CN102659559A - Method for preparing lanthanum cerium oxalate from rare earth polishing powder waste residue - Google Patents

Method for preparing lanthanum cerium oxalate from rare earth polishing powder waste residue Download PDF

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CN102659559A
CN102659559A CN2012101550315A CN201210155031A CN102659559A CN 102659559 A CN102659559 A CN 102659559A CN 2012101550315 A CN2012101550315 A CN 2012101550315A CN 201210155031 A CN201210155031 A CN 201210155031A CN 102659559 A CN102659559 A CN 102659559A
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cerium
lanthanum
rare earth
waste residue
polishing powder
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CN102659559B (en
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肖汉宁
张海峰
周筱桐
祝宝军
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HUNAN FENGYUAN YESHINE KINGCO NEW ENERGY Co.,Ltd.
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Hu'nan Hanlin New Materials Co Ltd
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Abstract

The invention relates to the technical field of material preparation, in particular to a method for preparing lanthanum cerium oxalate from rare earth polishing powder waste residue. The method comprises the following steps: reacting to leach the recovered rare earth polishing powder waste residue in concentrated sulfuric acid to obtain a lanthanum cerium sulfate solution; separating the lanthanum cerium sulfate solution from solid residue, and adding oxalic acid to obtain a lanthanum cerium oxalate precipitate; and filtering and separating the lanthanum cerium oxalate precipitate, washing to neutrality, and drying to obtain the finished lanthanum cerium oxalate product. Fluorides such as hydrogen fluoride are not required, the polishing powder waste residue is scientifically and reasonably utilized comprehensively, and the whole recovery process is environment-friendly. The method has the characteristics of small investment, low recovery cost, simple process flow, high recovery rate, environment friendliness and the like.

Description

A kind of method of from the polishing powder from rare earth waste residue, producing the lanthanum oxalate cerium
Technical field
The present invention relates to material preparation technology, further be meant a kind of method of from the polishing powder from rare earth waste residue, producing the lanthanum oxalate cerium.
Background technology
[0002] polishing powder from rare earth has been widely used in the precise polished of glass devices such as display screen glass, opticglass, ornaments and precision instrument with its unique physics, chemical property and good polishing performance.Along with the increase and the national protective mining to the rare earth Mineral resources of polishing powder from rare earth consumption, polishing powder from rare earth is becoming tight supply day on the one hand; On the other hand, the polishing powder from rare earth waste residue that in the polishing powder from rare earth use, forms is also in continuous increase.
The polishing powder from rare earth waste residue mainly be adhere to each position of polissoir progressively the block waste material of agglomerative with recycle in the screen overflow that filters out, and from the polishing powder from rare earth waste liquid product of precipitate and separate.Staple in the polishing powder from rare earth waste residue is to contain the light rare earths oxide compound of cerium and lanthanum and the glass granules that grinding and polishing is got off; In addition; Also can mix mill skin (organic polymer), metal or the MOX etc. that have on some glass chip, the polishing machine; The waste residue of precipitate and separate also contains precipitation agent aluminum chloride that manual work sneaks into etc. from the polishing powder waste liquid; These waste residues can't be used simple method regenerated using, not only cause the waste of rare earth resources, also become the main source that polishing powder uses enterprise's solid slag.
Some reports to the polishing powder from rare earth regenerated using are all arranged at present both at home and abroad; Like Japanese Patent JP11319F55 the method that employing hydrofluoric acid is removed glass ingredient in the polishing powder is proposed; Though this method can effectively be removed the compositions such as silicon in the glass; But grease and other impurity are difficult to remove, and the polishing performance of the rare earth oxide after handling is still undesirable.Domestic patent " renovation process of inefficacy polishing powder from rare earth " also is in the slurries of polishing powder from rare earth, to add certain density water-soluble alkali and/or soluble fluoride carries out chemical treatment (ZL03119524.5); After the heated and stirred of certain hour; Through sedimentation, cleaning and filtration operation, reclaim solid.More than all be to adopt the fluoride dissolution glass ingredient to come removal of contamination to the processing of polishing powder from rare earth waste residue, complex technical process not only, but also can bring the post-processed and the problem of environment pollution caused of fluorochemical.The contriver once disclosed the recovery and reuse method (number of patent application: 201110053793.X) of a kind of polishing powder from rare earth waste residue and waste liquid; Though the polishing powder from rare earth that this method can recovery part can reuse from polishing powder from rare earth waste residue and waste liquid can not fundamentally solve the recovery and the problem of complex utilization of polishing powder from rare earth waste residue.The someone discloses a kind of method (number of patent application: 201110164888.9), also be through utilizing physical methods such as gravitational segregation to obtain the rare earth component after the grinding refinement of from quartzy waste residue, making the rare earth component recently.All there are certain limitation in chemical process and the physical method of more than handling polishing powder from rare earth, so apply limited.Most of enterprises are still at present the polishing powder from rare earth waste residue are handled as common waste residue, not only cause the waste of valuable rare earth resources, but also cause certain environmental pollution.In recent years because of the control of country to rare-earth ore resource, part rare-earth smelting enterprise begins to reclaim the polishing powder from rare earth waste residue and is incorporated in the rare-earth mineral, reclaims rare earth composition through smelting again.Though this method ability efficient recovery rare earth composition adopts traditional smelting technology process complicated, cost recovery is high, and is bigger to the pollution of environment.Therefore, invent a kind of low cost, eco-friendly recovery and comprehensive utilization technique to the polishing powder from rare earth waste residue, significant to can be recycled of the scientific utilization of China's polishing powder from rare earth waste residue and valuable rare earth resources.
Summary of the invention
The technical problem that the present invention will solve is; Deficiency to existing physical method and the existence of chemical method recycling polishing powder from rare earth waste residue technology; Invent a kind of fluorochemicals such as hydrogen fluoride that need not use; Method with relatively mild chemical process is flooded rare-earth separating polishing powder waste residue middle-weight rare earths composition realizes the comprehensive utilization of polishing powder from rare earth waste residue.Characteristics such as the present invention has less investment, cost recovery is low, technical process is simple, recovery utilization rate is high, environmentally friendly.
Technical scheme of the present invention does,
A kind of method of from the polishing powder from rare earth waste residue, producing the lanthanum oxalate cerium, concrete steps are:
(1) the polishing powder from rare earth waste residue is carried out physical separation, impurity elimination, and waste particle is crushed to below the particle diameter 10mm, the waste residue after broken;
(2) add the vitriol oil in the waste residue after fragmentation, control reaction temperature is at 120 ℃ ~ 180 ℃, reacts the discharging when making material be cooled to below 100 ℃ after 10 hours of 3 h ~, lanthanum sulfat cerium extract; The add-on of the vitriol oil confirms that by the rare earth oxide content in the waste residue theory that all forms sulfuric acid rare earth salt by rare earth oxide needs 1.1 times ~ 1.5 of molar weight extraordinarily to go into the vitriol oil;
(3), with the method for centrifugal or press filtration lanthanum sulfat cerium extract is separated with solid residue then with lanthanum sulfat cerium extract thin up and stir;
(4) in separating the lanthanum sulfat cerium extract that obtains, add oxalic acid, obtain lanthanum oxalate cerium deposition, the add-on of oxalic acid is a terminal point with the white precipitate that the lanthanum oxalate cerium no longer occurs;
(5) with centrifugal or press filtration method lanthanum oxalate cerium throw out is separated and washing to neutral, isolated waste liquid and lanthanum oxalate cerium throw out, lanthanum oxalate cerium throw out 100 ℃ ~ 120 ℃ dryings, is promptly obtained lanthanum oxalate cerium finished product.
Below the present invention is further specified:
In step (5), add lime in the isolated waste liquid and precipitate, obtain gypsum and clear water, the add-on of lime should confirm that reaching 6 ~ 7 with the pH value in the final waste liquid is terminal point according to the pH value of acid waste liquid.
Step (1) middle-weight rare earths polishing powder waste residue is meant the cerium oxide that is used for after the polishing of liquid crystal display, opticglass and lanthanum trioxide quality total content at the polishing powder waste residue more than 15%, and wherein the atomic ratio of cerium and lanthanum is 1:0.1 ~ 0.5.
Vitriol oil preferred mass concentration described in the step (2) is 98% the vitriol oil.Suitably the excessive vitriol oil helps improving the leaching yield of rare earth.
Solid residue in the step (3) is with deionized water wash 3 times ~ 8 times, the sulfuric acid rare earth salt that leaches with abundant recovery.
Step (4) mesoxalic acid can be that the oxalic acid powder also can be an oxalic acid aqueous solution, and preferred mass concentration is the oxalic acid aqueous solution of 20%-30%.
The atomic ratio of cerium and lanthanum is 1:0.1 ~ 0.5 in step (5) the mesoxalic acid lanthanum cerium finished product.
With 85% ~ 98% rare earth composition in the recyclable polishing powder from rare earth waste residue of the inventive method; The solid separated residue can be used as the raw material of producing architectural pottery in the above-mentioned steps (3); Precipitate the gypsum that obtains at last and can be used for preparing gypsum building material; Clear water is recyclable, and therefore, removal process does not produce environment to be polluted.
Compared with prior art, advantage of the present invention is:
From the polishing powder from rare earth waste residue, produce the method for lanthanum oxalate cerium and need not use fluorochemicals such as hydrogen fluoride, it is simple to reclaim technology, and the recovery of rare earth composition reaches 85%-98%; Solid slag after the recovery can be used as the raw materials for production of architectural pottery; In the acid waste water with after the by product gypsum can be used for making building and ornament materials, the clear water reusable edible not only makes the polishing powder waste residue obtain scientific and reasonable comprehensive utilization; And the whole recovery process is environmentally friendly, and is pollution-free.
Embodiment
Embodiment 1:
(1) get 1000 kilograms of rare earth polishing powder waste residues, after physical separation goes out obvious impurity, with its grain breakage to particle diameter 10mm, the waste residue after broken;
(2) with putting in the waste residue after the fragmentation in 2500 liters the glassed steel reaction vessels; The vitriol oil that adds 900 kilogram 98% is used the heat-conducting oil heating reaction kettle, floods reaction 8 hours down at 150 ℃; Discharging when in reaction kettle, naturally cooling to below 100 ℃ then gets lanthanum sulfat cerium extract;
(3) be 3000 liters with lanthanum sulfat cerium extract thin up to total amount, stir, with pressure filter lanthanum sulfat cerium extract is separated with solid residue then and with deionized water wash solid residue 6 times;
(4) in the lanthanum sulfat cerium infusion solution that separate to obtain, adding mass concentration is 20% oxalic acid aqueous solution, obtains the lanthanum oxalate cerium deposition of white, finishes when oxalic acid solution no longer obvious sediment occurs until adding;
(5) with pressure filter lanthanum oxalate cerium throw out is separated, and extremely neutral with deionized water wash, after 100 ~ 120 ℃ of dryings, promptly obtain lanthanum oxalate cerium finished product, wherein the atomic ratio of cerium and lanthanum is 1:0.2;
(6) isolating acid waste liquid in the step (5) is added lime and precipitate, reach at 6.5 o'clock up to the pH of solution value and stop to add lime, obtain by product gypsum and clear water.
Embodiment 2:
(1) get 1000 kilograms of rare earth polishing powder waste residues, after physical separation goes out obvious impurity, with its grain breakage to particle diameter 10mm, the waste residue after broken;
(2) with putting in the waste residue after the fragmentation in 2500 liters the glassed steel reaction vessels; The vitriol oil that adds 1000 kilogram 98% is used the heat-conducting oil heating reaction kettle, floods reaction 5 hours down at 180 ℃; Discharging when in reaction kettle, naturally cooling to below 100 ℃ then gets lanthanum sulfat cerium extract;
(3) be 3000 liters with lanthanum sulfat cerium extract thin up to total amount, stir, with pressure filter lanthanum sulfat cerium extract is separated with solid residue then and with deionized water wash solid residue 8 times;
(4) in the lanthanum sulfat cerium infusion solution that separate to obtain, slowly add 25% oxalic acid aqueous solution equably, obtain the lanthanum oxalate cerium deposition of white, until add oxalic acid solution when no longer obvious sediment occurring till;
(5) with pressure filter lanthanum oxalate cerium throw out is separated, and extremely neutral with deionized water wash, after 100 ~ 120 ℃ of dryings, promptly obtain lanthanum oxalate cerium finished product, wherein the atomic ratio of cerium and lanthanum is 1:0.3;
(6) isolating acid waste liquid in the step (5) is added lime and precipitate, till the pH of solution value reaches at 6.5 o'clock, obtain by product gypsum and clear water.
Embodiment 3:
(1) get 1000 kilograms of rare earth polishing powder waste residues, after physical separation goes out obvious impurity, with its grain breakage to particle diameter 10mm, the waste residue after broken;
(2) with putting in the waste residue after the fragmentation in 2500 liters the glassed steel reaction vessels; The vitriol oil that adds 800 kilogram 98% is used the heat-conducting oil heating reaction kettle, floods reaction 10 hours down at 120 ℃; Discharging when in reaction kettle, naturally cooling to below 100 ℃ then gets lanthanum sulfat cerium extract;
(3) be 3000 liters with lanthanum sulfat cerium extract thin up to total amount, stir, with pressure filter lanthanum sulfat cerium extract is separated with solid residue then and with deionized water wash solid residue 5 times;
(4) in the lanthanum sulfat cerium infusion solution that separate to obtain, slowly add the oxalic acid powder equably, obtain the lanthanum oxalate cerium deposition of white, until add the oxalic acid powder when no longer obvious sediment occurring till;
(5) with pressure filter lanthanum oxalate cerium throw out is separated, and extremely neutral with deionized water wash, after 100 ~ 120 ℃ of dryings, promptly obtain lanthanum oxalate cerium finished product, wherein the atomic ratio of cerium and lanthanum is 1:0.5;
(6) isolating acid waste liquid in the step (5) is added lime and precipitate, till the pH of solution value reaches at 6.5 o'clock, obtain by product gypsum and clear water.

Claims (6)

1. method of from the polishing powder from rare earth waste residue, producing the lanthanum oxalate cerium, concrete steps are:
(1) the polishing powder from rare earth waste residue is carried out physical separation, impurity elimination, and waste particle is crushed to below the particle diameter 10mm, the waste residue after broken;
(2) add the vitriol oil in the waste residue after fragmentation, control reaction temperature is at 120 ℃ ~ 180 ℃, reacts the discharging when making material be cooled to below 100 ℃ after 10 hours of 3 h ~, lanthanum sulfat cerium extract; The add-on of the vitriol oil confirms that by the rare earth oxide content in the waste residue theory that all forms sulfuric acid rare earth salt by rare earth oxide needs 1.1 times ~ 1.5 of molar weight extraordinarily to go into the vitriol oil;
(3), with the method for centrifugal or press filtration lanthanum sulfat cerium extract is separated with solid residue then with lanthanum sulfat cerium extract thin up and stir;
(4) in separating the lanthanum sulfat cerium extract that obtains, add oxalic acid, obtain lanthanum oxalate cerium deposition, the add-on of oxalic acid is a terminal point with the white precipitate that the lanthanum oxalate cerium no longer occurs;
(5) with centrifugal or press filtration method lanthanum oxalate cerium throw out is separated and washing to neutral, isolated waste liquid and lanthanum oxalate cerium throw out, lanthanum oxalate cerium throw out 100 ℃ ~ 120 ℃ dryings, is promptly obtained lanthanum oxalate cerium finished product.
2. the method for from the polishing powder from rare earth waste residue, producing the lanthanum oxalate cerium according to claim 1; It is characterized in that; In step (5), add lime in the isolated waste liquid and precipitate, obtain gypsum and clear water, it is terminal point that the add-on of lime reaches 6 ~ 7 with the pH value in the waste liquid.
3. the method for from the polishing powder from rare earth waste residue, producing the lanthanum oxalate cerium according to claim 1; It is characterized in that; Step (1) middle-weight rare earths polishing powder waste residue is meant the cerium oxide that is used for after the polishing of liquid crystal display, opticglass and lanthanum trioxide quality total content at the polishing powder waste residue more than 15%, and wherein the atomic ratio of cerium and lanthanum is 1:0.1 ~ 0.5.
4. the method for from the polishing powder from rare earth waste residue, producing the lanthanum oxalate cerium according to claim 1 is characterized in that, the vitriol oil described in the step (2) is that mass concentration is 98% the vitriol oil.
5. the method for from the polishing powder from rare earth waste residue, producing the lanthanum oxalate cerium according to claim 1 is characterized in that, the solid residue in the step (3) is with deionized water wash 3 times ~ 8 times, the sulfuric acid rare earth salt that leaches with abundant recovery.
6. the method for from the polishing powder from rare earth waste residue, producing the lanthanum oxalate cerium according to claim 1 is characterized in that, the atomic ratio of cerium and lanthanum is 1:0.1 ~ 0.5 in step (5) the mesoxalic acid lanthanum cerium finished product.
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Cited By (6)

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CN109207737A (en) * 2018-11-23 2019-01-15 湖南景翌湘台环保高新技术开发有限公司 A method of extracting aluminium, silica and rare earth from useless polishing powder from rare earth
CN111439773A (en) * 2020-05-18 2020-07-24 龙南县和利稀土冶炼有限公司 Method for recovering rare earth oxide from rare earth oxide waste residues
CN113351197A (en) * 2020-03-04 2021-09-07 北京矿冶科技集团有限公司 Preparation method of SCR denitration catalyst
CN113998802A (en) * 2021-11-12 2022-02-01 中建材环保研究院(江苏)有限公司 Polishing powder recovery process for glass grinding wastewater
CN114703366A (en) * 2022-04-24 2022-07-05 中南大学 Method for treating waste CRT fluorescent powder by concentrated sulfuric acid directional transformation
US11753308B1 (en) 2020-12-02 2023-09-12 Beijing University Of Technology Method for separating and extracting rare-earth and regenerating rare-earth polishing powder from rare-earth polishing powder waste

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109207737A (en) * 2018-11-23 2019-01-15 湖南景翌湘台环保高新技术开发有限公司 A method of extracting aluminium, silica and rare earth from useless polishing powder from rare earth
CN109207737B (en) * 2018-11-23 2020-02-07 湖南景翌湘台环保高新技术开发有限公司 Method for extracting aluminum, silicon oxide and rare earth from waste rare earth polishing powder
CN113351197A (en) * 2020-03-04 2021-09-07 北京矿冶科技集团有限公司 Preparation method of SCR denitration catalyst
CN111439773A (en) * 2020-05-18 2020-07-24 龙南县和利稀土冶炼有限公司 Method for recovering rare earth oxide from rare earth oxide waste residues
US11753308B1 (en) 2020-12-02 2023-09-12 Beijing University Of Technology Method for separating and extracting rare-earth and regenerating rare-earth polishing powder from rare-earth polishing powder waste
CN113998802A (en) * 2021-11-12 2022-02-01 中建材环保研究院(江苏)有限公司 Polishing powder recovery process for glass grinding wastewater
CN114703366A (en) * 2022-04-24 2022-07-05 中南大学 Method for treating waste CRT fluorescent powder by concentrated sulfuric acid directional transformation

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