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WO2004074398A1 - Procede de recuperation de poudre fluorescente - Google Patents

Procede de recuperation de poudre fluorescente Download PDF

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Publication number
WO2004074398A1
WO2004074398A1 PCT/JP2004/000627 JP2004000627W WO2004074398A1 WO 2004074398 A1 WO2004074398 A1 WO 2004074398A1 JP 2004000627 W JP2004000627 W JP 2004000627W WO 2004074398 A1 WO2004074398 A1 WO 2004074398A1
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WIPO (PCT)
Prior art keywords
phosphor
phase
powder
oil phase
separation
Prior art date
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Ceased
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PCT/JP2004/000627
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English (en)
Japanese (ja)
Inventor
Toyohisa Fujita
Atsushi Shibayama
Guangiun Mei
Takao Kawai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shinko Pantec Co Ltd
Tohoku Techno Arch Co Ltd
Original Assignee
Tohoku Techno Arch Co Ltd
Kobelco Eco Solutions Co Ltd
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Publication of WO2004074398A1 publication Critical patent/WO2004074398A1/fr
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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

Definitions

  • the present invention relates to a method for separating and recovering a fluorescent powder mixed powder used inside a fluorescent lamp tube (including a cathode ray tube).
  • the present invention relates to a solid-state separation technique for separating three-wavelength fluorescent powder containing a rare-earth element recovered from a discarded fluorescent tube into each of the three-wavelength components without substantially dissolving the mother crystal.
  • waste fluorescent tubes including CRTs are now beginning to separate and collect some of the glass, frame metal, and mercury.
  • the fluorescent powder coated inside the fluorescent tube has not been reused in the past because the used fluorescent powder has deteriorated luminous efficiency. Further, it was difficult to separate the particles of the fluorescent powder, and the particles were either discarded without being collected or placed in a high-temperature melting furnace.
  • fluorescent light using rare-earth compounds containing rare-earth compounds with narrow peaks at half-width in the red, blue and green visible light regions has recently been developed.
  • Tubes have become widespread.
  • these fluorescent powders contain, for example, europium (Eu) ion (II) for blue, terbium (Tb) ion (111) for green, and europium (III) for red.
  • Eu europium
  • Tb terbium
  • III europium
  • the phosphors are separated and recovered from waste (a large amount) that uses the phosphors, such as used fluorescent tubes and cathode ray tubes, in order to make effective use of the rare earth elements contained therein. Is required to be reused.
  • Patent Literature 1 rare earth metal compounds containing rare earth metal elements are subjected to mechanochemical treatment and then eluted in acid to prepare
  • Patent Document 2 a method of selectively separating and extracting rare metal components by applying a mechanochemical treatment to a waste fluorescent material containing a rare metal component and then eluting it with an acid
  • Patent Document 1 A method has been proposed in which a powder is eluted into an acid and then separated by a coprecipitation method (Non-Patent Document 1).
  • Non-Patent Document 1 it is necessary to dissolve the compound in an acid, and it is necessary to perform a treatment to reduce the compound to the original compound later, which is not a costly and economically useful method. Impractical.
  • the luminance of the fluorescent powder recovered from the waste fluorescent tube has been reduced due to deterioration.However, as a method of regenerating such fluorescent powder, the deteriorated fluorescent powder is fired at a high temperature in a reducing atmosphere. A method of regenerating has also been proposed (Patent Document 3). In this method, since the treatment with acid or the like is not performed, the original crystal form is maintained, and the optimum treatment temperature is said to be different for each type of phosphor. No separation method is described.
  • each of the three wavelength phosphors ie, blue, green, and red phosphors
  • the regeneration process is easy. Not only that, it is very advantageous for efficient separation, collection and recycling.
  • the present invention is a.
  • the starting material is waste, and the phosphor in the waste is subjected to separation and recovery treatment, and / or (2) the starting material is blue phosphor powder, red phosphor powder, and green phosphor.
  • (B) including a step of performing liquid-liquid separation between an oily solution containing a surfactant and an organic solution comprising a polar compound
  • the surfactant is a cationic surfactant, and / or (d) an anionic surfactant, and the oily solution contains lucans.
  • the aqueous solution (a) of the above [4] is selected from the group consisting of: (i) potassium sodium tartrate and (ii) alkaline salts of carbonic acid or alkaline earth salts.
  • the oily solution (1) comprises a substance selected from the group consisting of 2-tenol trifluoroacetone and n- heptane
  • the oily solution (2) comprises
  • the cationic surfactant (c) is selected from the group consisting of laurylamine and stearylamine, containing those selected from the group consisting of black form and 1-pentanol.
  • the anionic surfactant (d) is sodium laurylbenzenesulfonate or sodium 1-octanesulfonate;
  • the method for recovering a phosphor according to the above [4] which is selected from the group consisting of:
  • an aqueous solution containing sodium sodium tartrate and sodium carbonate is used as an aqueous phase
  • an n-heptane solution containing 2-tenol trifluoracetone is used as an oil.
  • the aqueous phase is mixed with the phosphor powder mixture, then the aqueous phase and the oil phase are mixed, and then separated into an aqueous phase and an oil phase, and the phosphor powder is separated from the oil phase.
  • the aqueous solution obtained in the first process is used as an aqueous phase, and a mixture of clog form and 1-pentanol is used as an oil phase, Phase and the oil phase are mixed, then separated into an aqueous phase and an oil phase, and a phosphor powder is obtained from each of the oil phase and the aqueous phase, or
  • the phosphor powder mixture recovered from the polar organic phase obtained in the first process is mixed with N, N-dimethylformamide to form a polar organic phase, which contains sodium 1-octanesulfonate
  • N, N-dimethylformamide which contains sodium 1-octanesulfonate
  • the n-heptane solution is used as an oil phase, the polar organic phase and the oil phase are mixed, then separated into a polar organic phase and an oil phase, and the phosphor powder is separated from the oil phase and the polar organic phase, respectively.
  • the green phosphor powder is obtained from the oil phase.
  • a method in which a powder mixture containing a blue phosphor powder, a red phosphor powder, and a green phosphor powder is separated into phosphor powders of each color by liquid-liquid separation, and is collected by about 1% tartaric acid.
  • the fluorescent powder mixture is placed in an aqueous phase and stirred, and then the aqueous phase and the oil phase are mixed at a ratio of about 3: 2, and a small amount of 1-pentanol is added.
  • a method in which a powder mixture containing a blue phosphor powder, a red phosphor powder, and a green phosphor powder is separated into phosphor powders of each color by liquid-liquid separation, and is collected by about 1.7 X containing 10- 4 ⁇ 3 xl O- 4 rao l / L dodecyl ⁇ Mi N'asete preparative concentrations of eta - heptane solution to an oil phase, New, using ⁇ - dimethylcarbamoyl Ruhorumuami de as a polar organic phase
  • the polar organic phase and the oil phase are mixed at a ratio of about 1: 1 to separate the polar organic phase and the oil phase, and then the green fluorescent powder is separated from the oil phase.
  • compounds having extremely similar properties such as BaMgAl 1 () 0 17 : Eu 2+ which is a blue fluorescent powder and CeMgAl 1 Q 0 17 : Tb 3+ which are a green fluorescent powder
  • BaMgAl 1 () 0 17 : Eu 2+ which is a blue fluorescent powder
  • CeMgAl 1 Q 0 17 : Tb 3+ which are a green fluorescent powder
  • Fig. 1 shows the separation flow sheet of the fluorescent powder mixture when liquid-liquid separation is performed between an aqueous solution (aqueous phase) and an oily solution (oil phase).
  • FIG. 2 shows the separation flow sheet of the fluorescent powder mixture when performing liquid-liquid separation between the organic phase (polar organic solvent phase) and the oil solution (oil phase).
  • FIG. 3 shows the results of measuring the zeta potential of the three-color fluorescent powder shown in Example 3.
  • Fig. 4 shows the results of extraction treatment using TTA-containing oil phase at different pH (condition: TTA 1 ° PST 1%, oil phase Z aqueous phase ratio 1/3).
  • Figure 5 shows the relationship between extraction and pH in a black-mouthed form ZPST solution system (condition: PST 0.05, oil / water phase ratio 2/3).
  • Fig. 6 shows the effect of pH on the separation of red fluorescent powder from other fluorescent powders in a black-mouthed form ZPST solution system (conditions: powder (solid) / liquid ratio 30 g / L, 1-pentanoe). 1/4).
  • Fig. 7 shows the effect of PST concentration on the separation of red fluorescent powder from other phosphor powders in the Cloguchi Form Z PST solution system (conditions: powder (solid), liquid ratio 30 g / L, 1-pentane Knol Z black mouth Holm ratio 1/4, neutral pH).
  • Fig. 8 shows the effect of the 1-pentanol / copper-form ratio on the separation of red fluorescent powder from other phosphor powders in the liquid-form / PST solution system (conditions: powder (solid) / Liquid ratio 30 g / L, PST 0.25%, neutral pH).
  • Fig. 9 shows the effect of powder (solid) concentration on the separation of red fluorescent powder from other phosphor powders in a black-mouthed form / PST solution system (conditions: oil phase Z aqueous phase ratio 2/3, PST 0.25 %, Neutral pH).
  • Figure 10 shows the effect of the number of treatment repetitions on the separation of red fluorescent powder from other phosphor powders in a closed-mouth form / PST solution system (conditions: oil phase / water phase ratio 2/3, PST 0.25%, neutral pH).
  • Figure 11 shows the effect of the amount of 1-pentanol used on the grade and distribution of blue fluorescent powder (conditions: PST 1%, pH 10.3, TTA 0.251%).
  • FIG. 12 shows the results of zeta potential measurement of the three-color fluorescent powder shown in Example 4.
  • FIG. 13 shows the effect of DAA concentration on the extraction and separation of the green phosphor from the phosphor mixture.
  • FIG. 14 shows the effect of the stearylamine concentration on the extraction and separation of the green phosphor from the phosphor mixture.
  • Figure 15 shows the effect of SDBS concentration on the extraction and separation of red phosphor from a mixture of blue and red phosphors
  • FIG. 16 shows the effect of SDBS concentration on the extraction separation of blue phosphor from a mixture of blue and red phosphors.
  • the first 7 Figure shows the effect of the red phosphor CH 3 on extractables separation of (CH 2) 7 S0 3 Na concentration of blue and red phosphor mixture.
  • the first 8 diagram shows the effect of blue CH 3 (CH 2) on the extractables away phosphor 7 S0 3 Na concentration of blue and red phosphor mixture.
  • the present invention has made it possible to separate fluorescent powder in a waste fluorescent tube with high efficiency as a solid without deteriorating the crystal form, including those having extremely similar crystal forms.
  • a rare metal such as a rare earth element is contained in a predetermined compound form, and a fine powder mixture of a phosphor having a specific color rendering effect is obtained by liquid-liquid separation, for example, from a three-wavelength fluorescent tube or the like.
  • the waste phosphor mixture that is used will provide technology to separate blue, green, and red monochromatic phosphor powders, respectively.
  • the rare metal may include a rare earth element.
  • the rare earth element includes 15 elements from La (lanthanum) having an atomic number of 57 to Lu (lutetium) having an atomic number of 71 and chemical properties. It may include 17 elements in addition to the two elements Sc (scandium) and Y (ittrium), which are similar to each other.
  • the phosphor used in fluorescent tubes contains many rare metals such as Y, La, Eu, Ce, and Tb.
  • the phosphor (hereinafter simply referred to as “phosphor”) contained in the discarded three-wavelength high color rendering fluorescent tube or the like is a powdery substance in which blue, green, and red single-color phosphors are mixed. And those composed of the following four types of composite oxides.
  • blue phosphor ' ⁇ ⁇ BaMgAlwO ⁇ Eu or (Sr, Ca, Ba) 1Q (P0 4) 6 Cl 2 such as Eu 2+, BaMgAl 10 0 17 or (Sr, Ca, Ba) 10 (P0 4 ) 6 C1 2 which was mainly composed of Containing Eu 2+
  • the liquid-liquid separation of the fine powder mixture of the phosphor includes a liquid-liquid separation between an aqueous solution and an oily solution, and a liquid-liquid separation between an oily solution containing a surfactant and an organic solution comprising a polar compound.
  • a crystal of a substance which is a constituent of a fine powder mixture to be separated is dissolved, or It is preferable that they do not substantially adversely affect, for example, by dissolving some of the components, and if so, they can be appropriately selected from those known to those skilled in the art in the art. Can be used, but preferably those which aid in a suitable separation.
  • organic compounds such as water, aqueous alcohol, hydrocarbons, and halogenated hydrocarbons can be used.
  • organic compounds such as polar organic compounds, hydrocarbons, and halogenated hydrocarbons can be used.
  • a separation agent can be promoted by adding a chelating agent, a metal scavenger, a surfactant, a pH adjuster, alcohols and the like.
  • a process of separating a mixture of phosphor, green, and red phosphor fine powders by liquid-liquid separation between an aqueous solution and an oil solution will be described below. Separation by the process, the water-soluble, such as P0 4 ions in separation subject It can be used preferably when no matter is included.
  • an aqueous solution that is, an aqueous solution of an organic compound having a hydroxyl group and / or a carboxyl group is used as an aqueous phase.
  • the organic compound a compound having a desired separation property is preferable, and if such a compound can be used, it can be appropriately selected from those known to those skilled in the art in the field.
  • an organic compound having a plurality of hydroxyl groups and a Z or a plurality of carboxyl groups is preferred.
  • Typical examples of the organic compound include those having about 1 to 10 carbon atoms, but tartaric acid and the like are preferable.
  • the compound may be a salt, and examples of the salt include salts with an alkali metal, an alkaline earth metal, and the like.
  • potassium sodium tartrate can be particularly preferably used.
  • the concentration of the compound in the aqueous solution can be determined by conducting experiments to achieve optimal separation.For example, when sodium tartrate is used, about 0 to 3. The concentration can be 0%, preferably about 0.2-1.5%, particularly about 0.5-1.0%.
  • the aqueous phase can be pre-added with a pH adjuster, and the addition of an appropriate pH adjuster favors separation.
  • the pH adjuster include acids, alkalis, and salts, and include, for example, sodium hydroxide and sodium carbonate. In the present invention, sodium carbonate can be particularly preferably used.
  • the aqueous phase can be adjusted to an appropriate value as appropriate, but is preferably one having the required separation properties, for example, in the range of pH 5 to 12, and preferably in the range of pH 7 to 11. Particularly preferred is a pH range of about 9 to 10.5. In a preferred representative case, ⁇ ⁇ ⁇ 3.
  • An oily solution that is, a specific constituent element or a specific structure of one of the blue, green, and red phosphors as an oil phase (eg, for example, a reagent having an affinity for a crystalline form, for example, a chelating agent, a metal scavenger, or a surfactant added to a solvent is used.
  • a reagent having an affinity for a crystalline form for example, a chelating agent, a metal scavenger, or a surfactant added to a solvent
  • sulfur, oxygen or nitrogen containing heterocyclic residue substituted fluorinated diketone compounds can be used.
  • 2-tenol trifluoroacetone can be particularly preferably used.
  • the concentration of the compound in the solvent can be determined by conducting experiments so as to achieve optimal separation.For example, when using 2-tenol trifluoracetone, about 1.0 to 50 g / L, preferably about 1.5 to 10 g / L, and more preferably about 2.0 to 3 g / L. Especially at a concentration of about 2.5 g / L.
  • the solvent for the oil phase those having no water miscibility can be suitably used, and those having the required separation properties are preferred. If such solvents are used, those known to those skilled in the art can be used. Any of these can be selected and used as appropriate, but preferred are hydrocarbons.
  • the hydrocarbons may be straight-chain or branched and / or saturated or unsaturated, but preferably straight-chain or branched and saturated hydrocarbons.
  • the carbon number of the hydrogens is preferably in the range of a liquid at room temperature, so that it can be appropriately selected and used, and it is preferable that the hydrogens have 5 to 16 carbon atoms.
  • the class can be selected from, for example, n-pentane, n-hexane, ⁇ -heptane, n-decane, n-dodecane, n-hexadecane and the like, and particularly preferably 11-hexane.
  • alcohols can be added to the system to assist the separation, and may be preferable.
  • the alcohols to be added can be appropriately selected from those known to those skilled in the art and used, and preferably include 11-pentanol.
  • water potassium tartrate is used.
  • the aqueous phase thus obtained is then mixed with an oily solution (organic phase) of a 0.25% solution of n-heptane in 2 enoinoletri fluoroacetone.
  • the ratio between the aqueous phase and the organic phase may be any as long as the required separation properties can be obtained, but can be determined by conducting experiments so as to achieve optimal separation.
  • the typical ratio is 3: 2.
  • the amount of the mixed powder to be added to the solution can be determined by conducting experiments so as to achieve the optimum separation. About 3%. Small amounts of 1-pentanol can be added to make the separation effective. After stirring the whole, it is left still.
  • the first process only the blue fluorescent powder is extracted into the organic phase, and the organic phase is filtered and then dried to obtain a blue fluorescent powder.
  • the mixture of green and red fluorescent powders remains in the aqueous phase after the removal of the organic phase.
  • the aqueous phase is subjected to a second process of the present separation.
  • an aqueous solution that is, the aqueous phase obtained in the first process can be used as the aqueous phase.
  • the oily solution used in the second process ie, the oil phase, preferably has an affinity for the green phosphor or lacks an affinity for the red phosphor.
  • a liquid material can be used, for example, a water-immiscible material can be suitably used, and a material having a required separation property is preferable. If such a material is used, it is known to those skilled in the art. These can be appropriately selected from the following and used, and preferred are those selected from the group consisting of halogenated hydrocarbons and hydroxyl group-containing hydrocarbons. As the halogenated hydrocarbons, chloroform is preferred. Hydroxyl group Preferred hydrocarbons include those that are miscible with halogenated hydrocarbons, for example, 1-pentanol is a preferred example.
  • a preferred oil phase includes a mixture of a halogenated hydrocarbon and a hydroxyl group-containing hydrocarbon, and a particularly preferred oil phase is a mixture of 11-pentanol and chloroform.
  • the ratio may be such that the required separation properties can be obtained, but it can be determined by conducting experiments to achieve the optimum separation. it can.
  • the mixing ratio of 1-pentanol and black form is particularly preferably 1: 4 or a range similar thereto.
  • the aqueous phase (containing green fluorescent powder and red fluorescent powder) obtained in the first process is mixed with 1-pentanol in a 1: 4 ratio.
  • the resulting mixture is mixed with an oil phase liquid obtained by mixing the mixture with a lip mouth form and stirring the resulting mixture.
  • the ratio between the aqueous phase and the organic phase is not particularly limited as long as the required separation properties can be obtained, but can be determined by conducting experiments so as to achieve the optimum separation.
  • a typical ratio of the aqueous phase to the organic phase is 3: 2. After stirring the whole, it is left still. In this second process, only the green fluorescent powder enters the organic phase, and the red fluorescent powder remains in the aqueous phase, thereby achieving separation.
  • a process of separating a blue, green, and red phosphor fine powder mixture by liquid-liquid separation between an organic solution composed of a polar compound and an oil solution will be described below.
  • a polar compound can be used as an organic solution, that is, an organic phase.
  • a polar organic compound may be appropriately selected from those known to those skilled in the art as a polar organic compound and used, and preferably an acid amide is used.
  • the acid amides include monoalkyl or dialkyl such as formamide and dimethylformamide (DMF). Rukiruhorumuami de like but, for example, D have to preferred such as DMF
  • a surfactant added to a solvent is used.
  • cationic surfactants can be used.
  • an organic compound containing an amino group can be suitably used.
  • laurylamine (n-dodecylamine), tetratodecylamine, hexadecylamine, and stearic acid Lilamine (n-octadodecylamine) and the like can be preferably used, but n-dodecylamine can be particularly preferably used.
  • Concentration in the solvent of the compound can and this to determine by experiments the earthenware pots by achieve separation of optimal, for example, n - when using Dodeshirua Mi Nasete DOO, about 0.5x10 one 4 ⁇ 7x10 - 4 raol / L of the can and the concentration and the child, is a preferred correct ones about 1 X10- 4 Ri concentration der of ⁇ 5 X10- 4 mol / L, is a good Ri favored correct thing about 1.5 xl0- 4 the concentration of ⁇ 4 xlO- 4 mol / L, in particular at a concentration of about 1.7 xl (T 4 ⁇ 3 X10 "1 mol / L.
  • the hydrocarbons may be linear or branched and / or saturated or unsaturated, but are preferably linear or branched.
  • the number of carbon atoms of the hydrocarbons is preferably in the range as long as a liquid at room temperature can be appropriately selected and used, and preferably the number of carbons is preferably 5 to 16.
  • the hydrocarbons may be selected from, for example, n-pentane, n-hexane, n-heptane, n-decane, n-dodecane, n-hexadecane, and the like.
  • N-butane can be selected particularly preferably.
  • DMF is used as an organic phase, and a mixture of blue, green, and red phosphors contained in a three-wavelength high-color-rendering fluorescent tube or the like is mixed therein and stirred.
  • the amount of the mixed powder to be added to the liquid can be determined by conducting experiments so as to achieve the optimal separation, but typically, it may be about 6% by weight.
  • the organic phase obtained by earthenware pots Tsuginiko about 1. 7 xl O- 4 ⁇ 3 X 10- 4 mo l / L concentration n of - dodecyl ⁇ Min acetate heptane solution tape preparative to n- containing Mix with oily liquid (oil phase).
  • the ratio between the oil phase and the organic phase may be any as long as the required separation properties can be obtained, but it can be determined by conducting experiments so as to achieve optimal separation.
  • a typical ratio of the oil phase to the organic phase is 1: 1. After stirring the whole, it is left still.
  • the heavier heptane phase goes to the upper part
  • the heavier DMF phase goes to the lower part
  • only the green-blue fluorescent powder is extracted into the heptane phase at the upper part.
  • the mixture of green and red fluorescent powders remains in the DMF organic phase after the removal of the oil phase.
  • the powder mixture is subjected to a second process of the present separation.
  • the polar compound of the first process can be used as an organic solution, that is, an organic phase.
  • the polar compound for example, DMF is preferable.
  • a surfactant added to a solvent is used.
  • an anionic surfactant can be used.
  • the anionic surfactant include an organic compound containing sulfonic acid. Suitable examples thereof include sulfonic acids having an aliphatic hydrocarbon residue or an aromatic hydrocarbon residue, and examples thereof include alkyl sulfonates, alkyl benzene sulfonates, and alkyl naphthalene sulfonates. Preferred examples thereof include sodium 1-octanesulfonate and sodium laurylbenzenesulfonate, and sodium 1-octanesulfonate can be particularly preferably used.
  • the concentration of the compound in the solvent can be determined by conducting experiments to achieve optimal separation. For example, when sodium 1-octanesulfonate is used, about 1 X10- 3 ⁇ : lOxlO- 3 mol / L of the can and the concentration and the child, is a preferred correct thing at a concentration of about 1.5 X10- 3 ⁇ 8 xlO-3 mol / L, good Ri preferred Shiimono is a concentration der about 2X10- 3 ⁇ 5 X10- 3 mol / L is, in particular, at a concentration of about 3 xlO- 3 mol / L.
  • the solvent for the oil phase the same solvent as that used in the first process can be used.
  • the hydrocarbon can be selected from, for example, n-pentane, n-hexane, n-heptane, 11-decane, n-dodecane, 11-hexadecane, etc., and is particularly preferably used. You can select n-heptane.
  • DMF is used as an organic phase.
  • the powder mixture of the blue fluorescent powder and the red fluorescent powder obtained in the first process is mixed and stirred.
  • the organic phase thus obtained is then mixed with an oily solution of an n-heptane solution (oil phase) containing sodium tocotansulphonate at a concentration of about 0.05%.
  • the ratio between the oil phase and the organic phase may be any as long as the required separation properties can be obtained, but it can be determined by conducting experiments so as to achieve the optimum separation.
  • a typical ratio of the oil phase to the organic phase is 1: 1.
  • the amount of added powder mixture in the mixture can be determined by experimentation to achieve optimal separation, but typically is about 2% by weight of the mixture. is there. After stirring the whole, it is left still. In this second process, only the blue fluorescent powder is extracted into the upper heptane phase (oil phase), and the lower DMF phase (organic phase) is extracted. Phase), only red fluorescent powder is extracted. The phases are separated, filtered and dried, whereby blue phosphor powder and red phosphor powder are separated and collected.
  • the blue phosphor, the red phosphor, and the green phosphor are recovered in a mixed state.
  • the separation / recovery phosphor is usually discarded and collected as a waste fluorescent tube or the like. Therefore, in performing the separation / recovery treatment of the present invention, a pretreatment is first performed. Accordingly, it is preferable to separate and collect only the phosphor to be treated. For example, in order to recover only the phosphor from the waste fluorescent tube, the powder containing the phosphor is separated from the metal and glass by cutting or crushing the waste fluorescent tube as described above. By removing mercury from the collected and separated and recovered powder by distillation or the like, only the phosphor can be recovered.
  • the method is not limited to the separation of fluorescent powders containing rare earth compounds, but is applicable to the separation of mixed powders of fine particles of compounds containing any metal elements.
  • red fluorescent powder (Y 2 0 3 principal to those containing Eu 3+ a)
  • Blue fluorescent powder (mainly BaMgAl 100 I7 containing Eu 2+ ), and
  • the mixture (mixture of fine powder of about several ⁇ size) was separated into liquid and liquid by an aqueous solution and an oil layer.
  • experimental sample mixed powders red, blue, and green fluorescent powders mixed at a weight ratio of 1: 1: 1 respectively
  • a sample for separation was prepared and used as a sample for separation.
  • the amount of mixed powder added to the solution is about 3% of the combined solution of the aqueous and organic phases. 1 one pentanol (CH 3 (CH 2) 4 0H) in the child 0.05 m 1 added pressure thereto, yo Ri separation to be effective. Then stir for 5 minutes. Only blue fluorescent powder is extracted on the oily solution side (in the heptane organic phase), and the oily solution is filtered and dried to obtain blue fluorescent powder.
  • the aqueous phase containing the mixed powder from which the heptane organic phase has been removed is treated as follows, and then separated into green fluorescent powder and red fluorescent powder.
  • the organic phase is mixed with the aqueous phase.
  • the ratio of the aqueous phase to the organic phase is 3 : 2 and the mixture is stirred, only the green fluorescent powder enters the organic phase and can be separated from the red fluorescent powder in the aqueous phase.
  • Table 1 shows the results of separation of the three types of fluorescent powders artificially mixed in a 1: 1: 1 ratio according to this treatment method.
  • Figure 1 shows the separation flow sheet 1 for the fluorescent powder mixture in this treatment method.
  • red fluorescent powder (Y 2 0 3 principal to those containing Eu 3 + a)
  • the mixture (mixture of fine powders of about several ⁇ size) was separated into liquid and liquid by an organic phase and an oil layer.
  • the lower phase is filtered to obtain a mixed powder of red and blue fluorescent powder.
  • This mixed powder is put in DMF and stirred.
  • This 1 - contrary octane sulfonic Sanna sampled each Li um (CH 3 (CH 2) 7 S0 3 Na) heptane put DMF phase and same amount of the dissolved 0.05% 5 minutes.
  • the amount of mixed powder in the mixed liquid is about 2% by weight.
  • Blue fluorescent powder is contained in the upper heptane phase and red fluorescent powder is contained in the lower DMF phase. Each of them is filtered and dried to obtain separated powder.
  • Table 2 shows the results of separating the three types of fluorescent powder artificially mixed at a ratio of 1: 1: 1.
  • Figure 2 shows the separation flow sheet 2 for the fluorescent powder mixture in this treatment method.
  • Pure three-color fluorescent powder is a commercially available phosphor that is widely used in fluorescent lamps and low-voltage displays, with particle sizes ranging from 1 to ⁇ , with an average particle size of 5 below ⁇ .
  • the specific gravity was measured, it was 4.295 for the red fluorescent powder, 3.506 for the blue fluorescent powder, and 4.062 for the green fluorescent powder.
  • Table 3 shows the composition of the fluorescent powder samples, and Fig. 3 shows the results of the zeta potential.
  • the zeta potential and particle size were determined using an ELS-8000 Seta-Potentiometer (Otsuka Electronic Co., Ltd., Japan). [Table 3]
  • Example 2 In the same manner as in Example 1, a solution prepared by dissolving the TTA in heptane as organic phase, was used an aqueous solution containing appropriate quantities of the PST and Na 2 C0 3 as the aqueous phase. Put the mixture of the above three colors of fluorescent powder in the aqueous phase and shake for 1-2 minutes. Next, the organic phase is mixed with the aqueous phase at a ratio of 2: 3 (volume ratio of organic phase: aqueous phase), and the resulting mixture is shaken at room temperature for 5 minutes. A small amount of 1-pentanol was added to improve the separation. The blue fluorescent powder was recovered from the organic phase by filtration and drying.
  • FIG. 4 shows the results of extractions at different pHs with the organic phase of TTA dissolved in heptane.
  • the blue fluorescent powder was selectively extracted into the organic phase in the pH range of 7 to 11 and the red and green fluorescent powders were hardly extracted.
  • the pH value of the solution was about 10.34, the extraction efficiency of blue fluorescent powder was almost 100%.
  • FIG. 3 there is a considerable difference between the zeta potentials of the three fluorescent powders at the pH values. In other words, the zeta potential of blue fluorescent powder is larger than others. There appeared to be a relationship between extraction and the surface charge of the particles. Thus, it can be seen that blue fluorescent powder can be separated from others by TTA.
  • Figure 5 shows the results for the black-mouthed form ZPST solution system.
  • the blue fluorescent powder and green fluorescent powder were extracted in the organic phase (lower phase). At an extraction rate of more than 90% in the pH range of 7 to ll, the red fluorescent powder was dispersed in the aqueous phase, with less than 10% partitioning to the organic phase. Thus, it was shown that two solvent extraction processes could potentially be used to separate a mixture of three fluorescent powders into a fluorescent powder of each color.
  • Table 4 summarizes the relationship between the extraction results of blue fluorescent powder and green fluorescent powder using TTA and pH.
  • Optimum pH is about 10. 3 and Shiiko Togawakaru preferred Ri by better to use Na 2 C0 3 to pH adjustment of the aqueous phase to use NaOH.
  • Table 5 shows the results of the effect of the concentration of TTA on the separation of blue fluorescent powder and green fluorescent powder. As the concentration of TTA decreases, the extraction efficiency increases more quickly. Under certain conditions, the best results were obtained at a TTA concentration of 2.5 g / L. However, if the concentration of TTA was too low, blue fluorescent powder could not be extracted, resulting in poor distribution.
  • the ratio of powder (solid) to liquid and the concentration of PST on the separation of blue fluorescent powder and green fluorescent powder were also investigated. As a result, it was concluded that ⁇ 2.5 g / L, pH 10.3, solid / liquid ratio 30 g / L, and PST 1% were the optimal conditions.
  • the preferred value of the 1-pentanol / co-form ratio was 0.2 to 0.5, and the red phosphor had a grade and distribution of more than 90%.
  • 1-Pentanol has the function of increasing the extractability of black-mouthed form.
  • the effect was also investigated on the powder (solid) concentration.
  • Figure 9 shows the effect of the ratio of powder (solid) to liquid on separation.
  • the preferred solid / liquid ratio was 5-30 g / L, with too much or too little powder being undesirable.
  • Increasing the number of extractions improves the separation of red fluorescent powder. For example, three extractions resulted in better separation than one extraction.
  • Figure 1 ⁇ shows the results when the extraction operation was repeated under the same extraction conditions. Repeat the extraction procedure twice or three times to separate the red fluorescent powder from the others And preferred V,
  • prodiso3 ⁇ 4 0.03 0.058 0.111 0.158
  • Table 7 shows the composition of the fluorescent powder samples, and Fig. 12 shows the results of the zeta potential.
  • red fluorescent powder and blue fluorescent powder were separated in a DMF / heptane system using DMF in which sodium 1-octanesulfonate was dissolved.
  • the upper heptane phase contains blue fluorescent powder, and the lower DMF phase contains red fluorescent powder. Each of them is filtered and dried to obtain separated powder.
  • Figure 13 shows the results of investigating the effect of DAA concentration on this separation.
  • a preferred range of DAA concentration was 1 X10- 4 ⁇ 2 X10- 4 mol / L.
  • the results for stearylamine are shown in Table 9 and Figure 14. As is evident from Fig. 14, the behavior when stearylamine was used had a tendency similar to that of DAA. Stearylamine concentration is 2X10—! It can be seen that preferably controlled to ⁇ 3 X10 one 4 mol / L.
  • a negative Ion surfactant monolaurate Lil benzenesulfonic Sanna Application Benefits ⁇ beam were (SDBS C 18 H 29 S0 3 Na) and separation using 1 Okutansuruhon Sanna Application Benefits um.
  • the results obtained with the heptane / DMF system are shown in FIGS. Good results der when the concentration of SDBS is about 3 xlO _3 mol / L I got it.
  • Table 10 shows the results of examining the effect of the difference in the solvent when the separation operation was performed using sodium 1-octanesulfonate. There was no significant difference except for n-dodecane, with a grade and distribution of more than 90%. For heptane, over 95% grade and distribution were obtained for blue and red phosphors.
  • Table 11 shows the results of the first process of this separation (separation of the green phosphor). It also shows the results of the second process (separation of red and blue phosphors).
  • the concentration of the powder (solid) is preferably about 30 g / L in the first process of the present separation, and about 35 g / L in the second process.
  • Table 13 shows the results of investigating the effect of the mixture of the starting fluorescent powder mixture (mixed powder) on the separation.
  • First process of separation Suteariruami down 1. 85 X 10- 4 mo l / L, concentration 24 g / L of powder (solid), hepta down / DMF ratio (volume ratio) 1: was performed in 1 condition .

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Abstract

L'invention concerne un procédé pour récupérer une poudre fluorescente, caractérisé en ce que la poudre fluorescente est séparée et récupérée par un processus de séparation liquide-liquide à partir d'un mélange de poudres contenant ladite poudre fluorescente. Ledit procédé repose sur une technique de séparation des substances solides, selon laquelle un mélange de trois poudres fluorescentes pour trois longueurs d'onde contenant des éléments des terres rares, récupéré à partir d'un tube fluorescent usé, est séparé en chacune des poudres avec la longueur d'onde respective, sensiblement sans dissolution de leurs cristaux mères. Dans certains modes de réalisation, on utilise de la 2-thénoyltrifluoroacétone, du tartrate de sodium et de potassium, du carbonate de sodium, du n-heptane, du chloroforme, du N,N-diméthylformamide, de la dodécylamine, du 1-octanesulfonate de sodium, de l'éthanol, du 1-pentanol, de l'eau ou similaire, la séparation pouvant être effectuée de manière simple et économique avec un bon rendement.
PCT/JP2004/000627 2003-02-20 2004-01-23 Procede de recuperation de poudre fluorescente Ceased WO2004074398A1 (fr)

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JP5149384B2 (ja) 2008-07-14 2013-02-20 信越化学工業株式会社 長残光蛍光体の製造方法
CN102333842B (zh) * 2009-02-27 2014-10-22 信越化学工业株式会社 长余辉荧光体陶瓷及其制造方法
WO2014078056A1 (fr) * 2012-11-14 2014-05-22 General Electric Company Procédé de récupération d'une luminophore
WO2014081547A1 (fr) * 2012-11-22 2014-05-30 General Electric Company Procédé de récupération de phosphore
WO2014144463A1 (fr) 2013-03-15 2014-09-18 The University Of Houston System Procédés et systèmes de récupération de métaux des terres rares
EP2969276A4 (fr) * 2013-03-15 2017-01-18 The University Of Houston System Procédés et systèmes de récupération de métaux des terres rares

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4159931A (en) * 1977-05-07 1979-07-03 International Standard Electric Corporation Color-television screen-coating room
JPH02504162A (ja) * 1988-04-29 1990-11-29 ヴイデオコロール 三色テレビジョン受像管に用いられる蛍光体を再生する「非粉砕」法
JP2002302670A (ja) * 2001-04-04 2002-10-18 Shinko Pantec Co Ltd 蛍光体の再生処理方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4159931A (en) * 1977-05-07 1979-07-03 International Standard Electric Corporation Color-television screen-coating room
JPH02504162A (ja) * 1988-04-29 1990-11-29 ヴイデオコロール 三色テレビジョン受像管に用いられる蛍光体を再生する「非粉砕」法
JP2002302670A (ja) * 2001-04-04 2002-10-18 Shinko Pantec Co Ltd 蛍光体の再生処理方法

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