CN102936656A - Method for removing fluorine in bastnaesite sulfuric acid leaching liquid by aluminiferous adsorbing agent - Google Patents

Method for removing fluorine in bastnaesite sulfuric acid leaching liquid by aluminiferous adsorbing agent Download PDF

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CN102936656A
CN102936656A CN2012104703384A CN201210470338A CN102936656A CN 102936656 A CN102936656 A CN 102936656A CN 2012104703384 A CN2012104703384 A CN 2012104703384A CN 201210470338 A CN201210470338 A CN 201210470338A CN 102936656 A CN102936656 A CN 102936656A
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fluorine
hamartite
aluminium
sulfuric acid
sorbent material
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薛向欣
何金桂
李勇
黄小卫
杨合
茹红强
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Northeastern University China
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Northeastern University China
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Abstract

The invention belongs to the technical field of rare earth wet metallurgy and specifically relates to a method for removing fluorine in a bastnaesite sulfuric acid leaching liquid by an aluminiferous adsorbing agent. The method includes roasting aluminum hydroxide for 2-6 hours at the temperature of 450 DEG C to 600 DEG C to prepare an activated aluminum oxide aluminiferous adsorbing agent, diluting the bastnaesite sulfuric acid leaching liquid for 10-100 times, adjusting the acidity in 0.1-1.0 mol*L-1, adding the aluminiferous adsorbing agent with the addition amount of 0.5-10g/50ml, oscillating for 10-60minutes, performing solid-liquid separation to obtain aluminiferous adsorbing agent solids loaded with fluorine and a defluorination sulfuric acid leaching liquid. By means of the method, fluorine-containing three wastes are reduced by removing fluorine, the pollution to the environment caused by the processes is greatly reduced, and simultaneously, the sulfuric acid leaching liquid before extraction is subjected to fluorine removal, so that the effect of the fluorine on the following extraction and separation of the rare earth can be eliminated. Besides, the adsorbing agent which is used for absorbing can be recycled, and the cost is greatly reduced.

Description

A kind of use contains the method that the aluminium sorbent material is removed fluorine in the hamartite sulphuric leachate
Technical field
The invention belongs to the rare-earth wet method metallurgical technology field, be specifically related to a kind of use and contain the method that the aluminium sorbent material is removed fluorine in the hamartite sulphuric leachate.
Background technology
Hamartite is the rare-earth mineral of whole world reserves maximum, accounts for more than 70% of total amount of rare earth, is the complex chemical compound of rare earth carbonate and rare earth fluorine, and molecular formula is REFCO 3, mainly take light rare earths as main, fluoro-carbon-cerium ore concentrate generally contains approximately 50wt.% of cerium, fluorine-containing 7 ~ 9wt.%.
Being applied at present the decomposition of hamartite and the technique of Extraction of rare eart nearly more than 10 plants, be summed up and mainly contain acid system and alkaline process, acid system wherein mainly adopts hydrochloric acid or sulfuric acid Bastnaesite Extraction of rare earth, the main method of present industrial Bastnaesite at China's sulfuric acid strengthening roasting, but because the existence of F, decomposition course produces HF gas contamination environment, and this explained hereafter long flow path, industrial chemicals consumption is large, require high to the corrosion resistant of equipment simultaneously, and alkaline process adopts dense NaOH to decompose concentrate, can alleviate comparatively speaking fluorine to the pollution of environment, but alkaline process requires the of high grade of concentrate, require same high to the corrosion resistant of equipment simultaneously, and the heating problems of alkaline process is not well solved so far, therefore at present industrial seldom employing.No matter acid system or alkaline process, the mineral decomposition course must adopt soda acid, thereby can produce spent acid alkali or exhaust emission environment, and these methods finally must adopt hydrochloric acid to change into rare earth chloride, so the impurity solubility rate is high, can affect the rate of recovery of rare earth simultaneously.Therefore, hamartite is carried out the Green Chemistry Extraction of rare earth, realize that the efficient utilization of rare earth resources is the direction of China's rare-earth industry future development.
The China rare earth journal first phase in 2000 (mechanism of two (2-ethylhexyl) phosphonic acids extracting cerium from fluorine-containing rare earth sulfuric acid solution) discloses a kind of oxidizing roasting-sulfuric acid leaching-extraction process, wherein sulfuric acid leaching can make the rare earth in the hamartite, the useful resources such as fluorine and thorium all leaches, resource in the hamartite is all utilized, secondly, quadrivalent cerium is extracted from the hamartite sulphuric leachate with fluorine, in the back extraction process, realize separating of cerium and thorium and fluorine, few cerium trivalent rare earth obtains the single rare earth product through extracting and separating, so the method is a kind of economic Clean method.But approximately 7 ~ 9% fluorine in association in the hamartite, because its extremely strong electronegativity and coordination ability, under sulfuric acid system, fluorine is mainly with title complex [CeF 2] 2+And REF 3Form exists, make fluorine and rare earth not easily separated, and in operating process, produce third phase owing to some reducing impurity in extraction agent and the thinner easily makes extraction system, make extraction process be difficult to carry out, therefore, the problem of fluorine is that can this technique realize industrialized key in the solution flow process.
Disclose the acidic aqueous solution that a kind of usefulness contains defluorinating agent such as Chinese patent CN1648264A and fluorine has been removed the method that it is separated with cerium from the organic phase of load fluorine cerium; Chinese patent CN1114365A has introduced and added aluminum ion in washing lotion, makes itself and fluorine form a kind of more stable complex compound.Above method has alleviated the fluoride pollution problem that produces in the hamartite hydrometallurgy, also can eliminate fluorine to the interference of back extraction cerium, has certain using value, but all be after extraction, to utilize fluorine complexing agent complexing fluorion, fluorion after the processing is still stayed in the system, therefore can't fundamentally get rid of the interference of fluorion.If before extraction, fluorine is removed from sulphuric leachate, make fluorine/Rare Earth Separation, carrying out rare earth leaches and separates again, can eliminate fluorine to the impact of subsequent treatment process, in present defluorination method, absorption method is simple owing to technique, reduced investment, and defluorination effect is better, is the defluorination method of the most widespread use.In numerous sorbing materials, contain the aluminium sorbent material in acidic solution for anionite, and aluminium has stronger coordination ability to fluorine, therefore fluorine had good selectivity, defluorination effect is better, the defluorination capacity is comparatively stable, is most widely used defluorination material.Aluminium sorbent material behind the Adsorption of fluoride has again the preferably attached regenerative power of desorption simultaneously.
Summary of the invention
Smelt the problem that isolation technique produces owing to the existence of fluorine for existing hamartite, the invention provides a kind of use and contain the method that the aluminium sorbent material is removed fluorine in the hamartite sulphuric leachate, purpose is to contain aluminium sorbent material Adsorption of fluoride by adding in the hamartite sulphuric leachate that obtains to hamartite oxidizing roasting-sulfuric acid leaching, make fluorine and Rare Earth Separation, thereby eliminate fluorine to the impact of subsequent treatment process, greatly alleviated the pollution of flow process to environment.And the sorbent material after the absorption carried out desorption and regeneration, thereby reduce cost.
The technical scheme of realization the object of the invention is carried out according to following steps:
(1) with aluminium hydroxide in 450～600 ℃ of roasting 2 ~ 6h, make and contain aluminium adsorbent activity aluminum oxide;
(2) with hamartite in 400 ~ 800 ℃ of oxidizing roasting 1-4h, adding concentration in the hamartite after the oxidizing roasting is 0.5 ~ 6.0molL -1Sulfuric acid, leach 0.5-4h in 50 ~ 100 ℃, the solvent and solute weight ratio of sulfuric acid and hamartite is (10 ~ 1): 1, obtain the hamartite sulphuric leachate;
(3) with 10 ~ 100 times of hamartite sulphuric leachate dilutions, adjusting acidity is 0.1 ~ 1.0molL -1, add and to contain the aluminium sorbent material, containing aluminium sorbent material add-on is leach liquor after 0.5 ~ 10g/50ml dilution, and then vibration 10 ~ 60min carries out solid-liquid separation, and what obtain the load fluorine contains aluminium adsorbent solids and defluorinate sulphuric leachate.
Adding concentration to containing of load fluorine in the aluminium sorbent material is 0.1 ~ 1molL -1Regenerator sulfuric acid, hydrochloric acid, sodium hydroxide, yellow soda ash or alum liquor, stirring reaction 4 ~ 24h, the load fluorine contain aluminium sorbent material defluorinate regeneration, recycle, the add-on of regenerator is 25 ~ 100ml/g.
The defluorinate sulphuric leachate can carry out the extracting and separating Rare Earth Elements Determination.
Compared with prior art, characteristics of the present invention and beneficial effect are:
(1) the present invention is to contain Ce 4+, F -And RE 3+Hamartite oxidizing roasting-sulfuric acid leaching after the hamartite sulphuric leachate that obtains be object, add in the leach liquor and contain the aluminium sorbent material because aluminium and fluorine have stronger coordination binding ability, thereby make fluorine generation Coordination Adsorption, Ce 4+With the free ion form, with RE 3+Jointly be present in aqueous phase, then pass through solid-liquid separation, reach the purpose of fluorine/Rare Earth Separation;
(2) the present invention has reduced the generation of fluorine-containing three refuses by defluorination, has greatly alleviated the pollution of flow process to environment, simultaneously the sulphuric leachate before extracting is carried out defluorination, can eliminate fluorine to the extraction of follow-up rare earth and the impact that separates.Sorbent material after the absorption can carry out regeneration, greatly reduces cost.
Description of drawings
Fig. 1 is that use of the present invention contains the schema that the aluminium sorbent material is removed fluorine in the hamartite sulphuric leachate.
Fig. 2 is the EDS collection of illustrative plates that contains the aluminium sorbent material behind the load fluorine in the embodiment of the invention 1.
Embodiment
Acidity is with the EDTA-Ca complex rare-earth in technological process of the present invention, use the standard caustic soda solution titration, the ferrous ammonium sulphate redox titration of the concentration of cerium, the concentration of rare earth element EDTA complexometric titration, fluorine is used ion-selective electrode method with Trisodium Citrate complexing aluminium;
The instrument model that the present invention adopts is the PXSJ-216 ionometer, the PF-1 fluoride ion electrode.
The adsorption rate of fluorine ηBe defined as follows:
Figure 2012104703384100002DEST_PATH_IMAGE001
In the formula: C o , C e Treat the concentration (mol/l) of measured ion before and after the-absorption.
The hamartite that adopts originates from Mianning, sichuan Province.
Embodiment 1
(1) with aluminium hydroxide in 450 ℃ of roasting 6h, make and contain aluminium adsorbent activity aluminum oxide;
(2) with hamartite in 400 ℃ of oxidizing roasting 4h, adding concentration in the hamartite after the oxidizing roasting is 1.0molL -1Sulfuric acid, leach 4h in 50 ℃, the solvent and solute weight ratio of sulfuric acid and hamartite is 5:1, obtains the hamartite sulphuric leachate;
(3) with 10 times of hamartite sulphuric leachate dilutions, adjusting acidity is 0.1molL -1, F wherein -Concentration is 5.2 * 10 -3MolL -1, Ce 4+Concentration is 2.7 * 10 -3MolL -1, RE 3+Concentration is 3.2 * 10 -3MolL -1, adding and contain aluminium adsorbent activity aluminum oxide 2.5g/50ml, then vibration 30min carries out solid-liquid separation, records aqueous phase: F -Concentration is 1.42 * 10 -3MolL -1, Ce 4+Concentration is 2.5 * 10 -3MolL -1, RE 3+Concentration is 2.92 * 10 -3MolL -1, ηBe 72.69%.
The EDS figure that contains the aluminium sorbent material behind the load fluorine as shown in Figure 2, the appearance of fluorine element shows that fluorine is adsorbed to alumina surface among the figure, and rare earth element do not occur, illustrates that activated alumina can realize separating of fluorine and rare earth.
Adding concentration to containing of load fluorine in the aluminium sorbent material is 0.4molL -1The regenerator sodium hydroxide solution, stirring reaction 4h, the load fluorine contain aluminium sorbent material defluorinate regeneration, recycle, the add-on of regenerator is 25ml/g.
Embodiment 2
(1) with aluminium hydroxide in 550 ℃ of roasting 4h, make and contain aluminium adsorbent activity aluminum oxide;
(2) with 500 ℃ of oxidizing roasting 3h of hamartite, adding concentration in the hamartite after the oxidizing roasting is 0.5molL -1Sulfuric acid, leach 2h in 70 ℃, the solvent and solute weight ratio of sulfuric acid and hamartite is 10:1, obtains the hamartite sulphuric leachate;
(3) with 50 times of hamartite sulphuric leachate dilutions, adjusting acidity is 0.5molL -1, F wherein -Concentration is 7.05 * 10 -3MolL -1, Ce 4+Concentration is 4.27 * 10 -3MolL -1, RE 3+Concentration is 7.6 * 10 -3MolL -1, adding and contain aluminium adsorbent activity aluminum oxide 0.5g/50ml, then vibration 10min carries out solid-liquid separation, records aqueous phase: F -Concentration is 1.5 * 10 -3MolL -1, Ce 4+Concentration is 4.14 * 10 -3MolL -1, RE 3+Concentration is 7.2 * 10 -3MolL -1, ηBe 78.72%.
Adding concentration to containing of load fluorine in the aluminium sorbent material is 0.1molL -1The regenerator sulphuric acid soln, stirring reaction 12h, the load fluorine contain aluminium sorbent material defluorinate regeneration, recycle, the add-on of regenerator is 50ml/g.
Embodiment 3
(1) with aluminium hydroxide in 600 ℃ of roasting 2h, make and contain aluminium adsorbent activity aluminum oxide;
(2) with 800 ℃ of oxidizing roasting 1h of hamartite, adding concentration in the hamartite after the oxidizing roasting is 6.0molL -1Sulfuric acid, leach 0.5h in 100 ℃, the solvent and solute weight ratio of sulfuric acid and hamartite is 8:1, obtains the hamartite sulphuric leachate;
(3) with 30 times of hamartite sulphuric leachate dilutions, adjusting acidity is 1molL -1, F wherein -Concentration is 9.4 * 10 -3MolL -1, Ce 4+Concentration is 5.96 * 10 -3MolL -1, RE 3+Concentration is 8.94 * 10 -3MolL -1, adding and contain aluminium adsorbent activity aluminum oxide 10g/50ml, then vibration 60min carries out solid-liquid separation, records aqueous phase: F -Concentration is 1.8 * 10 -3MolL -1, Ce 4+Concentration is 5.82 * 10 -3MolL -1, RE 3+Concentration is 8.63 * 10 -3MolL -1, ηBe 80.85%.
Adding concentration to containing of load fluorine in the aluminium sorbent material is 0.5molL -1The regenerator sodium carbonate solution, stirring reaction 24h, the load fluorine contain aluminium sorbent material defluorinate regeneration, recycle, the add-on of regenerator is 100ml/g.
Embodiment 4
(1) with aluminium hydroxide in 600 ℃ of roasting 2h, make and contain aluminium adsorbent activity aluminum oxide;
(2) with 800 ℃ of oxidizing roasting 1h of hamartite, adding concentration in the hamartite after the oxidizing roasting is 6.0molL -1Sulfuric acid, leach 0.5h in 100 ℃, the solvent and solute weight ratio of sulfuric acid and hamartite is 8:1, obtains the hamartite sulphuric leachate;
(3) with 30 times of hamartite sulphuric leachate dilutions, adjusting acidity is 1molL -1, F wherein -Concentration is 9.4 * 10 -3MolL -1, Ce 4+Concentration is 5.96 * 10 -3MolL -1, RE 3+Concentration is 8.94 * 10 -3MolL -1, adding and contain aluminium adsorbent activity aluminum oxide 10g/50ml, then vibration 60min carries out solid-liquid separation, records aqueous phase: F -Concentration is 1.8 * 10 -3MolL -1, Ce 4+Concentration is 5.82 * 10 -3MolL -1, RE 3+Concentration is 8.63 * 10 -3MolL -1, ηBe 80.85%.
Adding concentration to containing of load fluorine in the aluminium sorbent material is 1.0molL -1The regenerator hydrochloric acid soln, stirring reaction 24h, the load fluorine contain aluminium sorbent material defluorinate regeneration, recycle, the add-on of regenerator is 50ml/g.
Embodiment 5
(1) with aluminium hydroxide in 600 ℃ of roasting 2h, make and contain aluminium adsorbent activity aluminum oxide;
(2) with 800 ℃ of oxidizing roasting 1h of hamartite, adding concentration in the hamartite after the oxidizing roasting is 6.0molL -1Sulfuric acid, leach 0.5h in 100 ℃, the solvent and solute weight ratio of sulfuric acid and hamartite is 8:1, obtains the hamartite sulphuric leachate;
(3) with 30 times of hamartite sulphuric leachate dilutions, adjusting acidity is 1molL -1, F wherein -Concentration is 9.4 * 10 -3MolL -1, Ce 4+Concentration is 5.96 * 10 -3MolL -1, RE 3+Concentration is 8.94 * 10 -3MolL -1, adding and contain aluminium adsorbent activity aluminum oxide 10g/50ml, then vibration 60min carries out solid-liquid separation, records aqueous phase: F -Concentration is 1.8 * 10 -3MolL -1, Ce 4+Concentration is 5.82 * 10 -3MolL -1, RE 3+Concentration is 8.63 * 10 -3MolL -1, ηBe 80.85%.
Adding concentration to containing of load fluorine in the aluminium sorbent material is 0.5molL -1The regenerator alum liquor, stirring reaction 24h, the load fluorine contain aluminium sorbent material defluorinate regeneration, recycle, the add-on of regenerator is 25ml/g.

Claims (3)

1. a use contains the method that the aluminium sorbent material is removed fluorine in the hamartite sulphuric leachate, it is characterized in that carrying out according to following steps:
(1) with aluminium hydroxide in 450～600 ℃ of roasting 2 ~ 6h, make and contain aluminium adsorbent activity aluminum oxide;
(2) with hamartite in 400 ~ 800 ℃ of oxidizing roasting 1-4h, adding concentration in the hamartite after the oxidizing roasting is 0.5 ~ 6.0molL -1Sulfuric acid, leach 0.5-4h in 50 ~ 100 ℃, the solvent and solute weight ratio of sulfuric acid and hamartite is (10 ~ 1): 1, obtain the hamartite sulphuric leachate;
(3) with 10 ~ 100 times of hamartite sulphuric leachate dilutions, adjusting acidity is 0.1 ~ 1.0molL -1, add and to contain the aluminium sorbent material, containing aluminium sorbent material add-on is leach liquor after 0.5 ~ 10g/50ml dilution, and then vibration 10 ~ 60min carries out solid-liquid separation, and what obtain the load fluorine contains aluminium adsorbent solids and defluorinate sulphuric leachate.
2. a kind of use according to claim 1 contains the method that the aluminium sorbent material is removed fluorine in the hamartite sulphuric leachate, it is characterized in that adding concentration to containing of described load fluorine in the aluminium sorbent material is 0.1 ~ 1molL -1Regenerator, stirring reaction 4 ~ 24h, what make the load fluorine contains aluminium sorbent material defluorinate regeneration, recycle, the add-on of regenerator is 25 ~ 100ml/g.
3. a kind of use according to claim 2 contains the method that the aluminium sorbent material is removed fluorine in the hamartite sulphuric leachate, it is characterized in that described regenerator is sulfuric acid, hydrochloric acid, sodium hydroxide, yellow soda ash or alum liquor.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104445095A (en) * 2014-12-18 2015-03-25 中南大学 Method for purifying smelting waste acid
CN106222455A (en) * 2016-07-29 2016-12-14 乐山东承新材料有限公司 A kind of method of bastnaesite recovery fluorine
CN108889287A (en) * 2018-07-23 2018-11-27 江西睿锋环保有限公司 A kind of regeneration method of aluminium oxide defluorinating agent
CN108993382A (en) * 2018-06-25 2018-12-14 湖南烯富环保科技有限公司 A kind of defluorination material and its regeneration method based on bacteria residue
CN110205502A (en) * 2019-05-29 2019-09-06 中南大学 A kind of method that use adsorbent containing aluminium removes fluorine in lepidolite ore neutrality leachate
CN111139367A (en) * 2019-12-30 2020-05-12 江西赣锋循环科技有限公司 Method for deeply removing fluorine from LiCl solution recovered from waste battery
CN114920202A (en) * 2022-05-31 2022-08-19 江西天行化工有限责任公司 Preparation method of hydrogen fluoride

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60228627A (en) * 1984-04-25 1985-11-13 Mitsui Mining & Smelting Co Ltd Method for removing fluorine in wet treating of worthy metal
CN1323908A (en) * 2001-03-20 2001-11-28 北京方正稀土科技研究所有限公司 Optimal dissolving method of preparing rare earth fluorochloride material liquid from bastnasite concentrate
CN1514029A (en) * 2002-12-10 2004-07-21 中国科学院长春应用化学研究所 Method of extracting rare earth from apatite
CN1648264A (en) * 2004-08-06 2005-08-03 有研稀土新材料股份有限公司 Organic phase fluorine removing method after bastnaesite oxidation roasting-sulfuric acid leaching-extracting
CN102228746A (en) * 2011-07-01 2011-11-02 德阳市南邡再生资源有限公司 Method for removing fluorine from zinc sulfate solution with active alumina
CN102653823A (en) * 2012-05-25 2012-09-05 东北大学 Method used for separating rare earth from bastnaesite sulphuric acid leach solution and preparing ice stone

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60228627A (en) * 1984-04-25 1985-11-13 Mitsui Mining & Smelting Co Ltd Method for removing fluorine in wet treating of worthy metal
CN1323908A (en) * 2001-03-20 2001-11-28 北京方正稀土科技研究所有限公司 Optimal dissolving method of preparing rare earth fluorochloride material liquid from bastnasite concentrate
CN1514029A (en) * 2002-12-10 2004-07-21 中国科学院长春应用化学研究所 Method of extracting rare earth from apatite
CN1648264A (en) * 2004-08-06 2005-08-03 有研稀土新材料股份有限公司 Organic phase fluorine removing method after bastnaesite oxidation roasting-sulfuric acid leaching-extracting
CN102228746A (en) * 2011-07-01 2011-11-02 德阳市南邡再生资源有限公司 Method for removing fluorine from zinc sulfate solution with active alumina
CN102653823A (en) * 2012-05-25 2012-09-05 东北大学 Method used for separating rare earth from bastnaesite sulphuric acid leach solution and preparing ice stone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨威等: "《水源污染与饮用水处理技术》", 31 August 2006, 哈尔滨地图出版社 *

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Publication number Priority date Publication date Assignee Title
CN104445095A (en) * 2014-12-18 2015-03-25 中南大学 Method for purifying smelting waste acid
CN104445095B (en) * 2014-12-18 2016-05-25 中南大学 A kind of method of smelting dirty acid purification
CN106222455A (en) * 2016-07-29 2016-12-14 乐山东承新材料有限公司 A kind of method of bastnaesite recovery fluorine
CN108993382A (en) * 2018-06-25 2018-12-14 湖南烯富环保科技有限公司 A kind of defluorination material and its regeneration method based on bacteria residue
CN108993382B (en) * 2018-06-25 2021-09-07 湖南烯富环保科技有限公司 Defluorination material based on mushroom dregs and regeneration method thereof
CN108889287A (en) * 2018-07-23 2018-11-27 江西睿锋环保有限公司 A kind of regeneration method of aluminium oxide defluorinating agent
CN108889287B (en) * 2018-07-23 2021-08-06 江西睿锋环保有限公司 Regeneration method of aluminum oxide defluorinating agent
CN110205502A (en) * 2019-05-29 2019-09-06 中南大学 A kind of method that use adsorbent containing aluminium removes fluorine in lepidolite ore neutrality leachate
CN110205502B (en) * 2019-05-29 2020-07-17 中南大学 Method for removing fluorine in lepidolite neutral leaching solution by using aluminum-containing adsorbent
CN111139367A (en) * 2019-12-30 2020-05-12 江西赣锋循环科技有限公司 Method for deeply removing fluorine from LiCl solution recovered from waste battery
CN114920202A (en) * 2022-05-31 2022-08-19 江西天行化工有限责任公司 Preparation method of hydrogen fluoride
CN114920202B (en) * 2022-05-31 2023-06-06 江西天行化工有限责任公司 Preparation method of hydrogen fluoride

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Application publication date: 20130220