EP2652078A2 - Verfahren zur rückgewinnung seltener erden aus leuchtstofflampen sowie zugehörige leuchtstoffe und lichtquellen - Google Patents
Verfahren zur rückgewinnung seltener erden aus leuchtstofflampen sowie zugehörige leuchtstoffe und lichtquellenInfo
- Publication number
- EP2652078A2 EP2652078A2 EP12713700.8A EP12713700A EP2652078A2 EP 2652078 A2 EP2652078 A2 EP 2652078A2 EP 12713700 A EP12713700 A EP 12713700A EP 2652078 A2 EP2652078 A2 EP 2652078A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- rare earth
- phosphors
- separation
- phosphor
- rare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/52—Recovery of material from discharge tubes or lamps
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/01—Recovery of luminescent materials
-
- 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
-
- 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
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
Definitions
- the invention is based on a method for the recovery of rare earths from fluorescent lamps according to the preamble of claim 1. Such methods are particularly suitable for linear, but also for compact fluorescent lamps.
- process for the treatment of phosphors are in particular disused or incorrectly produced Entla ⁇ dungslampen incurred as Feinstfr redesign when disassembling the lamps in the usual today Kapp-separation process or shredder process meant.
- the currently known process approaches for the treatment of waste phosphorus mainly describe processes that have a goal of recovering the individual components, in particular of rare earth-containing phosphors. Examples are DE 196 17 942, DE 34 10 989, DE 10 2006 025 945 and K. Takahashi et al .: Extraction of rare earth metals with a multistage mixer-settler extraction column, Chem. Eng. Be. 57, 2002, p. 469-478.
- EP-A 2 027 591 describes a process based on a multi-stage acid leaching with subsequent precipitation Rare earth with oxalic acid.
- the halophosphate is separated from the three-band phosphor mixture.
- the remaining rare earth phosphor mixture is again treated with an acid at least 90 ° C. From the filtrate rare earth oxides are precipitated by the addition of oxalic acid as a Mischo- xalat.
- Fluorescent lamps with mixed phosphors, halophosphates as well as three-band phosphors are known, for example, from WO 2002/35577.
- the object of the present invention is to provide a method which allows the recovery of elements such as terbium, europium and yttrium for use in phosphor production at least without significant loss of quality, in particular ⁇ even without any loss of quality allowed.
- a phosphor-containing fraction separated from the lamp bulb is generated.
- This phosphor powder is present as a mixture of halophosphate, three-band, and special phosphors, which is contaminated, inter alia, by glass splinters and metals and -ifferent with strong mercury. A direct return to the production process is therefore not possible.
- the novel process therefore pursues the goal of recycling the phosphor waste in a regulated manner.
- the rare earths (SE) are recovered as individual components, preferably as SE oxides, in a quality which corresponds to the products produced from natural ores and which thus permits unrestricted use in the production of new phosphors.
- Previous recycling processes end either in a phosphor of poor quality, which is useless for the lamp manufacturing, or in a method that is less effective, so that only a fraction of the Ab ⁇ case existing rare earth phosphors is used.
- the main advantage of the new method is that the Re ⁇ cycling cycle includes a rare earth separation process and thus unreservedly to theechoesindust- rie used usable high-purity rare earth oxides, which can not be obtained in principle with other methods.
- the aim of the newly developed method described below is to obtain by precipitation a synthetic rare earth compound after various separation, dissolution and digestion processes whose share of economically significant rare earths is at least as high as in natural occurring ores.
- the proportion of terbium and Euro Pium is due to the fact that a phosphor mixture is used as starting material, is significantly higher than in na ⁇ -natural occurrence.
- the old phosphor is a mixture of different phosphors whose main components are halophosphate and three-band phosphors.
- This phosphor mixture is mainly used with lamp components such as bulb glass, metal (coils, power supply, socket), plastic (socket, insulation ments) and putty contaminated.
- lamp components such as bulb glass, metal (coils, power supply, socket), plastic (socket, insulation ments) and putty contaminated.
- Vorbe ⁇ treatment quenching
- the process can be made up of the following modules. These can be combined as desired.
- Schemes 1 to 4 illustrate possible examples of processes. These process steps ⁇ have not been used for fluorescent material recycling. It is achieved for the first time to extract the rare earths as far as possible and to convert them back into raw materials, especially in the form of oxides. This process sequence is optimized in such a way that the yield of the expensive rare earths just required for the production of phosphorus is maximized for a given process outlay. The great advantage of this recovery, that only those raw materials needed for the lamp phosphors are contained ⁇ th in the input material, while at ungf syndromelichen ores all possible other rare earths are contained, which are difficult to separate.
- the first step is the mechanical separation of coarse parts.
- Coarse residual components of the fluorescent lamp as glass Split ⁇ ter, metal, plastic or cement-residue to be removed.
- the screening can be carried out in one or more stages depending on the process.
- the mesh size of the finest screening also depends on the method used and is typically 25 ⁇ mesh size for a dry or 20 ⁇ for a wet screening process.
- the fine material is further processing tet ⁇ with chemical processes.
- the second step is the separation of the halophosphate.
- the first is the cold lye.
- Acids eg hydrochloric acid
- grei ⁇ fen in the temperature range below 30 ° C yttrium-europium oxide, the most acid-soluble of the three-band phosphors, only slightly or not at all on.
- the remaining components, in particular the aluminates, are stable under these conditions and remain in the insoluble residue.
- a second option is the hot lye.
- Sel ⁇ th earth oxides dissolve in contrast to halophosphates only in the range between 60 ° C and 90 ° C in acids (eg HCl).
- acids eg HCl
- the calcium ions are present in very high concentrations in the solution, they precipitate due to their solubility product in the case of rare earth oxalate precipitation and should be separated off.
- the separation of calcium and rare earths takes place by precipitation as sulfate. After the solid-liquid separation remains calcium sulfate (gypsum) in the residue, the filtrate contains the rare earths.
- a simplified separation of calcium ions from Halophos ⁇ phat is achieved by the illustrated method for halophosphate separation with sulfuric acid.
- the interfering Ca 2+ ions in the further course of the procedure are completely precipitated as insoluble calcium sulfate.
- the other phosphor powder component such as acid-soluble SE-oxides and sparingly soluble SE-phosphates, are also permeated by the strong sulfuric acid solution attacked in room temperature.
- sparingly soluble sulfates double bil ⁇ that go by washing the residue with cold water in solution can in acid.
- the ⁇ ser proportion may preferably be reduced by gravity separation before the wet chemical treatment. Together with the halophosphate other Verun ⁇ purifications are advantageously separated in this step, the density of which is below the selected for waste separation of halophosphate density value.
- Another third step is the extraction of the slightly acid - soluble SE compounds.
- rare earth oxide (Y 2 C> 3: Eu) is present in the old phosphor mainly soluble at elevated temperature, preferably between 60 ° and 90 ° C.
- the dissolution of the SE - oxides is possible in hydrochloric acid or in Schwechat ⁇ ric acid.
- the rare earth oxides completely dissolve and the sparingly soluble alumina remains in the residue.
- Another fourth step is the extraction of the poorly acidic SE compounds.
- Another fifth step is the digestion of the verblei ⁇ reproduced SE - containing components.
- aluminate phosphors used in fluorescent lamps, in particular barium magnesium aluminate, europium doped (BAM) and cerium magnesium aluminate, terbium doped (CAT).
- a first option is the alkaline digestion.
- These phosphors are digested in alkaline digestion either with potash or caustic soda or with soda / potash melt.
- the aluminate mixture is converted by treatment with 150 ° C hot 35% sodium or potassium hydroxide under pressure in the mixture of insoluble hydroxides.
- sparingly soluble phosphates such as lanthanum phosphate, are closed ⁇ .
- the aluminates are melted with a soda / potash mixture.
- the melt cake is extracted with hot water or with acid.
- the undissolved residues are centrifuged in both cases and dumped as waste.
- a second option for the fifth step which can be carried out in addition to or as an alternative to the first option, is the acid digestion.
- the aluminates are digested in acid, for example phosphorus or sulfuric acid, at elevated temperature and, if necessary, at elevated pressure.
- acid for example phosphorus or sulfuric acid
- the solutions contain the rare earths.
- sulfuric acid double sulfates are extracted as needed with cold water from the residues.
- a sixth step is finally the final treatment and precipitation.
- the rare earths are precipitated from the solutions obtained in the various process steps.
- the precipitation of the rare earths takes place either with oxalic acid solution as oxalate or with ammonia to precipitate the rare earth in the form of basic salts.
- the oxalates are then calcined to oxides.
- the thus obtained rare earth are set a ⁇ for rare earths and processed compounds after the separation to any SE Compounds as "synthetic ore table" in the standard separation process.
- the phosphor powder precipitates as a separated fraction.
- the mercury-containing phosphor waste are arranged as "particularly überwachungsbedürfti ⁇ ger waste" and should be as hazardous waste Invited ⁇ device.
- the target sound recycling process reduces the mass and volume of the intended for disposal of hazardous waste, which contributes to the reduction in transportation and Deponiekos ⁇ th, and for Relief of the landfill and protection of human habitat.
- phosphor waste represents a raw material potential.
- the recovery of precious SE elements in a form that allows reuse in phosphor production relieves the natural resources.
- the relevant substances are not processed on landfill, but sorted into directly usable SE compounds.
- these connections oxides preferably, without limitation, into established processes. Both the convincedsab ⁇ run itself and the quality of the final product entspre ⁇ chen the standard procedure.
- Fluorescent recycling makes sense not only for ecological reasons, but also for economic reasons. In addition to important raw materials, the energy needed to extract raw materials is saved.
- the new recycling technology meets the requirements of modern waste management.
- the fluorescent recycling helps build the modern recycling systems, where the material cycles are actually closed on the economic and around ⁇ mentally friendly manner.
- a phosphor-containing fraction separated from the lamp bulb is generated.
- This phosphor powder consists of a mixture of halophosphate, three-band and special phosphors, which is contaminated inter alia by glass fragments and metals and also varying degrees with mercury. A direct sunlight ⁇ tion in the production process is therefore not possible.
- the phosphorus-containing fraction is due to the rare earth content of typically 10 wt -.%, Calculated as oxide, a not insignificant raw material potential, especially since the content of the scarce and thus expensive rare earth elements terbium and europium is higher than in the best known natural ores. 90% of these deposits are in China and have already been exploited in the medium term.
- the aim is to develop a process that succeeds in recovering the rare earths (SE) economically as individual or mixed components, preferably as SE oxides, in a quality comparable to that produced from natural ores corresponds and can be used without restriction, eg in the fluorescent production.
- SE rare earths
- the central development goals are:
- Obtained fluorescent phosphor-containing fraction can be obtained a synthetic rare earth compound, the proportion of economically important rare earth is typically significantly higher than in naturally occurring ores, in particular at least 30 wt .-%, preferably min ⁇ least 45 wt .-%, particularly preferably at least 60% by weight.
- the share of terbium and europium is conditionally in that a phosphor mixture is used as starting material, much higher than in natural occurrences.
- the aim of the newly developed method for rare earths is a simplified separation based on this concentrate. Here only the rare earths used in phosphors have to be separated from each other.
- the process can be made up of the following modules. These can be combined as desired. Steps 1 to 4 illustrate possible examples of process flows.
- o ion chromatography (separation step 3)
- o separation step 4 is any combination Nati ⁇ on from the previous separation steps 1 to 3
- the dissolution of the rare earth-containing primary material as a first fundamental process step is typically carried out by using as raw materials rare earth mixed oxides from lamp recycling. These are dissolved in mineral acids, eg HCl, HN0 3 .
- the removal of interfering non-rare earth elements is the second process step. If the materials are not in sufficient purity, the interfering elements, e.g. Fe, Ca, Al, by ion exchange or by selective precipitation, e.g. Oxalate precipitation, to be removed. If solids containing solids are removed when removing interfering elements, they are preferably dissolved after the first process step. This process step is not essential. In the case of direct separation from extracts, this step may have already been or may not be required in another context.
- Fluorescent lamps are typically typically recycled only the following rare earth elements: yttrium, europium, gadolinium, terbium, cerium, and lanthanum. So these are just six of the fourteen SE elements.
- the cited elements do not interfere is that they are trivalent ions that show no luminescent transitions.
- the non-interfering elements need not be completely removed. Compared with the expensive separation from natural raw materials, which typically contains a large proportion of the possible 14 rare earth elements, resulting in a simplification of the separation object from synthetic raw materials waste ⁇ recycling for the production of rare earth-containing materials for the phosphor production.
- the first two processes of the separation step are based on liquid-liquid separation.
- the first method that uses liquid-liquid extraction is the use of columns. Decisive for the quality or purity of the elements to be obtained is the length of the column or column, see, for example, DE-A 1 769 005.
- the columns can be built several meters high with only one set of pumps and stirrers.
- One meter of column length typically corresponds to more than one mixer-settler unit. The required investment costs are therefore lower as a mixer-settler method designed for equal separation efficiency, which is described below.
- a disadvantage of this system design is that, for example, during maintenance or modified separation task a large part of the system must be shut down or rebuilt.
- the second method of the separation step which uses liquid-liquid extraction, is the use of mixer-settler.
- SE elements to be separated and the deliberate leaving of permissible SE impurities.
- europium, gadolinium and terbium are eluted from the ion exchange resin packing by the complexing agent solution in this order under certain process conditions. Since gadolinium may be present to a certain extent both in a europium and in a terbium fraction and its proportion is generally low, it is possible to obtain only a cut of europium and terbium solution which are used to produce precursors containing SE is suitable for phosphor production.
- This rare earth separation is typically by ion exchange chromatography.
- a geeigne ⁇ tes acidic ion exchange resin such as sulfonic acid, loaded with the to be separated rare earths.
- the rare earths are sequentially eluted with a suitable aqueous complexing agent solution, for example EDTA.
- EDTA aqueous complexing agent solution
- any desired process Combination takes place in order to optimize the production process, taking into account the respective boundary conditions
- the next process step is then the production of a rare earth precursor.
- the rare earths are precipitated from the solutions obtained in the various process steps.
- the precipitation of the rare earths is typically carried out by means of oxalic acid solution to precipitate the rare earth in the form of basic salts.
- oxalic acid solution to precipitate the rare earth in the form of basic salts.
- single or mixed phosphates can be produced.
- annealing can he ⁇ follow in the example, the oxalates are annealed to produce oxides.
- the rare-earth compounds thus obtained can be used in their entirety in the production of new and highly efficient phosphors.
- the phosphor powder precipitates as a separated fraction.
- the mercury-containing fluorescent wastes are classified as' very überwachungsbedürfti ⁇ ger waste "and must be as special waste Invited ⁇ siege.
- the presented targeted recycling process reduces the mass and volume of the landfill seen before ⁇ hazardous waste. This contributes to the reduction of transport port- and landfill costs as well as to relieve the landfill and to protect the human habitat.
- the phosphor waste Due to their constituents, especially phosphates and rare earth elements, the phosphor waste represents an important raw material potential.
- the method described allows a simplified and very economic separation of the rare earths from a syn- thetic ore, which has been prepared for example by means of the method known from EP-A 2 027 591.
- the compounds produced in this process are particularly suitable for the production of high-efficiency phosphors.
- Concentrate is the essential and necessary final step in ei ⁇ nem new recycling process that is useful not only for ecological but also for economic reasons.
- the waste materials that accumulate at the end of the recycling process applied to old luminescent waste are significantly less damaging to the environment than the luminescent powder mixture primarily produced as waste. This reduction of pollutants facilitates the disposal of residual waste still accumulating.
- the new recycling technology meets the requirements of modern waste management.
- the fluorescent recycling is an important component for the development of modern recycling systems that are based on that material cycles on host ⁇ nomic and environmentally friendly way to be closed.
- EXPLANATION Preparation of a red-emitting phosphor; Difference to the production of a green emitting phosphor.
- a method for recovering rare earths from LAM pen-waste containing a plurality of phosphors, the rare-th earth elements, said a step of Separa ⁇ tion is carried out of rare earths, characterized in that the separation means at least one of the following methods is carried out, wherein at least one separation step is carried out:
- a method according to claim 1 characterized in that a limited number of different rare earth elements is present in the wastes in appreciable concentration.
- a method according to claim 3 characterized in that only a first part of the present in a limited selection
- Rare earth elements are required for precursor production while a second part is inert.
- step c) comprises at least one of the following steps in any order:
- step a) comprises at least one screening with a mesh size which is at most 25 ⁇ .
- step b) is carried out by cold or hot leaching.
- step cl) in hydrochloric acid and / or sulfuric acid he follows ⁇ , preferably at 60 to 90 ° C.
- step c2) is carried out as acidic or alkaline digestion.
- step d) as alkaline or acid digestion is carried out ⁇ .
- step e) the rare earths are precipitated, either with oxalic acid solution or with ammonia.
- Fig. 1 is a flow chart for a phosphor recycling according to the invention
- FIGS. 2 to 5 each show an alternative flowchart
- Figure 6 is a schematic diagram of the separation section
- Figure 7 shows a fluorescent lamp with stabilized lumines ⁇ material.
- FIG. 1 shows a scheme for the recycling process.
- Halo ⁇ phosphate is separated in the first step of the process by cold leaching.
- the extraction of the rare earths is dependent on the solubility of the present compounds in three separate stages.
- the liquid phases are collected and precipitated together or individually, for example by means of ⁇ oxalate. From the precipitate, the rare earths are then separated, in particular converted into oxides, wherein
- FIG. 2 shows a further exemplary embodiment of the recycling process, deviating from Scheme 1 halophosphate and easily soluble rare earth-containing phosphors are dissolved together. It follows the digestion of the sparingly soluble rare earth phosphors in two stages. The liquid phases are collected and precipitated together or individually, by means of example ⁇ oxalate. The Selte ⁇ earths are then separated from the precipitate, transferred in particular oxides, said mixed oxides predominate, and then further processed.
- FIG. 3 shows a third exemplary embodiment for the course of recycling, deviating from Scheme 2, calcium ions are separated off after the dissolution of halophosphate and readily soluble rare earth-containing phosphors.
- the liquid phases are collected and precipitated together or individually, for example by means of oxalate. From the precipitate, the rare earths are then separated, in particular converted into oxides, wherein predominate mixed oxides, and then casualverar ⁇ processed.
- Figure 4 shows a fourth embodiment for the process of recycling, different from Scheme 1-3, in the first step, both light and heavy acid soluble Verbin ⁇ applications open at the same time separated and calcium ions.
- the liquid phases are collected and precipitated together or individually, for example by means of oxalate. From the precipitate, the rare earths are then separated, in particular converted into oxides, with predominantly mixed oxides, and then further processed.
- FIG. 5 shows a further exemplary embodiment.
- the liquid-containing SE not to mix with certain phosphors in recycling fluorescent useful in the extraction of SE in several stages ⁇ ren phase with others, but to process the spur separately.
- the liquid-containing SE not to mix with certain phosphors in recycling fluorescent useful in the extraction of SE in several stages ⁇ ren phase with others, but to process the spur separately.
- appropriate conditions eg extraction of the SE from the recycled luminescent material and SE separation process on the same
- the direct separation without prior felling and annealing is preferable.
- the rare earths are then separated and then processed.
- Further processing usually means a re-injection into the phosphor production.
- FIG. 6 shows the advantageous working principle of the separation of the rare earth ions.
- the separation cut between the various rare earths occurring here is so limited that, for example, the separation between Eu and Tb is deliberately placed in a series which does not take any consideration for a separation of Gd.
- Gd does not interfere with the extraction of the Eu nor with the production of the Tb for the phosphor production.
- the separation step is simplified to a considerable extent by providing a useless for the production Lampenpro ⁇ separation all rare earth is omitted. So elements like Gd or Y are not separated depending on the application. This idea greatly simplifies litigation and reduces costs.
- the end result is a customized Lö ⁇ solution for the recycling of waste materials at very specific purposes, in particular for the lighting industry. At a ⁇ application of this basic method is useful not only for the phosphor production, but also for other purposes.
- the commercial significance of the present invention lies in the fact that the cost of the rare earth separation is approximately twice as high as all of the previously necessary process steps. Any saving and Ver ⁇ simplification suggests precisely this separation step uplifting ⁇ lich for the overall calculation to book.
- Common phosphors in the waste to be recycled are tri-band phosphors such as LAP, BAM, and CAT.
- the most commonly used phosphors in the production of discharge lamps are halophosphate and the so-called Three-band phosphor, wherein the three-band phosphor displaces the halophosphate more and more.
- the three-band phosphor is a mixture of red, green and blue phosphors that contain rare earth components in the host lattice or as activators.
- the europium-doped yttrium oxide (Y203: Eu) has proved to be the ideal red component; as a green component Certerbiumaluminat (CAT), and as component Blaukom ⁇ barium magnesium aluminate (BAM) are preferably used.
- the size and stability of the light emission is adversely affected by trace impurities which lead to luminescence quenching. Impurities from other rare earth elements are particularly unfavorable. So for example, cause 50 ppm cerium in Y203: Eu already Lumines ⁇ zenzminderung by about 10%. The transitional elements of the 4th period are also generally considered critical. It was found that even 5 ppm iron luminescence by 7%.
- Various approaches have been described which have the goal of recovering the phosphors, in particular the rare earth phosphors. In such a ⁇ preparation method is proposed in which a two-stage acid leaching is provided with subsequent oxalate.
- the phosphor mixture consisting of one or more rare earth oxide phosphors and rare earth mixed oxide phosphors (aluminate phosphors) and optionally one or more halophosphate phosphors, is leached in a first stage by leaching with a one to two normal nitric acid from Halophosphate freed.
- the remaining Selte ⁇ nerd-phosphor mixture is treated in connection with a 4 to 14-normal nitric acid at least 90 ° C. After solid-liquid separation, the remaining solid consisting of the sparingly soluble rare earth mixed oxide phosphors is washed, dried and annealed. From the
- BAM is present as a spinel and should also have an oxidation protection.
- BAM is basically to be understood as Bal-xMgA110O17: Eu 2+ X. It contains divalent EuII whose oxidation must be prevented to EuIII ver ⁇ .
- the oxidation mechanism stems from the fact that normal spinel MgA1204 readily attaches itself. Due to a Diffusionsprozes ⁇ ses the unwanted three ⁇ valent europium oxide is of divalent europium.
- the sauwer ⁇ term ion of rare-earth elements such as Gd particular La or Y is similar in size to the divalent Eu ion.
- the Gd as an inert rare earth element deliberately not completely separated from the effective rare earth element Eu, therefore, a blue Eu-doped phosphor such as BAM is not only cheap, but in optimal quality made with stable color spot for use with fluorescent lamps.
- this also applies to other combinations of active and inert rare earth elements which can be stabilized by this separation cut technology.
- a concrete embodiment is a fluorescent lamp using three-band phosphor.
- a light-emitting BAM ⁇ material is used on the basis of the method illustrated, in which acts as an effective rare-earth element Eu, while tolerates as inert rare earth elements La and / or Gd and / or Y to-.
- the activator Eu is intentionally added a tolerable amount of inert rare earth elements.
- the total amount of inert rare earth elements is preferably in a range of 100 to 500 ppm, based on the proportion of effective as activator Eu.
- Another phosphor which is suitable for such stability ⁇ capitalization for example BALM, so the (Ba, Sr) - Variant of BAM. It can be EuII doped phosphors good stabili ⁇ Sieren.
- EuIII doped phosphors such as Y203: Eu show poor color rendering and can not be stabilized in the desired mechanism.
- the effective activator is preferably EuII.
- the inert rare earth elements are additives to divalent La and / or Y and / or Gd.
- Figure 7 shows a fluorescent lamp 1 with a tubular piston 2 with base parts 3. inside the piston, two electrodes 4 are mounted opposite each other.
- the filling has Hg, in low pressure technique.
- Phosphor 5 is attached to the inner wall of the piston. It is, for example, a mixture of halophosphate and tripod ⁇ the phosphor, in particular a phosphor is used as the component BAM for the blue emission, which is stabilized by means of separating cut technique.
- the Eu obtained from the recycling concentrate is added as stabilizer La, Gd and Y.
- Composition may depend in particular on the waste material used.
- the index y is considerably smaller than the index x, y is preferably between 100 and 500 ppm.
- the stabilized phosphor can also for other light sources such as LED lamps or for substrates that are preceded by a conversion elements light sources ver ⁇ be spent.
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE201110007669 DE102011007669A1 (de) | 2011-04-19 | 2011-04-19 | Verfahren zur Rückgewinnung seltener Erden aus Leuchtstofflampen |
PCT/EP2012/056106 WO2012143240A2 (de) | 2011-04-19 | 2012-04-03 | Verfahren zur rückgewinnung seltener erden aus leuchtstofflampen sowie zugehörige leuchtstoffe und lichtquellen |
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EP2652078A2 true EP2652078A2 (de) | 2013-10-23 |
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EP12713700.8A Withdrawn EP2652078A2 (de) | 2011-04-19 | 2012-04-03 | Verfahren zur rückgewinnung seltener erden aus leuchtstofflampen sowie zugehörige leuchtstoffe und lichtquellen |
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EP (1) | EP2652078A2 (de) |
DE (1) | DE102011007669A1 (de) |
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DE102016223566A1 (de) | 2016-11-28 | 2018-05-30 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Leuchtstoffmischung aus löslichen und unlöslichen Leuchtstoffen und Verfahren zur Rückgewinnung der Leuchtstoffe |
EP3556873A1 (de) * | 2018-04-19 | 2019-10-23 | Paul Scherrer Institut | Verfahren zum recycling einzelner seltenerdmetalle aus fluoreszierenden pulverförmigen e-abfällen |
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CH470902A (de) | 1967-03-23 | 1969-04-15 | Kuehni App Bau Ag | Kolonneneinrichtung zur Gegenstromextraktion von Flüssigkeiten |
DE3410989A1 (de) * | 1984-03-16 | 1985-09-26 | Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH, 8000 München | Verfahren und vorrichtung zur aufarbeitung von stabfoermigen leuchtstofflampen |
DD246551A1 (de) * | 1986-03-07 | 1987-06-10 | Paedagogische Hochschule Wolfg | Verfahren zur rueckgewinnung von seltenerdverbindungen aus fluoreszenzlampen |
DE19617942C1 (de) * | 1996-04-29 | 1997-06-26 | Inst Technologie Und Umweltsch | Verfahren zur Wiederaufbereitung quecksilber- und phosphathaltiger Seltenerdleuchtstoffgemische |
DE19918793A1 (de) | 1999-04-26 | 2000-11-02 | Eberhard Gock | Verfahren zum Recycling von Dreibanden-Leuchtstoffen |
US6528938B1 (en) | 2000-10-23 | 2003-03-04 | General Electric Company | Fluorescent lamp having a single composite phosphor layer |
DE102006025945A1 (de) | 2006-06-02 | 2007-12-06 | Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH | Verfahren zur Rückgewinnung Seltener Erden aus Leuchtstofflampen |
-
2011
- 2011-04-19 DE DE201110007669 patent/DE102011007669A1/de not_active Withdrawn
-
2012
- 2012-04-03 WO PCT/EP2012/056106 patent/WO2012143240A2/de active Application Filing
- 2012-04-03 EP EP12713700.8A patent/EP2652078A2/de not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO2012143240A2 * |
Also Published As
Publication number | Publication date |
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WO2012143240A2 (de) | 2012-10-26 |
DE102011007669A1 (de) | 2012-10-25 |
WO2012143240A3 (de) | 2012-12-13 |
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