CN102534269A - Method for comprehensively recycling various rare earth from rare earth materials containing fluorine - Google Patents

Method for comprehensively recycling various rare earth from rare earth materials containing fluorine Download PDF

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CN102534269A
CN102534269A CN2012100815107A CN201210081510A CN102534269A CN 102534269 A CN102534269 A CN 102534269A CN 2012100815107 A CN2012100815107 A CN 2012100815107A CN 201210081510 A CN201210081510 A CN 201210081510A CN 102534269 A CN102534269 A CN 102534269A
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rare earth
fluorine
sulfuric acid
cerium
slag
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王全根
周继海
林强
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LESHAN SHENGHE RARE EARTH CO Ltd
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Abstract

The invention relates to a method for comprehensively recycling various rare earth from rare earth materials containing fluorine, in particular to a comprehensive utilization treatment separating method for cerium fluoride, fluorine cerium oxide, deep smelting slag and iron thorium slag, and belongs to the technical field of non-ferrous metal rare earth separation. The method for comprehensively recycling various rare earth from rare earth materials containing the fluorine comprises the following steps: a. stirring the rare earth materials containing the fluorine with sulfuric acid to generate hydrofluoric acid gas for preparing cryolite or hydrofluoric acid; and b. obtaining sulfuric rare earth solution by dipping the materials after stirring through water. The sulfuric acid directly acts on bastnaesite after roasting or other rare earth materials containing the fluorine (a cerium fluoride or fluorine cerium oxide product, the deep smelting slag and the iron thorium slag which are generated after reactions), further roasting is not required, a fluorine product is directly recycled through generated gas after the reactions at normal temperature, and the procedure in the prior art that sodium fluoride is formed by transforming alkali into fluorine and removed through washing is not required. The problem of environment protection of discharging of the fluorine is effectively solved, and the high yield of the rare earth is ensured.

Description

The method of the various rare earths of comprehensive reutilization from fluorine-containing rare earth material
Technical field
The invention belongs to non-ferrous metal Rare Earth Separation technical field, be specifically related to cerium fluoride fluorine cerium oxide, dark molten slag and the utilization of iron thorium slag for comprehensive and handle separation method.
Background technology
Along with the continuous expansion of rare earth industry size, rare earth resources course of processing resource utilization is low, seriously polluted etc., and problem is on the rise.
Separating cerium mainly is to adopt oxidizing roasting, a suboptimum to dissolve, filter with other rare earths in the industry at present; The commentaries on classics of filter residue alkali, washing, two suboptimums dissolve, three suboptimums dissolve, filtration has obtained few cerium rare earth chloride and cerium enriched substance; To reach the purpose of defluorinate, 1. technology see Fig. 1 for details.
This technology is at first through roasting; Contain in the fluoro carbonate carbon to the rare earth in the rawore and decompose and become rare earth oxyfluoride, trivalent cerium is oxidized to tetravalence, and variation has also taken place the raw ore physical property simultaneously; Being hardened to become very much by the raw ore surface spreads all over crackle, and the ore deposit is changed loose object into and helped stripping.
Then, according to the insoluble ceric principle of Hydrogen chloride, slowly add acid, dissolve about 30% trivalent rare earth, temperature of reaction is 55-60 ℃.Carry out solid-liquid separation, through filtration obtain containing cerium lower once lack cerium solution.Filter residue is rare earth fluoride and fluorine rare earth oxide.
Filter residue hydro-oxidation sodium is also heated 100 ℃--and alkali was carried out in 130 ℃ of conversions in 10 hours is changeed defluorinate, makes rare earth fluoride fluorine rare earth oxide change into rare earth hydrate, and fluorine is generated as Sodium Fluoride and gets into washing step.
Then, obtain the rare earth hydrate of fluorine through 11～13 washings, abundant flush away Sodium Fluoride.Obtain containing the higher part rare earth chloride of cerium with 40% trivalent rare earth in the further dissolved hydrogen rare earth oxide of Hydrogen chloride again.Owing to burn oldlyer during the roasting of part concentrate; Can not stripping under the condition of Hydrogen chloride, alkali changes fails defluorinate, therefore needs to dissolve through three suboptimums; Improve acidity and strengthen stripping; Solution through carrying secretly in the washing solids obtains rich cerium slag (content of cerium is >=95% in the rich cerium slag, and F is 1-2%) after the filtration.At last, obtain few cerium rare earth chloride with removal of impurities in.
Concentrate oxidizing roasting chemical equation:
ReFCO 3→REOF(CeOF)+CO 2↑.....................(1)
6CeOF+O 2→2CeO 3O 4F 3(2CeO 2·CeF 3)..................(2)
2REOF(CeOF)+H 2O＝RF 2O 3(Ce 2O 3)+2HF↑..............(3)
3Ce 2O 3+O 2＝4CeO 2·Ce 2O 3...............(4)
The excellent reaction equation of dissolving of hydrochloric acid:
3ReOF+6HCl→2ReCl 3+REF 3↓+3H 2O............ ...(5)
ThO 2+4HCl→ThCl 4+2H 2O............(6)
Fe 2O 3+6HCl→2FeCl 3+3H 2O...............(7)
RE 2O 3+6HCl→2RECl 3+H 2O...............(8)
Alkali transforms learns reaction equation:
ReF 3+3NaOH→Re(OH) 3+3NaF.........(9)
Two suboptimums dissolve:
Re(OH) 3+3HCl→ReCl 3+3H 2O…………(11)
In and removal of impurities:
FeCl 3+3NaOH→Fe(OH) 3↓+3NaCl………………(12)
ThCl4+4NaOH→Th(OH)4↓+4NaCl………………(13)
RECl 3+3NaOH→RE(OH) 3↓+3NaCl………………(14)
Re 3++3F -→REF 3↓………………(15)
There is following problem and shortage in this technology: the ore deposit after the roasting is excellent molten through repeatedly, and alkali changes, washes, filters, and technical process is long: since long flow path cost height, the carrying repeatedly of material, and labour intensity is big; Need washing after the commentaries on classics of filter residue alkali, the washing back produces the fluorine-containing in a large number wastewater that subtracts, this discharge of wastewater serious environment pollution, and high to its treatment cost, difficulty is big.
Applicant's early development of the application a kind of novel process (Chinese patent ZL 200810046146.4) that does not need defluorinate, 2. process step sees Fig. 2 for details.It is that catalyzer carries out that hydrochloric acid is excellent to be dissolved that material after this technology roasting adds sulfuric acid, because under the effect of sulfuric acid catalyst, the preferential and F complexing of Ce is CeF 3Deposition gets into slag, and trivalent rare earth gets into liquid state, is about to lack the cerium rare earth chloride through solid-liquid separation and separates with cerium fluoride.The content of cerium is merely 6～18% in few cerium rare earth chloride after excellent the dissolving, and the content of the cerium in the gained cerium fluoride is not less than 93%; Fluorine content is not less than 12%, and is shorter than the flow process of existing technology, and a step reaches former technology multistep and just can reach the purpose that leaches trivalent rare earth.Realized separating of cerium and rare earth chloride effectively.This technology is not handled after need fluorine not being converted into Sodium Fluoride again, the environmental issue that so effective solution fluorine discharging brings, and the fluorine discharging reduces by 60～80 kilograms of/ton ore deposits.
Its chemical equation is following:
Concentrate oxidizing roasting:
ReFCO 3→REOF(CeOF)↑+CO 2..................(16)
6CeOF+O 2→2Ce 3O 4F 3(2CeO 2·CeF 3)............(17)
2REOF(CeOF)+H 2O＝RF 2O 3(Ce 2O 3)↑+2HF............(18)
3Ce 2O 3+O 2＝4CeO 2·Ce 2O 3............(19)
Hydrochloric acid is excellent to be dissolved:
ReOF+3HCl→ReCl 3+3HF+H 2O............(2O)
CeCl 3+3F-H 2SO 4→CeF 3↓+3Cl -............(21)
ThO 2+4HCl→ThCl 4+2H 2O............(22)
Fe 2O 3+6HCl→2FeCl 3+3H 2O............(23)
In and removal of impurities:
FeCl 3+3NaOH→Fe(OH) 3↓+3NaCl............(24)
ThCl 4+4NaOH→Th(OH) 4↓+4NaCl............(25)
RE 3++F -→REF 3↓............(26)
Above-mentioned two technology common ground: lack in the cerium re chloride need and removal of impurities; Reach the purpose of sedimentation iron, thorium to 4-4.5 through adjust pH; Having the part rare earth forms in the rare earth hydrate sedimentation, particularly solution free fluorion and can complexing part rare earth forms rare earth fluoride and sneak into and cause the rare earth loss in the iron thorium slag.In addition, the rich cerium slag that 1. technology obtain prepares the Cerium II Chloride product through the dark step of dissolving, and has " dark molten slag " and produces.Have the part rare earth in the dark molten slag, cause the rare earth loss.
Those skilled in the art are necessary to eliminate the pollution that fluorine and thorium etc. produce from beginning of production, realize the efficient utilization of resource and clean production, effectively realize multiple comprehensive utilizations of resources such as fluorine, thorium and rare earth.
Summary of the invention
The object of the present invention is to provide a kind of fluorine that do not discharge, the method for the various rare earths of comprehensive reutilization from the material of fluorine-containing and rare earth.Said rare earth can be cerium (Ce) or non-Ce rare earth (RE).Fluorine-containing and material rare earth of the present invention can be baked hamartite, fluorine-containing dark molten slag, fluorine-containing iron thorium slag etc.
In addition, technology is 2. because market cerium fluoride demand is limited, if technology can cause products production greater than market capacity after 2. popularizing, cerium fluoride, fluorine cerium oxide also need to handle.Therefore, the inventive method also is applicable to the processing of cerium fluoride, fluorine cerium oxide product.
Technical scheme of the present invention may further comprise the steps:
A, with fluorine-containing rare earth material and sulfuric acid mix, the formation hydrofluoric acid gas of mix process is used to prepare sodium aluminum fluoride or hydrofluoric acid;
Material behind b, the mix has obtained rare earth sulfate solution through water logging.
The said sulfuric acid of step a is concentration greater than 98% sulfuric acid, can adopt technical grade sulfuric acid.
The vitriolic consumption: fluorine-containing rare earth material middle-weight rare earths oxide compound and vitriolic weight ratio are 1: 1.5-2.
In the such scheme, the add-on of water is controlled at the solution middle-weight rare earths concentration that makes after the leaching and is controlled at 90-110g/L during step b water logging.Generally, during water logging the add-on of water be weight of material 3-5 doubly, preferred 4 times.The water logging time is 2-5.
B step gained rare earth sulfate solution separates obtaining various rare-earth products through extraction.
Beneficial effect of the present invention: the present invention directly acts on the hamartite after the roasting with sulfuric acid; Or other fluorine-containing rare earth material (through reacting cerium fluoride fluorine cerium oxide product, molten deeply waste residue, the iron thorium waste residue that the back generates); Do not need roasting again; Directly reclaim the fluorine product through the gas that generates after the normal-temperature reaction, need not resemble in the prior art and remove through the washing of alkali conversion fluorine formation Sodium Fluoride.Efficiently solve the environmental issue of fluorine discharging, and guaranteed the high yield of rare earth.The gained sulfuric acid rare earth can be carried cerium through extraction, carry thorium, also can utilize in the rare earth sulfate solution a spot of free fluorine production high purity to fluoridize cerium.Realize the efficient utilization and the cleaner production of resource.
The inventive method can be recycled rare earth hydrate and low amount of fluorinated rare earth in the iron thorium waste residue that is difficult in the prior art handle, has solved radiothorium and has polluted and the fluoride pollution problem.Simultaneously, the inventive method is simple, and product diversification, high-endization.
Description of drawings
Fig. 1 is prior art processes route map (technology 1.);
Fig. 2 is ZL 200810046146.4 process route charts (technology 2.);
Fig. 3 is a process route chart of the present invention.
Below mode through specific embodiment, the present invention is done further detailed description, be limitation of the present invention but should not be construed as.
Embodiment
A, with the material M of fluorine-containing and rare earth 1(content of rare earth a%) and 98% sulfuric acid mix (stirrings) can form hydrofluoric acid gas by vigorous reaction in the mix process, and hydrofluoric acid gas adopts multi-stage spray to absorb to prepare sodium aluminum fluoride or hydrofluoric acid; Spray can be that alum liquor prepares sodium aluminum fluoride, also can be that water absorbs preparation hydrofluoric acid.
The contingent chemical reaction of mix process is following:
2REOF+3H 2SO 4→RE 2(SO 4) 3+2HF↑+2H 2O............(27)
2REF 3+3H 2SO 4→Ce 2(SO 4) 3+6HF↑............(32)
Particularly, Th, Ce can be following reactions:
Th(OH) 4+2H 2SO 4→Th(SO 4) 2+4H 2O............(28)
Ce(OH) 4+H 2SO 4→Ce(SO 4) 2+4H 2O............(30)
2CeF 3+3H 2SO 4→CeF 2SO 4+6HF↑............(31)
Material behind b, the mix has obtained sulfuric acid rare earth through water logging.The heavy M of recrement 2(content of rare earth b%)
Figure BDA0000146935800000041
The add-on of water: generally press weight of material and add 3-5 times of water, make the rare earth concentration of stripping be controlled at 100 gAbout/L, concentration is too high can to form the sulfuric acid rare earth crystallization.
The gained sulfuric acid rare earth can separate obtaining rare-earth products such as thorium, cerium through extraction.
Above-mentioned steps a vitriolic amount is 1 with material middle-weight rare earths oxide compound and 98% vitriolic weight ratio: 1.5-2.The inventive method does not need roasting, and normal temperature can carry out.The sulfuric acid consumption is unsuitable too much, otherwise during follow-up further processing, the Natural manganese dioxide consumption is excessive.
For effective leaching, 2-5 hour water logging time was advisable.
Leach sulfuric acid rare earth and note two problems, 1, the too high meeting of acidity causes Natural manganese dioxide readjustment pH value consumption too big,
Because through vigorous reaction and heat release, material has been half-dried dose of shape in the mix process for ore deposit and sulfuric acid.So the content of rare earth in the solution is because too high what and recently the calculating through the rare earth in the recrement after the water logging that influences the leaching of mensuration rare earth oxide with the input oxide compound of iron content.Ratio through measuring the total rare earth (TRE) that total rare earth content can be obtained and drop in the slag is calculated leaching yield.
Leaching yield=1-M 2* b%/M 1* a%
It below is specific embodiment.
Two appearance of embodiment 1 dark slag (numbering 1., 2.)
Raw material: dark slag 200g (contain fluorine about 10%, REO 55.1%, promptly contains rare earth oxide 110.2 grams);
1. (200*55.1%)=110.2 restrain rare earth
2. (200*55.1%)=110.2 restrain rare earth
98% industrial sulphuric acid;
Add sour ratio: weight ratio REO: sulfuric acid=1: 1.55,170.81 milliliters of sulfuric acid
With sulfuric acid mix (stirring) fluorine-containing and two appearance of the dark slag of material rare earth (numbering 1., 2.) and 98%, after the mix reaction, slag is leather hard, and the HF gas that vigorous reaction forms carries out multi-stage spray through water and absorbs, and obtains hydrofluoric acid solution.Material behind the mix adds 800 milliliters, and water logging has obtained sulfuric acid rare earth, and 1. number sample water logging reaction is 2 hours, and 2. number sample is 2.5 hours.
Recrement is weighed:
1. be 90 grams, wherein content of rare earth 14%, also surplus 12.6 grams of slag middle-weight rare earths;
2. be 87 to restrain wherein content of rare earth 12%, also surplus 10.44 grams of slag middle-weight rare earths.
Rare earth leaching yield: 1. 2. number appearance (1-10.44/110.2)=90.5% of number appearance (1-12.6/110.2)=88.56%.
Two appearance of embodiment 2 cerium fluorides (the table numbering 3., 4.)
Raw material: 200 gram cerium fluorides (wherein content of rare earth 62.7%, fluorine content 14%)
3. (200*62.7%)=125.3 restrain rare earth
4. (200*62.7%)=125.3 restrain rare earth
Industrial sulphuric acid (98%);
Add sour ratio: weight ratio REO: sulfuric acid=1: 1.55,170.81 milliliters of sulfuric acid
With sulfuric acid mix (stirring) fluorine-containing and two appearance of the dark slag of material rare earth (numbering 3., 4.) and 98%, after the mix reaction, slag is leather hard, and the HF gas that vigorous reaction forms carries out multi-stage spray through water and absorbs, and obtains hydrofluoric acid solution.Material behind the mix adds 800 milliliters, and water logging has obtained sulfuric acid rare earth, and 3. number sample water logging reaction is 2 hours, and 4. number sample is 2.5 hours.
Recrement is weighed:
3. be 75 grams, wherein content of rare earth 18%, also surplus 13.5 grams of slag middle-weight rare earths;
4. be 74 to restrain wherein content of rare earth 14%, also surplus 9.94 grams of slag middle-weight rare earths.
Rare earth leaching yield: 3. 4. (1-14/125.5)=92.1% of (1-13.5/125.3)=89.2%.
Appearance of embodiment 3 iron thorium slags (the table numbering 5.)
Raw material: 300 gram iron thorium slags (wherein content of rare earth 24%, fluorine content 3%)
5. (300*24%)=72 restrain rare earth
Industrial sulphuric acid (98%);
Add sour ratio: weight ratio REO: sulfuric acid=1: 2,144 milliliters of sulfuric acid;
With sulfuric acid mix (stirring) fluorine-containing and two appearance of the dark slag of material rare earth (numbering 5.) and 98%, after the mix reaction, slag is leather hard, and the HF gas that vigorous reaction forms absorbs through 0.1M alum liquor multi-stage spray, obtains aluminun fluoride solution Al 3+Concentration is about 0.1mol/L, and the pH value of regulator solution is 4.5～5.5, the F/Al that presses than 5.5～6, Na/Al is than 3.0～3.1 to wherein adding sodium salt, temperature of reaction is more than 90 ℃, the reaction times is 60min, obtains sodium aluminum fluoride.
Solid substances behind the mix adds 800 milliliters, and water logging has obtained sulfuric acid rare earth, water logging reaction 3 hours.
Recrement 96 grams of weighing, wherein content of rare earth 3.6%, also surplus 3.46 grams of slag middle-weight rare earths,
Rare earth leaching yield: (1-3.46/72)=95.2%.
Numbering Weight (gram Raw material (REO) % Add the acid ratio The water logging time Solution H + Recrement heavy (gram) Recrement (REO) % Leaching yield
① 200 55.1％ 1.55 2 125 90 14％ 88.6％
② 200 55.1％ 1.55 2.5 118 87 12％ 90.5％
③ 200 62.7％ 1.55 2 130 75 18％ 89.2％
④ 200 62.7％ 1.55 2.5 121 71 14％ 92.1％
⑤ 300 24％ 2 3 140 96 3.6％ 95.2％

Claims (7)

1. the method for the various rare earths of comprehensive reutilization from fluorine-containing rare earth material is characterized in that may further comprise the steps:
A, with fluorine-containing rare earth material and sulfuric acid mix, the formation hydrofluoric acid gas of mix process is used to prepare sodium aluminum fluoride or hydrofluoric acid;
Material behind b, the mix has obtained rare earth sulfate solution through water logging.
2. according to claim 1 from fluorine-containing rare earth material the method for the various rare earths of comprehensive reutilization, it is characterized in that: the said sulfuric acid of step a is concentration greater than 98% sulfuric acid.
3. according to claim 2 from fluorine-containing rare earth material the method for the various rare earths of comprehensive reutilization, it is characterized in that: fluorine-containing rare earth material middle-weight rare earths oxide compound and vitriolic weight ratio are 1: 1.5-2.
According to claim 1-3 each described from fluorine-containing rare earth material the method for the various rare earths of comprehensive reutilization, it is characterized in that: the add-on of water is controlled at the solution middle-weight rare earths concentration that makes after the leaching and is controlled at 90-110 during step b water logging g/ L.
5. according to claim 4 from fluorine-containing rare earth material the method for the various rare earths of comprehensive reutilization, it is characterized in that: during step b water logging the add-on of water be weight of material 3-5 doubly.
6. according to claim 5 from fluorine-containing rare earth material the method for the various rare earths of comprehensive reutilization, it is characterized in that: the step b water logging time is 2-5.
According to claim 1-6 each described from fluorine-containing rare earth material the method for the various rare earths of comprehensive reutilization, it is characterized in that: b step gained rare earth sulfate solution separates obtaining various rare-earth products through extraction.
CN2012100815107A 2012-03-26 2012-03-26 Method for comprehensively recycling various rare earth from rare earth materials containing fluorine Pending CN102534269A (en)

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CN104591247A (en) * 2015-01-09 2015-05-06 东北大学 Method for fluorine recovery from bastnaesite by alkali pulp countercurrent washing
CN104843761A (en) * 2015-03-31 2015-08-19 福建省长汀金龙稀土有限公司 Method for recovering rare earth from rare earth fluoride fused salt electrolysis waste with effects of environmental protection and low cost
CN105177324A (en) * 2015-10-21 2015-12-23 江西理工大学 Method for recovering rare earths from vacuum-calcium-thermic-reduction rare-earth slag
CN106044833A (en) * 2016-06-07 2016-10-26 福建省长汀金龙稀土有限公司 Method for recovering rare earth fluoride from electrode scrap reclaimed material and slag of rare earth
CN106916975A (en) * 2017-03-07 2017-07-04 四川省冕宁县方兴稀土有限公司 A kind of method of Extraction of rare earth in thorium waste residue from iron
CN108913876A (en) * 2018-07-26 2018-11-30 德昌县志能稀土有限责任公司 A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium
CN109487089A (en) * 2019-01-07 2019-03-19 江西理工大学 A kind of method of rare earth fluoride molten-salt electrolysis Slag treatment
WO2020052311A1 (en) 2018-09-14 2020-03-19 包头稀土研究院 Method for processing fluorine-containing rare earth mineral particles
CN111636001A (en) * 2020-05-19 2020-09-08 四川省冕宁县方兴稀土有限公司 Acid-base combined method for treating bastnaesite and recovering rare earth from waste slag
CN113200563A (en) * 2021-04-29 2021-08-03 内蒙古科技大学包头师范学院 Method for preparing rare earth oxyfluoride
CN115181854A (en) * 2022-07-18 2022-10-14 乐山盛和稀土有限公司 Double-acid leaching method for fluorine-containing rare earth ore

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CN104591247A (en) * 2015-01-09 2015-05-06 东北大学 Method for fluorine recovery from bastnaesite by alkali pulp countercurrent washing
CN104843761A (en) * 2015-03-31 2015-08-19 福建省长汀金龙稀土有限公司 Method for recovering rare earth from rare earth fluoride fused salt electrolysis waste with effects of environmental protection and low cost
CN105177324A (en) * 2015-10-21 2015-12-23 江西理工大学 Method for recovering rare earths from vacuum-calcium-thermic-reduction rare-earth slag
CN105177324B (en) * 2015-10-21 2017-05-10 江西理工大学 Method for recovering rare earths from vacuum-calcium-thermic-reduction rare-earth slag
CN106044833A (en) * 2016-06-07 2016-10-26 福建省长汀金龙稀土有限公司 Method for recovering rare earth fluoride from electrode scrap reclaimed material and slag of rare earth
CN106044833B (en) * 2016-06-07 2017-10-27 福建省长汀金龙稀土有限公司 A kind of method of the recovering rare earth fluoride from rare earth electrode scrap reclaimed materials and clinker
CN106916975A (en) * 2017-03-07 2017-07-04 四川省冕宁县方兴稀土有限公司 A kind of method of Extraction of rare earth in thorium waste residue from iron
CN106916975B (en) * 2017-03-07 2018-08-14 四川省冕宁县方兴稀土有限公司 A method of the Extraction of rare earth from iron thorium waste residue
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Application publication date: 20120704