CN102952948A - Separation and purification method of rare earth metals in phosphor powder - Google Patents
Separation and purification method of rare earth metals in phosphor powder Download PDFInfo
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Abstract
The invention relates to a separation and purification method of rare earth metals in phosphor powder. The method mainly comprises technologies of enrichment of the rare earth elements, acquirement of rare earth oxide, and chemical vapor transportation of the rare earth elements. The chemical vapor transportation technology of the rare earth elements further comprises a chlorination reaction of the rare earth oxide into rare earth chloride, a reaction of sublimated anhydrous AlCl3 and the rare earth chloride to generate a rare earth compound gas RAlnCl3+3n, and distillation, gradient cooling and recycling of the rare earth compound gas to obtain a single rare earth chloride. The method is simple to operate, high in recovery efficiency, low in cost and easy to industrialize.
Description
Technical field
The present invention relates to the recovery and treatment method of fluorescent material, particularly relate to the separating and purifying method of fluorescent material middle-weight rare earths metal.
Background technology
Rare earth element and compound more and more apply in the various materials, as: the materials such as high performance magnetic material, fluorescent material, chemical sensor, high temperature semiconductors, magneto-optical disk and Rhometal.Therefore from these materials with different rare earths separations out, become now urgent problem.There are at present two kinds of methods to be used for commercial production, a kind of is as the basis take solid liquid system, utilize fractional crystallization or the precipitator method to separate, another kind is then take liquid-liquid system as the basis, utilize ion-exchange or solvent-extracted method to reach separation, more than two kinds of methods all need repeatedly to circulate, and separation efficiency is low.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of separating-purifying fluorescent material middle-weight rare earths metal, solves the problems such as existing method separation efficiency is low, complicated operation.
For solving the problems of the technologies described above, provide a kind of from fluorescent material the method for separating-purifying rare earth metal, mainly comprise the enrichment of rare earth element, obtain the technique of rare earth oxide; And the chemical vapor transportation technique of rare earth element.Wherein, the chemical vapor transportation technique of described rare earth element further may further comprise the steps:
1) chlorination reaction of rare earth oxide generates rare earth chloride;
2) anhydrous AlCl
3The distillation after and rare earth chloride following reaction occurs:
RCl
3+ n AlCl
3=RAl
nCl
3+3n, n=1,2,3,4 wherein, R represents rare earth element;
3) the rare earth compound gas RAl that generates
nCl
3+3nDistillation is reclaimed by the gradient cooling, obtains single rare earth chloride.
And the process of enriching of described rare earth element further may further comprise the steps:
1) with fluorescent material dissolving and filter to such an extent that contain the filtrate of rare earth ion;
2) get fluoride salt solution and add in the described filtrate that contains rare earth ion, reaction generates rare earth fluorine;
3) rare earth fluorine is added precipitate in the NaOH solution and transform to generate rare earth hydrate;
4) the rare earth hydrate high-temperature roasting becomes rare earth oxide.
The step 1 of described rare earth element process of enriching is that fluorescent material is dissolved in dilute sulphuric acid, fully stirs, and suction filtration must contain the filtrate of rare earth ion, simultaneously the filter cake of recyclable barium sulfate-containing and lead sulfate; Reaction generates rare earth fluorine in the step 2 of described rare earth element process of enriching, through suction filtration, rare earth fluorine remains in the filter cake, washing leaching cake, the filtrate that must contain the filter cake of pure rare earth fluorine and contain non-rare earth ion is further recycled filtrate: add NaOH in the filtrate of containing non-rare earth ion and regulate the non-rare earth ion of pH value to the excessive fluoride salt of 11-11.5 precipitation, generate aluminum hydroxide precipitation, zinc hydroxide precipitation and cadmium hydroxide precipitation, the filtrate cycle utilization that gets containing sodium fluoride behind the suction filtration.
Further, the step 1 of described rare earth element process of enriching is to get fluorescent material, by solid-to-liquid ratio be 1:20 to add concentration be the dilute sulphuric acid of 10%-15%, under 75-85 ℃ of temperature, dissolve, fully stir 2-3h, suction filtration must contain the filtrate of rare earth ion; In the step 2 of described rare earth element process of enriching, get NaF solution and add the described filtrate that contains rare earth ion, add-on is 3.5-4 times of original rare earth.
The step 1 of described Rare-Earth Element Chemistry vapor transportation technique is at N
2+ Cl
2Mixed gas, 1000 ℃ ± 5 ℃ of temperature, reaction times 1-3h is reacted into rare earth chloride with rare earth oxide.N
2Flow is 30 cubic centimetres/minutes, Cl
2Flow be 5 cubic centimetres/minute.
In the step 2 of described Rare-Earth Element Chemistry vapor transportation technique, anhydrous AlCl
3170-190 ℃ of distillation, rare earth chloride and aluminum chloride mol ratio are 1:1.
In the step 3 of described Rare-Earth Element Chemistry vapor transportation technique, the rare earth compound gas RAl of generation
nCl
3+3nAccording to each rare earth element volatility, volatilize successively at the lower of 1000 ℃-25 ℃ thermogrades, and precipitate in the cooling graphite annulus fragment of correspondence, collect the RAl that is deposited on the graphite annulus
nCl
3+3n, at N
2And Cl
2Protection under further the heating, make AlCl
3Therefrom separate, collect at last and obtain single rare earth chloride.Preferably, the rare earth compound gas RAl of different volatility
nCl
3+3nBe respectively 1000-830 ℃ graphite annulus fragment in thermograde, temperature is 830-670 ℃ graphite annulus fragment, and temperature is deposition successively on the graphite annulus fragment of 650 ℃-room temperature.
After the chemical vapor transportation technique of described rare earth element is collected or when two kinds or above rare earth compound, further be included in and add appropriate bases metal or alkaline rare earth metal reductive agent in the mishmetal, wherein a kind of rare earth trichloride is reduced into dichloro compound, utilize the difference of both volatility again to carry out the chemical vapor transportation separation, reduction obtains the pure rare-earth metals muriate, such as Europium trichloride, samarium trichloride, Yttrium trichloride etc.
Described Rare-Earth Element Chemistry vapor transportation technique also further comprises step 4, is that the rare earth chloride after step 3 is separated further is reduced to pure rare-earth metals, adopts the calciothermy of rare earth chloride:
2RCl
3+3Ca=2R+3CaCl
2
Wherein R represents rare earth element.
Technique scheme has following beneficial effect at least:
The invention provides a kind of method of simply, efficiently collecting the fluorescent material middle-weight rare earths, by first the rare earth element in the fluorescent material being carried out enrichment, remove a large amount of non-rare earths, the mode that adopts again chemical vapor transportation technology and vacuum distilling to combine realizes separating different rare earth elements, the method can be separated different rare earth elements efficiently, obtains highly purified rare earth chloride.
This thinking has two innovative points: 1. before carrying out Rare Earth Separation, first rare earth element is carried out enrichment, remove non-rare earth, the interference that can avoid non-rare earth that follow-up separation is caused; 2. adopt chemical vapor transportation that different rare earths are separated, operation of equipment is simple, and is cheap, is easy to realize industrialization.
Description of drawings
Fig. 1 is the process flow sheet of separating and purifying method the first technique of the present invention.
Fig. 2 is the structural representation of implementing separating and purifying method the second technique equipment used of the present invention.
Embodiment
Please refer to Fig. 1 and Fig. 2, is example by collecting CRT fluorescent material rare earth elements, makes a concrete analysis of separating and purifying method of the present invention.
The separating and purifying method of fluorescent material middle-weight rare earths metal of the present invention, it mainly comprises the first technique of rare earth element enrichment and the second technique of Rare-Earth Element Chemistry vapor transportation.
Wherein, as shown in Figure 1, the process of enriching of rare earth element further may further comprise the steps:
(1) fluorescent material among the CRT is dissolved in dilute sulphuric acid, fully stirs, suction filtration must contain the filtrate of rare earth ion, and reclaims the filter cake of barium sulfate-containing and lead sulfate;
(2) get fluoride salt solution and add the described filtrate that contains rare earth ion, reaction generates rare earth fluorine, and suction filtration, rare earth fluorine remain in the filter cake, and washing leaching cake must contain the filter cake of pure rare earth fluorine, and filtrate is reclaimed and the recycle fluoride salt;
(3) rare earth fluoride is added precipitate in the NaOH solution and transform to generate rare earth hydrate;
(4) rare earth hydrate places the retort furnace high-temperature roasting to become rare earth oxide, obtains the starting material of next step chemical vapor transportation.
In a specific examples, the process of enriching of rare earth element is:
Get cathodic ray-tube fluorescent powder, by solid-to-liquid ratio be 1:20 to add concentration be that the dilute sulphuric acid of 10%-15% dissolves under 75-85 ℃ of temperature, fully stir 2-3h, suction filtration must contain the filtrate of rare earth ion; Get fluoride salt (NaF) solution and add the described filtrate that contains rare earth ion, the amount that adds NaF is 3.5-4 times of original rare earth, reaction generates rare earth fluorine, suction filtration, rare earth fluorine remains in the filter cake, washing leaching cake 3 times must contain the filter cake of pure rare earth fluorine and contain the filtrate of non-rare earth ion; Reclaim excessive fluoride salt, get the filtrate of containing non-rare earth ion, add NaOH, can regulate the non-rare earth ion of pH value to the excessive fluoride salt of 11-11.5 precipitation, generate aluminum hydroxide precipitation, zinc hydroxide precipitation and cadmium hydroxide precipitation, the filtrate cycle utilization that gets containing sodium fluoride behind the suction filtration; Simultaneously, rare earth fluoride adds in the NaOH solution, can regulate pH to 11-13, precipitates to transform to generate rare earth hydrate; At last, rare earth hydrate places retort furnace high temperature (for example temperature 500-550 ℃) roasting to become rare earth oxide, obtains the starting material of next step chemical vapor transportation.
The chemical vapor transportation technique of rare earth element further may further comprise the steps:
(1) with the rare earth oxide of removing non-rare earth after the enrichment, put into reaction boat as shown in Figure 2, pass into N
2+ Cl
2Mixed gas, in 1000 ℃ ± 5 ℃ of temperature, the reaction 1-3h, rare earth oxide is reacted into rare earth chloride;
(2) then, anhydrous AlCl
3170-190 ℃ of distillation, with rare earth chloride following reaction occurs:
RCl
3(s, l)+n AlCl
3(g)=RAl
nCl
3+3n(g) (n=1,2,3,4) (R represents rare earth element); S represents solid-state, and l represents liquid state, and g represents gaseous state.Thereby generate rare earth compound gas RAl
nCl
3+3n, until RCl
3Till reacting completely, the reaction times is about (but being not limited to) 20-30min.
(3) the gradient cooling is reclaimed after the distillation: the different rare earth compound gas RAl of generation
nCl
3+3nBecause each rare earth element self, its volatility is different, successively volatilization in the Glass tubing of differing temps gradient (1000 ℃-25 ℃), when gas is run into cold graphite annulus (for example I, II, III, IV, V, VI, VII) postprecipitation in the above, collect the RAl that is deposited on the graphite annulus
nCl
3+3n, at N
2And Cl
2Protection under further the heating, make AlCl
3Therefrom separate, collect at last and obtain single rare earth chloride.
(4) according to using needs, the rare earth chloride after separating further can be reduced to pure rare-earth metals: the calciothermy that adopts rare earth chloride:
2RCl
3+ 3Ca=2R+3CaCl
2(R represents rare earth element)
Thereby further obtain rare earth metal.
Further, if collect rear or two kinds or above rare earth compound, the above-mentioned chemical vapor transportation processing method of repeated using, and in mishmetal, add the appropriate bases metallic reducing agent, wherein a kind of rare earth trichloride is reduced into dichloro compound, utilize the difference of both volatility to separate, reduction obtains the pure rare-earth metals muriate.
This chemical vapor transport device mainly comprises:
Be provided with the reacting pipe 3 of inlet mouth 1 and air outlet 2,2 directions are disposed with the first reaction boat 4 and inner tube 5 to the air outlet by inlet mouth 1 in reacting pipe 3, in this inner tube 5, be provided with the second reaction boat 6 near the first reaction boat 4 one ends, inner tube 5 inwalls a plurality of graphite annuluss 7 that have been sticked successively, reacting pipe 3 is outer to be disposed with heating unit (9,10) and the refrigerating unit 8 that the first reaction boat 4 and inner tube 5 is carried out heat treated.
Heating unit comprises that reacting boat 4 corresponding to first is arranged at reacting pipe 3 the first heater block 9 outward, and be arranged at the second outer heater block 10 of reacting pipe 3 corresponding to inner tube 5, refrigerating unit 8 is arranged at reacting pipe 3 outer nearly air outlets 2 one ends, wherein the first heater block 9 and the second heater block 10 comprise well heater 11 and thermopair 12, and refrigerating unit 8 is for being set around the water cooling tube outside the reacting pipe 3.
When utilizing reaction boat shown in Figure 2 to carry out chemical vapor transportation, can first the rare earth oxide of removing non-rare earth after the enrichment be put into the second reaction boat 6.
From the ventpipe 13 of inlet mouth 1 one ends pass into flow for (but being not limited to) 30 cubic centimetres/minute nitrogen (N
2) and flow for (but being not limited to) 5 cubic centimetres/minute chlorine (Cl
2), in inner tube 5, control temperature at 1000 ± 5 ℃ by the thermopair 12 of the second heater block 10, and kept 1-3 hour, make rare earth oxide be reacted into rare earth chloride.
Then, the Aluminum chloride anhydrous (AlCl in the first heater block 9 heating the first reaction boat 4
3) make its distillation to 170-190 ℃, AlCl after the distillation
3Bring inner tube 5 into air-flow.AlCl
3React with rare earth chloride, wherein rare earth chloride and the desirable 1:1 of aluminum chloride mol ratio finally generate different rare earth compound gas RAl
nCl
3+3n
Because the characteristics of each rare earth element self, its volatility is different, 2 directions are reduced to 25 ℃ by 1000 ℃ to the thermograde of inner tube 5 gradually to the air outlet by inlet mouth 1, when gas is run into cold graphite annulus 7 postprecipitations in the above, obtain single rare earth chloride after the collection, and then reduction obtains pure rare-earth metals.
As a kind of specific examples, the thermograde of inner tube 5 can be set to multistage, every section a kind of rare earth chloride of corresponding collection, and such as 1000-830 ℃, 830-670 ℃, 650 ℃-room temperature.Correspondingly, graphite annulus 7 can be divided into the 1-14 section, and front 1-5 section temperature is 1000-830 ℃, and 5-8 section temperature is 830-670 ℃, 9 to last 14 sections temperature be 650 ℃-room temperature.According to the rule that the electronic number of rare earth increases progressively, in each section graphite annulus 7 depositions, the content that arranges according to different elements in the rare earth of temperature range changes successively, and for example, when europium content was high in the rare earth, 830-670 ℃ of corresponding graphite annulus 7 used more.
As a kind of specific examples, if two kinds of rare earth chlorides are arranged on the same graphite annulus 7, need further to separate, because these two kinds of rare earth structural similitudies need wherein a kind of reduction to strengthen difference between the two.With samarium trichloride (SmCl
3) and Neodymium trichloride (NdCl
3) be example, reduce when adopting following reaction:
3SmCl
3?+?Al?=3?SmCl
2+AlCl
3
And NdCl
3Do not reduced SmCl by Al
2With NdCl
3Obvious difference strengthen, wherein reductive agent can adopt basic metal or alkaline rare earth metal.During concrete operations, rare earth chloride and the basic metal collected are for the first time put into reaction tray 6, repeat aforementioned chemical vapor transportation and carry out separated and collected.
Press preceding method, just can from CRT fluorescent material, isolate the rare earth chlorides such as Europium trichloride, samarium trichloride, Yttrium trichloride.The method is simple to operate, organic efficiency is high, and is with low cost, is easy to industrialization.
The above is the specific embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
Claims (10)
1. the separating and purifying method of fluorescent material middle-weight rare earths metal mainly comprises:
The enrichment of rare earth element, the technique of acquisition rare earth oxide; And
The technique of the chemical vapor transportation of rare earth element;
Wherein, the chemical vapor transportation of described rare earth element further may further comprise the steps:
1) chlorination reaction of rare earth oxide generates rare earth chloride;
2) anhydrous AlCl
3The distillation after and rare earth chloride following reaction occurs:
RCl
3+ nAlCl
3=RAl
nCl
3+3n, n=1,2,3,4 wherein, R represents rare earth element;
3) the rare earth compound gas RAl that generates
nCl
3+3nThe gradient cooling is reclaimed after the distillation, thus the rare earth chloride that obtains separating.
2. separating and purifying method as claimed in claim 1, it is characterized in that: the enrichment of described rare earth element further may further comprise the steps:
1) with fluorescent material dissolving and filter to such an extent that contain the filtrate of rare earth ion;
2) get fluoride salt solution and add in the described filtrate that contains rare earth ion, reaction generates rare earth fluorine;
3) rare earth fluorine is added precipitate in the NaOH solution and transform to generate rare earth hydrate;
4) the rare earth hydrate high-temperature roasting becomes rare earth oxide.
3. separating and purifying method as claimed in claim 2, it is characterized in that: the step 1 of described rare earth element process of enriching is that fluorescent material is dissolved in dilute sulphuric acid, fully stir, suction filtration must contain the filtrate of rare earth ion, simultaneously the filter cake of recyclable barium sulfate-containing and lead sulfate; Reaction generates rare earth fluorine in the step 2 of described rare earth element process of enriching, through suction filtration, rare earth fluorine remains in the filter cake, washing leaching cake, the filter cake and the filtrate that contains non-rare earth ion that must contain pure rare earth fluorine, further recycle filtrate: in containing the filtrate of non-rare earth ion, add NaOH and regulate the non-rare earth ion of pH value to the excessive fluoride salt of 11-11.5 precipitation, generate aluminum hydroxide precipitation, zinc hydroxide precipitation and cadmium hydroxide precipitation, the filtrate cycle utilization that gets containing sodium fluoride behind the suction filtration.
4. separating and purifying method as claimed in claim 2, it is characterized in that: the step 1 of described rare earth element process of enriching, to get fluorescent material, be that to add concentration be the dilute sulphuric acid of 10%-15% to 1:20 by solid-to-liquid ratio, under 75-85 ℃ of temperature, dissolve, fully stir 2-3h, suction filtration must contain the filtrate of rare earth ion; In the step 2 of described rare earth element process of enriching, get NaF solution and add the described filtrate that contains rare earth ion, add-on is 3.5-4 times of original rare earth; In the step 3 of described rare earth element process of enriching, rare earth fluoride adds in the NaOH solution, regulates pH to 11-13, precipitates to transform to generate rare earth hydrate.
5. separating and purifying method as claimed in claim 1, it is characterized in that: the step 1 of described Rare-Earth Element Chemistry vapor transportation technique is at N
2+ Cl
2Mixed-gas atmosphere in, 1000 ℃ ± 5 ℃ of temperature, reaction times 1-3h is reacted into rare earth chloride with rare earth oxide; In the step 2 of described Rare-Earth Element Chemistry vapor transportation technique, anhydrous AlCl
3170-190 ℃ of distillation, rare earth chloride and aluminum chloride mol ratio are 1:1; In the step 3 of described Rare-Earth Element Chemistry vapor transportation technique, the rare earth compound gas RAl of generation
nCl
3+3nAccording to each rare earth element volatility, under 1000 ℃-25 ℃ thermograde, volatilize successively, and precipitate in the cooling graphite annulus fragment of correspondence, collect the RAl that is deposited on the graphite annulus
nCl
3+3n, at N
2And Cl
2Protection under further the heating, make AlCl
3Therefrom separate, collect at last and obtain single rare earth chloride.
6. separating and purifying method as claimed in claim 5 is characterized in that: in the step 1 of described Rare-Earth Element Chemistry vapor transportation technique, and N
2Flow is 30 cubic centimetres/minutes, Cl
2Flow be 5 cubic centimetres/minute; In the step 2 of described Rare-Earth Element Chemistry vapor transportation technique, anhydrous AlCl
3The distillation time rear and that rare earth chloride reacts is 20-30 minute kind.
7. separating and purifying method as claimed in claim 5 is characterized in that: in the step 3 of described Rare-Earth Element Chemistry vapor transportation technique, and the rare earth compound gas RAl of different volatility
nCl
3+3nBe respectively 1000-830 ℃ graphite annulus fragment in thermograde, temperature is 830-670 ℃ graphite annulus fragment, and temperature is deposition successively on the graphite annulus fragment of 650 ℃-room temperature.
8. separating and purifying method as claimed in claim 1, it is characterized in that: in the step 3 of the chemical vapor transportation technique of described rare earth element, when still being two kinds or above rare earth chloride after the collection, further be included in and add appropriate bases metal or alkaline rare earth metal reductive agent in the mixed rare earth chlorides, wherein a kind of rare earth trichloride is reduced into dichloro compound, utilize the difference of both volatility again to carry out the chemical vapor transportation separating-purifying, reduction obtains single rare-earth metal chloride.
9. separating and purifying method as claimed in claim 8, it is characterized in that: described basic metal or alkaline rare earth metal reductive agent are metallic aluminium.
10. such as each described separating and purifying method among the claim 1-9, it is characterized in that: described Rare-Earth Element Chemistry vapor transportation technique further comprises step 4: the rare earth chloride after step 3 is separated further is reduced to pure rare-earth metals, adopts the calciothermy of rare earth chloride:
2RCl
3+3Ca=2R+3CaCl
2
Wherein R represents rare earth element.
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| CN106995884A (en) * | 2016-01-25 | 2017-08-01 | 安徽工业大学 | A kind of method of the Extraction of rare earth element from waste phosphor powder |
| CN107937738A (en) * | 2017-12-21 | 2018-04-20 | 李本根 | A kind of new purifying plant for rare earth feed liquid |
| CN110540227A (en) * | 2018-10-29 | 2019-12-06 | 天津包钢稀土研究院有限责任公司 | Preparation method of high-quality anhydrous rare earth chloride and bromide |
| CN113046578A (en) * | 2021-02-08 | 2021-06-29 | 五矿（北京）稀土研究院有限公司 | Preparation method of low-impurity rare earth feed liquid |
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| 王育红等: "化学气相传输法制备无水稀土氯化物", 《中国稀土学报》 * |
| 贾丽萍等: "稀土氧化物纳米材料的制备方法综述", 《稀土》 * |
| 陈华妮等: "稀土卤素气态配合物热力学性质的研究", 《化学进展》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2907882A1 (en) | 2014-02-14 | 2015-08-19 | Rolf Naumann | Recovery of rare earth metals |
| CN106995884A (en) * | 2016-01-25 | 2017-08-01 | 安徽工业大学 | A kind of method of the Extraction of rare earth element from waste phosphor powder |
| CN107937738A (en) * | 2017-12-21 | 2018-04-20 | 李本根 | A kind of new purifying plant for rare earth feed liquid |
| CN110540227A (en) * | 2018-10-29 | 2019-12-06 | 天津包钢稀土研究院有限责任公司 | Preparation method of high-quality anhydrous rare earth chloride and bromide |
| CN113046578A (en) * | 2021-02-08 | 2021-06-29 | 五矿（北京）稀土研究院有限公司 | Preparation method of low-impurity rare earth feed liquid |
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