraction is oxidized in an oxidizing atmosphere at a low temperature preventing metal oxidation.
  • the impurity residue is removed at a higher temperature and in an inert atmosphere, removing the non-metallic components adhered to the metal.
  • the process is preferably implemented continuously by means of the two mentioned heat treatments, resulting finally in a clean metal.
  • This metal can be suitable for direct use or for use after being subjected to a third subprocess of sintering at a temperature very close to the melting temperature of the metal.
  • the process further allows treating metals contaminated, for example, with oils or lacquers preventing the use of other processes requiring the addition of salts to separate the metal from its slag. It must be highlighted that one of the advantages of the process is that it is implemented continuously.
  • the recycling process for recycling metallic waste is particularly suitable when the metal is preferably in the form of granules having a reduced size and accompanied by non-metallic components, particularly organic products.
  • the first phase of the process allows, by means of two consecutive subprocesses 1 and 2 , removing all those organic materials, such as the coolants, foams, plastics, woods, etc., associated with the metal and reducing the percentage of contaminants in the recycled metal, such as the paint loads, without causing the oxidation thereof. Therefore, the process allows, in this first phase, obtaining the clean metal which be can be used directly as a secondary raw material in different industrial applications both in the form of shot or briquettes.
  • the application of subprocess 3 which allows compacting the metal at a temperature very close to but less than its melting point is contemplated if the final use so requires, obtaining a final quality similar to the molten metal.
  • the overall process proposed by the invention comprises combining three subprocesses: the objective of the first two subprocesses is to remove the impurities accompanying the metallic waste, while the objective of the third subprocess is to compact the metal by means of a sintering treatment.
  • subprocess 1 most the contaminating material particularly the organic fraction is removed.
  • the material is first heated to a temperature less than 300° C. in an oxidizing atmosphere.
  • the reactor or furnace where the treatment is performed is provided with a system keeping the material in motion, which can be made by means of systems such as vibrating trays, rotation, etc.
  • subprocess 2 the material resulting from the preceding subprocess is heated to 400-550° C. in an inert atmosphere to prevent oxidation.
  • this subprocess which is also in motion the remaining residues of contaminating material, for example, cinder and other impurities are removed.
  • the inorganic components adhered to the metallic surface are then separated by means of the combined action of temperature and mechanical treatment (friction, dilation, etc.). These inorganic components may originate from the original waste (ceramic materials, paint loads, etc.) or may have been generated in the preceding subprocess as a result of the incomplete combustion of the organic products (cinder).
  • the process of the present invention contemplates a third subprocess which allows transforming the granulated metal into a material similar to molten metal, the latter being suitable for use in most industrial processes, particularly in those requiring the melting thereof by means of conventional systems.
  • the decontaminated granulated metal originating from subprocess 2 is subjected to a sintering process, for which it must be heated to a temperature in which it adopts a semi-solid state, i.e., a pasty consistency, said temperature depending on each metal, for being subsequently pressed into the form of briquettes or the like.
  • This subprocess 3 thus completes the overall recycling process for recycling original metallic waste, when required.
  • FIG. 1 shows a flow chart of a preferred embodiment of the process of the invention where the subprocesses 1 , 2 and 3 can be distinguished.
  • the process consists of three subprocesses which can be classified into two phases:
  • Phase 1 The objective of subprocesses 1 and 2 is to remove impurities, particularly organic impurities (oils, plastics, etc.), by means of two consecutive treatments, one in oxidizing medium and a low temperature and the second in an inert medium at a higher temperature. The result is a clean metal which can be marketed or molten directly or can be sintered in the following phase.
  • Phase 2 when the application of the recycled material so requires, subprocess 3 receives the metallic material, particularly small metallic material, already free of impurities generated in subprocesses 1 and 2 for being sintered by means of pressing at a temperature less than the melting temperature.
  • the metallic material with impurities is introduced to remove moisture and organic compounds by means of oxidation at a temperature of approximately 300° C.
  • the objective is to remove most of said compounds in the form of gas preventing metal oxidation.
  • Oxygen or air must be introduced together with the material to be treated in a stoichiometric amount enough for oxidizing all the organic matter present.
  • the equipment in which this step is performed must be provided with a system causing the movement of the material, both for its forward movement and for allowing a homogenous heating and the exposure of the entire organic fraction to the oxidizing gas.
  • the heating can be performed both by means of a direct heating (e.g.: burner or resistances located inside the equipment) or through an outer sleeve provided with a heating system (e.g.: resistances, burners, hot air, etc., located in the sleeve).
  • a direct heating e.g.: burner or resistances located inside the equipment
  • a heating system e.g.: resistances, burners, hot air, etc., located in the sleeve.
  • the equipment further requires a control regulating the temperature to which the material is subjected. If the treated material contains an organic fraction the combustion of which does not allow reaching the process temperature, the heating system must provide the necessary additional heat.
  • the system must be controlled by means of various practices: diluting the metallic material to be treated with an inert material (minerals, another metal, etc.) which absorbs heat and is easily recoverable and/or supplying a gas less rich in oxygen and/or cooling by means of a fluid circulating through the outer sleeve.
  • the gases generated at that temperature can be duly treated before emission to the atmosphere.
  • the equipment required for said treatment depends on the specific material which is being treated and on the level of impurities that it contains, however, at most the following equipment is required: postcombustor, gas cooler and bag filter.
  • subprocess 2 the material treated in subprocess 1 is subjected, without it cooling down, to a temperature in the range of 400-450° C. to finish removing the impurities. Since it is a temperature at which the metal can oxidize, this step is performed in an inert medium free of oxygen. It has been verified that cinder build-ups and other impurities still present at the end of the previous treatment are thus removed. In this step, the equipment used must also be provided preferably with a system for moving the material since this movement together with the temperature produce a combined effect (dilation, friction, etc.) which allows obtaining a clean metallic material.
  • the inert gas can be extracted from the equipment, purified by means of particle removal in a cyclone and/or bag filter and recirculated again to the inside.
  • the heating system can be a direct heating system or an indirect heating system through a sleeve, with the exception of the direct systems which can introduce oxygen in the medium (e.g.: burners with flame).
  • the resulting metallic material can be marketed or molten directly or can proceed to the following subprocess 3 for being sintered.
  • a rapid cooling system can be necessary to prevent oxidation.
  • vibrating cooling trays, water cubes, cryogenic systems, or any other metal cooling means can be used, being able to include the need of an inert atmosphere.
  • the clean granular material generated in the preceding phase can be compacted by means of sintering under pressure.
  • the temperature of the material must be raised to 85-97% of the melting temperature of the metal treated in an inert medium and it must then be subjected to compaction by means of a press.
  • the material obtained in these conditions has a density close to 100% of that corresponding to molten metal.
  • Subprocess 3 is formed by a metering system for metering the hot metal, preferably at the same output temperature as subprocess 2 and by means of a system which allows an accurate metering (alveolar valves, chambers with a weighing and opening system depending on the weight detected), a system which allows raising the temperature to 85-97% of the melting temperature, such that the material is within the range of semi-solid state with a minimum liquid fraction allowing the optimum attachment of the materials in the compacting process and heated mold on which the material falls in order to be compacted by means of a press provided with one or two pistons, for example.
  • a cooling system can be necessary in some cases to enable reducing the cycle times, the piston is removed, the mold is opened and the compacted metal is extracted.
  • the process began with waste consisting of an aluminium shot contaminated with various organic materials.
  • the fraction less than 1 mm contained 11.45% of total carbon, whereas the fraction between 1-2 mm contained 9.77%.
  • the original material has been subjected to the subprocesses of phase I described above. Specifically, it has been subjected, in subprocess 1 , to a temperature of 295° C. for half an hour, 120% of oxygen stoichiometrically necessary for gasifying all the carbon having been circulated. It has been subjected subsequently, in subprocess 2 , to a temperature of 430° C. for half an hour in an inert argon atmosphere. The resulting material obtained has been classified into two fractions: less than 1 mm and 1-2 mm.
  • the carbon content of the first fraction has been reduced to 0.18% and the carbon content of the second fraction to 0.13%.
  • the effectiveness of the process described can thus be observed, the carbon removal performance being greater than 98% in both cases.
  • the oxygen analyzed in the metal before the treatment was 1.4% and the oxygen obtained after the treatment in subprocesses 1 and 2 was 0.3%. In other words, it can be observed that the process has not caused material oxidation and has allowed, in contrast, removing a part of the surface oxide present in the starting material.
  • the waste subjected to treatment is a bundle of copper wires 20 cm in length and 0.5 mm in diameter contaminated with a mixture of oily products.
  • the carbon content of the original material was 12%.
  • This material has been subjected to the subprocesses of phase I described above. Specifically, it has been subjected, in subprocess 1 , to a temperature of 300° C. for 45 minutes, 120% of oxygen stoichiometrically necessary for gasifying all the carbon having been circulated. It has been subjected subsequently, in subprocess 2 , to a temperature of 430° C. for 45 minutes in an inert argon atmosphere.
  • the carbon content of the resulting fraction is 0.2%, the carbon removal performance being greater than 98%.
  • the oxygen content remained invariable after the treatment steps.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
US14/654,393 2012-12-20 2013-11-25 Recycling process for recycling granulated metallic materials containing surface impurities Abandoned US20150360286A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12382519.2 2012-12-20
EP12382519.2A EP2746412B1 (en) 2012-12-20 2012-12-20 Recycling process for recycling granulated metallic materials containing surface impurities
PCT/ES2013/070814 WO2014096481A1 (es) 2012-12-20 2013-11-25 Proceso de reciclado de materiales metálicos granulados conteniendo impurezas superficiales

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US20150360286A1 true US20150360286A1 (en) 2015-12-17

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US14/654,393 Abandoned US20150360286A1 (en) 2012-12-20 2013-11-25 Recycling process for recycling granulated metallic materials containing surface impurities

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US (1) US20150360286A1 (zh)
EP (1) EP2746412B1 (zh)
CN (1) CN104884647B (zh)
ES (1) ES2559514T3 (zh)
MX (1) MX2015007859A (zh)
WO (1) WO2014096481A1 (zh)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITUB20154897A1 (it) * 2015-10-20 2017-04-20 Alessandro Cirocchi Procedimento termico per conferire duttilita ai fili di acciaio armonico provenienti dal recupero dei pneumatici

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3744779A (en) 1969-11-07 1973-07-10 Horizons Research Inc Scrap recovery apparatus
GB1370071A (en) 1972-01-04 1974-10-09 Thermetics Inc Scrap reclamation
CA2021638C (en) * 1990-07-20 1996-12-17 Francois Tremblay Decontamination and/or surface treatment of metals
DE4306207A1 (de) * 1993-02-27 1994-09-01 Rudolf Prof Dr Ing Jeschar Verfahren zum Einschmelzen von kunststoffbelasteten Schrotten mit fraktionierter Zersetzung der organischen Anteile in einem Schachtofen
EP0863216B1 (en) * 1997-03-05 2002-09-18 Ebara Corporation Method of treating metal/plastic composite waste material by heat decomposition
WO1998053108A1 (en) * 1997-05-16 1998-11-26 Seghers Better Technology Group Fluidised bed method for the recovery of metal from organics-containing metal waste
JPH11188335A (ja) * 1997-12-26 1999-07-13 Nippon Mining & Metals Co Ltd 廃銅線の処理方法
DE102005021656A1 (de) 2005-05-06 2006-11-09 Bayer Industry Services Gmbh & Co. Ohg Verfahren zur Rückgewinnung von Metallen aus Abfällen und anderen Materialien mit organischen Bestandteilen
ES2383208T3 (es) * 2007-01-09 2012-06-19 Tsl Engenharia, Manutenção E Preservação Ambiental Procedimiento para el reciclaje de materiales compuestos que contienen aluminio
GB2477753B (en) * 2010-02-11 2012-04-18 Rifat Al Chalabi Metal recovery process
CN102418065B (zh) * 2011-12-12 2013-07-03 中国矿业大学 复合金属碳化物耐磨涂层及其制备工艺

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Publication number Publication date
EP2746412A1 (en) 2014-06-25
CN104884647A (zh) 2015-09-02
EP2746412B1 (en) 2015-10-21
ES2559514T3 (es) 2016-02-12
CN104884647B (zh) 2017-05-17
MX2015007859A (es) 2015-09-29
WO2014096481A1 (es) 2014-06-26

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VICARIO GOMEZ, IBAN;ABUIN ARIZETA, ALBERTO;ANTONANZAS GONZALEZ, FRANCISCO JAVIER;AND OTHERS;REEL/FRAME:035893/0874

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