CN105039698A - Method of high-effectively recycling rare earth from waste CRT fluorescent powder - Google Patents

Method of high-effectively recycling rare earth from waste CRT fluorescent powder Download PDF

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Publication number
CN105039698A
CN105039698A CN201510189446.8A CN201510189446A CN105039698A CN 105039698 A CN105039698 A CN 105039698A CN 201510189446 A CN201510189446 A CN 201510189446A CN 105039698 A CN105039698 A CN 105039698A
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China
Prior art keywords
rare earth
hydrochloric acid
solid
rare
fluorescent material
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CN201510189446.8A
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Inventor
周培国
李媛媛
孙倩
祝芳
邹从欢
蔡诚
陆天宇
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Nanjing Forestry University
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Nanjing Forestry University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The invention provides a method of high-effectively recycling rare earth from waste CRT fluorescent powder, wherein the method includes the steps of 1) treating the waste CRT fluorescent powder with diluted hydrochloric acid as a pre-treatment agent; 2) leaching the rare earth elements with concentrated hydrochloric acid as a leaching agent; and 3) recycling yttrium and europium through secondary precipitation. The method is advantaged in that: 1) the use amount of acid in the leaching process and non-rare earth impurities in the leaching process are reduced, and the follow-up impurity removal difficulty is reduced, and the purity of recycled rare earth is greatly increased; 2) the method can not only avoid the influence of calcium in the fluorescent powder but also increase the leaching rate of the rare earth in the leaching process, so that the leaching rate is greatly increased by means of step-by-step dissolution with hydrochloric acid in different concentration; 3) not only is the precipitation rate improved but also the purity of the recycled rare earth is ensured effectively; 4) the method is simple in operation and is low in cost, can prevent environment pollution and recycle resources; and 5) the method is higher than 90% in recycling efficiency and is high in production benefit.

Description

A kind of high efficiente callback is given up the method for CRT fluorescent material middle-weight rare earths
Technical field
The present invention relates to a kind of method that fluorescent material middle-weight rare earths reclaims, be specifically related to a kind of high efficiente callback and give up the method for CRT fluorescent material middle-weight rare earths, belong to waste processing arts.
Background technology
Along with the quickening day by day of electronic product update speed, have the electron wastes of nearly 1,000,000 tons to produce every year, and televisor account for wherein significant proportion, CRT display screen scribbles the fluorescent material containing rare earth.These useless CRT fluorescent material overwhelming majority of current China are landfilled or arbitrarily abandon, not only contaminate environment, also waste valuable rare earth resources, not only there is economic benefit so reclaim the rare earth in discarded CRT fluorescent material, also there is very high social benefit simultaneously.
Summary of the invention
The invention provides a kind of high efficiente callback to give up the method for CRT fluorescent material middle-weight rare earths, its object is to 1) Purity of Rare Earth reclaimed is improved greatly; 2) leaching yield of leaching stage rare earth is improved; 3) not only improve deposition rate, and effectively ensure the purity of recovering rare earth; 4) organic efficiency will arrive more than 90%.
Technical solution of the present invention: a kind of high efficiente callback is given up the method for CRT fluorescent material middle-weight rare earths, comprises following processing step:
1) dilute hydrochloric acid is utilized to carry out pre-treatment;
2) hydrochloric acid of higher concentration is utilized to carry out acidolysis to pre-treatment gained solid;
3) technique adopting precipitation of hydroxide to combine with oxalic acid precipitation, recovering rare earth;
The present invention compared with prior art has the following advantages:
1) utilize dilute hydrochloric acid to carry out pre-treatment to useless CRT fluorescent material, decrease the consumption of leaching stage acid, decrease the non-rare earth impurity of leaching stage simultaneously, reduce follow-up removal of impurities difficulty, the Purity of Rare Earth reclaimed is improved greatly; 2) with the higher hydrochloric acid of concentration as leaching agent, not only can avoid the impact of calcium in fluorescent material, and improve the leaching yield of leaching stage rare earth, therefore, adopt the hydrochloric acid step-wise dissolution of different concns greatly can improve the leaching yield of rare earth; 3) technique adopting ammonia precipitation process to combine with oxalic acid precipitation, to reclaim the rare earth element in leach liquor, not only improves deposition rate, and effectively ensures the purity of recovering rare earth; 4) simple to operate, with low cost, not only prevent environmental pollution but also reclaimed resource; 5) organic efficiency can arrive more than 90%, and productivity effect is high.Resource has been reclaimed again in environmental pollution, and organic efficiency can arrive more than 90%, productivity effect is high.
Accompanying drawing explanation
Fig. 1 is schema of the present invention.
Embodiment
As shown in Figure 1, a kind of high efficiente callback is given up the method for CRT fluorescent material middle-weight rare earths, comprises following processing step:
1) dilute hydrochloric acid is utilized to carry out pre-treatment;
2) hydrochloric acid of higher concentration is utilized to carry out acidolysis to pre-treatment gained solid;
3) technique adopting ammonia precipitation process to combine with oxalic acid precipitation, recovering rare earth.
Described processing step 1) utilize dilute hydrochloric acid to carry out pre-treatment, specifically concentration is adopted to be 0.2-0.8mol/L hydrochloric acid, solid-to-liquid ratio be 1:10-1:20, temperature is 30-55 DEG C, carry out pre-treatment to useless CRT fluorescent material under the condition that stirs, reaction 0.5-2h, removes non-rare earth impurity that is comparatively easy in fluorescent material and acid-respons; Cross the filtrate filtered containing a large amount of impurity, obtain the remaining solid that Purity of Rare Earth is higher.
Described 2) hydrochloric acid of higher concentration is utilized to carry out acidolysis to pre-treatment gained solid, specifically adopt the hydrochloric acid of 2-4mol/L, be 1:5-1:10 in solid-to-liquid ratio, under the condition that temperature is 40-65 DEG C, stir, acidleach is carried out to the remaining solid of gained after pre-treatment, extraction time is 1-2h, and filtering gained liquid is re dip solution.
Described 3) technique adopting ammonia precipitation process to combine with oxalic acid precipitation, recovering rare earth.
Adopt the rare earth in the method recovery leach liquor of ammonia precipitation process-solid-liquid separation-oxalic acid secondary sedimentation, comprise
1. utilize ammonia precipitation process, adopt oxyhydroxide precipitation classification that the larger non-rare earth impurity of rare earth element and oxyhydroxide solubility product is separated, then carry out solid-liquid separation, effectively the purity of raising rare-earth products;
2. one-level being precipitated gained solid to add acid dissolve and obtain rare-earth enrichment liquid, is 60-80 in temperature oadding concentration under the condition of C is that 50g/L oxalic acid precipitates, and digestion time is 2-4h, filters, and obtains hydrated rare-earth oxalate;
3. by hydrated rare-earth oxalate dry 0.5-1h at 105 DEG C, 650-850 DEG C of calcining 20-45min afterwards, obtain rare earth oxide, the rate of recovery reaches more than 90%.
Below in conjunction with example, the invention will be further described:
In the embodiment of the present invention, the main component of pending CRT fluorescent material is Y 2o 2s:Eu 3+or Y 2o 3: Eu 3+(red), (Zn, Cd) S:Cu, Al(is green) and ZnS:Ag(indigo plant), know that the existing forms of element Y and Zn in this discarded CRT fluorescent material is mainly Y by the XRD figure spectrum analysis of pending CRT fluorescent material 2o 2s and ZnS, also contain the impurity such as the glass mixed in part CRT picture tube shattering process and Al metal membrane in sample in addition, the composition of CRT fluorescent material pending in example of the present invention, as following table, represents with per-cent:
Phosphor constituents table (%)
Zn S Y Al Eu Ca Si Pb Other
27.8 23.4 14.5 10.6 1.00 0.26 3.54 1.51 17.39
1) CRT fluorescent material carries out pre-treatment; The occurrence status of useless CRT fluorescent material middle-weight rare earths is mainly Y 2o 2s, its Stability Analysis of Structures, comparatively slow with acid-respons, the impurity that ZnS, Al etc. are soluble in acid can preferentially react; Carry out pre-treatment with dilute hydrochloric acid, the impurity that major part is soluble in acid enters in solution, and rare earth element sluggish, only have and be seldom partly dissolved; Cross the filtrate and glass cullet that filter containing a large amount of impurity, the remaining solid that Purity of Rare Earth is relatively high can be obtained; The gas produced in preprocessing process is passed in liming and is reclaimed.
Be 55 DEG C with the hydrochloric acid of 0.8mol/L in temperature in step, stirring velocity is stir 2h under the condition of 200r/min to carry out pre-treatment to CRT fluorescent material, and wherein best solid-to-liquid ratio is 1:20.
2) adopt the hydrochloric acid of higher concentration as leaching agent, acidolysis carried out to the remaining solid of pretreatment stage gained, obtains re dip solution:
Be 65 DEG C with the hydrochloric acid of 4mol/L in temperature in step, stirring velocity is stir 2h under the condition of 200r/min to carry out acidolysis to remaining solid, and wherein solid-to-liquid ratio is 1:10, leaches in step and there occurs a large amount of reactions:
3) rare earth in the method recovery leach liquor of ammonia precipitation process-solid-liquid separation-oxalic acid secondary sedimentation is adopted; First precipitate with ammoniacal liquor in this step, pH about 7.5 makes rare earth element and the larger non-rare earth impurity of oxyhydroxide solubility product (as Al 3+, Fe 3+deng) and the less non-rare earth impurity of oxyhydroxide solubility product constant (as Mg 2+, Fe 2+deng) be separated, filter; Then the solid 3ml concentrated hydrochloric acid of gained is dissolved, with concentration be 50g/L oxalic acid carry out secondary sedimentation, be add oxalic acid under the condition of 80 DEG C to precipitate in temperature, digestion time is 4h, then filter, obtain hydrated rare-earth oxalate and obtain highly purified rare-earth oxalate, the reaction related to is as follows:
The thermal decomposition process of hydrated rare-earth oxalate roughly can be divided into dehydration, resolves into subcarbonate, be decomposed into oxide compound three main phase further, between 55-380 DEG C, progressively remove moisture; 380-650 oresolve into subcarbonate between C, change to oxide compound when temperature is greater than 735 DEG C of subcarbonates, its reaction equation is:
Hydrated rare-earth oxalate will be obtained prior to 105 in this step odry 1h in C baking oven, calcine 1h in retort furnace at 850 DEG C afterwards, obtain rare earth oxide, the rate of recovery reaches more than 90%.

Claims (4)

1. high efficiente callback is given up a method for CRT fluorescent material middle-weight rare earths, it is characterized in that the method comprises following processing step:
1) dilute hydrochloric acid is utilized to carry out pre-treatment;
2) hydrochloric acid of higher concentration is utilized to carry out acidolysis to pre-treatment gained solid;
3) technique adopting ammonia precipitation process to combine with oxalic acid precipitation, recovering rare earth.
2. a kind of high efficiente callback according to claim 1 is given up the method for the rare earth in CRT fluorescent material, it is characterized in that described processing step 1) utilize dilute hydrochloric acid to carry out pre-treatment: adopt concentration to be 0.2-0.8mol/L hydrochloric acid, solid-to-liquid ratio be 1:10-1:20, temperature be 30-55 DEG C stir condition under pre-treatment is carried out to useless CRT fluorescent material, reaction 0.5-2h, removes non-rare earth impurity that is comparatively easy in fluorescent material and acid-respons; Cross the filtrate filtered containing a large amount of impurity, obtain the remaining solid that Purity of Rare Earth is higher.
3. a kind of high efficiente callback according to claim 1 is given up the method for the rare earth in CRT fluorescent material, it is characterized in that described processing step 2) utilize the hydrochloric acid of higher concentration to carry out acidolysis to pre-treatment gained solid: the hydrochloric acid adopting concentration 2-4mol/L, be 1:5-1:10 in solid-to-liquid ratio, temperature is under the condition of the stirring of 40-65 DEG C, acidleach is carried out to the remaining solid of gained after pre-treatment, extraction time is 1-2h, and filtering gained liquid is re dip solution.
4. a kind of high efficiente callback according to claim 1 is given up the method for the rare earth in CRT fluorescent material, it is characterized in that described processing step 3) adopt the technique that combines with oxalic acid precipitation of ammonia precipitation process, recovering rare earth: adopt the rare earth in the method recovery leach liquor of ammonia precipitation process-solid-liquid separation-oxalic acid secondary sedimentation, specifically comprise
1. utilize ammonia precipitation process, adopt oxyhydroxide precipitation classification that the larger non-rare earth impurity of rare earth element and oxyhydroxide solubility product is separated, then carry out solid-liquid separation, effectively the purity of raising rare-earth products;
2. one-level being precipitated gained solid to add acid dissolve and obtain rare-earth enrichment liquid, is 60-80 DEG C in temperature
Condition under to add concentration be that 50g/L oxalic acid precipitates, digestion time is 2-4h, filters, and obtains hydrated rare-earth oxalate;
3. by hydrated rare-earth oxalate dry 0.5-1h, 650-850 DEG C afterwards at the temperature of 105 DEG C
Calcining 20-45min, obtain rare earth oxide, the rate of recovery reaches more than 90%.
CN201510189446.8A 2015-04-21 2015-04-21 Method of high-effectively recycling rare earth from waste CRT fluorescent powder Pending CN105039698A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ306432B6 (en) * 2016-05-13 2017-01-18 DEKONTA, a.s. A method of selective regeneration of rare earth elements and/or toxic metals harmful to the environment from e-waste, particularly from cathode-ray tubes and CRT monitors
CN106967891A (en) * 2017-03-29 2017-07-21 江西理工大学 A kind of method of gradient recovering rare earth in mixing waste from fluorescent RE powder
CN108300477A (en) * 2018-01-31 2018-07-20 武汉理工大学 A method of it recycling yttrium from waste phosphor powder and prepares rare earth up-conversion
CN108517426A (en) * 2018-05-15 2018-09-11 北京工业大学 The method that the CRT fluorescent powder middle rare earth that gives up under a kind of temperate condition efficiently separates recycling
WO2022116870A1 (en) * 2020-12-02 2022-06-09 北京工业大学 Method for recovering rare earths from waste cerium-based rare-earth polishing powder by two-step acid leaching stepwise separation
CN115491512A (en) * 2021-06-17 2022-12-20 江苏宁达环保股份有限公司 Method for extracting and recovering noble metal from cathode ray tube fluorescent powder

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CN102634667A (en) * 2012-04-26 2012-08-15 中国科学院城市环境研究所 Method for recycling rear-earth elements form abandoned fluorescent lamps
CN102828030A (en) * 2012-09-13 2012-12-19 北京工业大学 Method for recycling rare earth elements in rare earth fluorescent powder waste by ultrasonic-submolten salt process
CN103131862A (en) * 2013-03-13 2013-06-05 龙南县中利再生资源开发有限公司 Pretreatment decomposition method for extracting high-purity rare earth oxide from phosphor powder waste material

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CN102634667A (en) * 2012-04-26 2012-08-15 中国科学院城市环境研究所 Method for recycling rear-earth elements form abandoned fluorescent lamps
CN102828030A (en) * 2012-09-13 2012-12-19 北京工业大学 Method for recycling rare earth elements in rare earth fluorescent powder waste by ultrasonic-submolten salt process
CN103131862A (en) * 2013-03-13 2013-06-05 龙南县中利再生资源开发有限公司 Pretreatment decomposition method for extracting high-purity rare earth oxide from phosphor powder waste material

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ306432B6 (en) * 2016-05-13 2017-01-18 DEKONTA, a.s. A method of selective regeneration of rare earth elements and/or toxic metals harmful to the environment from e-waste, particularly from cathode-ray tubes and CRT monitors
CN106967891A (en) * 2017-03-29 2017-07-21 江西理工大学 A kind of method of gradient recovering rare earth in mixing waste from fluorescent RE powder
CN106967891B (en) * 2017-03-29 2018-10-09 江西理工大学 A method of the gradient recovering rare earth from rare earth phosphor mixing waste
CN108300477A (en) * 2018-01-31 2018-07-20 武汉理工大学 A method of it recycling yttrium from waste phosphor powder and prepares rare earth up-conversion
CN108300477B (en) * 2018-01-31 2020-10-16 武汉理工大学 Method for preparing rare earth up-conversion material by recovering yttrium element from waste fluorescent powder
CN108517426A (en) * 2018-05-15 2018-09-11 北京工业大学 The method that the CRT fluorescent powder middle rare earth that gives up under a kind of temperate condition efficiently separates recycling
CN108517426B (en) * 2018-05-15 2020-02-04 北京工业大学 Method for efficiently separating and recycling rare earth in waste CRT fluorescent powder under mild condition
WO2022116870A1 (en) * 2020-12-02 2022-06-09 北京工业大学 Method for recovering rare earths from waste cerium-based rare-earth polishing powder by two-step acid leaching stepwise separation
CN115491512A (en) * 2021-06-17 2022-12-20 江苏宁达环保股份有限公司 Method for extracting and recovering noble metal from cathode ray tube fluorescent powder

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Application publication date: 20151111