CN102952946B - Method for removing fluorine in bastnaesite sulfuric acid leaching liquid by using zirconium-containing adsorbent - Google Patents
Method for removing fluorine in bastnaesite sulfuric acid leaching liquid by using zirconium-containing adsorbent Download PDFInfo
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Abstract
The invention belongs to the technical field of rare earth wet metallurgy, and particularly relates to a method for removing fluorine in bastnaesite sulfuric acid leaching liquid by using a zirconium-containing adsorbent. The method comprises the following steps of firstly, preparing zirconium salt into solution being 0.05-0.5 mol.L<-1>, stirring and activating by adding a precipitating agent, obtaining zirconium-containing adsorbent hydrated zirconium oxide by drying a solid product obtained by suction filtration, diluting bastnaesite sulfuric acid leaching liquid by 10-100 times by adding water, regulating the acidity to be 0.1-1.0 mol.L<-1>, adding 0.2-1.0g/50ml of a prepared zirconium-containing adsorbent, oscillating for 10-40 minutes, and then carrying out solid-liquid separation, and obtaining to obtain solid zirconium-containing adsorbent loaded with fluorine and defluorination sulfuric acid leaching liquid. According to the method disclosed by the invention, the generation of three fluorine-containing waste products is reduced through fluorine removing, the environment pollution due to a procedure is greatly relieved, meanwhile, the influence for on the extraction and the separation of follow-up rare earth due to the fluorine can be removed by simultaneously removing the fluorine from sulfuric acid liquid before extraction, the zirconium adsorbent after the adsorption can be reutilized, and the cost is greatly reduced.
Description
Technical field
The invention belongs to rare-earth wet method metallurgical technology field, be specifically related to the method for a kind of use containing fluorine in zirconium sorbent material removal hamartite sulphuric leachate.
Background technology
Hamartite (REFCO
3) be the rare-earth mineral of whole world reserves maximum, account for the more than 70% of total amount of rare earth, its composition is take light rare earths as main, and fluoro-carbon-cerium ore concentrate generally contains the about 50wt.% of cerium, fluorine-containing 7 ~ 9wt.%.
The decomposition of hamartite at present and the technique of Extraction of rare eart mainly contain acid system and alkaline process, alkaline process is wherein to adopt dense NaOH to decompose concentrate, require the of high grade of concentrate, equipment corrosion-resistant required high, and the heating problems of alkaline process is not well solved so far, therefore industrial little employing at present; Acid system mainly adopts hydrochloric acid or sulfuric acid, and wherein first salt acid system need be decomposed into rare earth oxide by hamartite high-temperature roasting, can emit the gas such as HF, HCl, causes environmental pollution, a part of F
-with RE
3+and Ce
4+enter solution, affect the extraction of rare earth, and this technique rare-earth morphology transforms repeatedly, and liquid-solid lock out operation is many, and chemical materials consumption is large, be eliminated gradually, and concentrated sulfuric acid roasting method is due to the existence of fluorine element, in technological process, easily produce HF gas and sulfuric acid mist, not only contaminate environment but also large to equipment corrosion, technical process is long, and raw material consumption amount is large.Visible no matter acid system or alkaline process decomposition technique, all can produce a large amount of spent acid and fluorine-containing three refuses and contaminate environment, therefore, development of new green rare-earth smelting technology, the efficient utilization that realizes rare earth resources is the key subjects that China's rare-earth industry future development faces.
Oxidizing roasting-sulfuric acid leaching is the hamartite Extraction of rare earth method growing up the sixties in 20th century, sulfuric acid leaching can make the valuable resources such as rare earth, fluorine and the thorium in hamartite all leach, resource in hamartite is all utilized, and is one of following prior development direction of hamartite.But the fluorine of association has extremely strong electronegativity and coordination ability in hamartite, under sulfuric acid system, fluorine is mainly with title complex [CeF
2]
2+and REF
3form exists, and F/Ce or F/RE be difficult separation completely extremely, has a strong impact on the extracting and separating of follow-up rare earth, and therefore, the problem that solves fluorine in flow process is the key of the method.Get rid of in the impact of fluorine and the method for interference at present, adopting more is by fluorine shielding and precipitator method defluorination with chemical mode.As disclosing one, Chinese patent CN1133346A as the washing lotion of fluorine complexing agent, the organic phase of cerium-carrying is carried out to back extraction using the boride (boric acid, borax) that contains 0.2 ~ 50 grams per liter, to prevent from forming the method for fluorine cpd; Chinese patent CN1114365A has introduced and in washing lotion, has added aluminum ion, makes itself and fluorine form a kind of more stable complex compound.But the feature of above method is after extraction, to utilize fluorine complexing agent complexing fluorion, and fluorion after treatment is still stayed in system, therefore cannot fundamentally get rid of the interference of fluorion, Chinese patent CN1093115A and U.S. Pat 5207995A have introduced fluoro-carbon-cerium ore concentrate hydrochloric acid and boric acid solution processing, make fluorochemical become tetrafluoroborate ion, then remove tetrafluoroborate by the precipitator method, the method can be removed the fluorine in raw material, but the loss for the treatment of processes middle-weight rare earths is larger.
Aforesaid method can alleviate the fluoride pollution problem producing in hamartite hydrometallurgy, also can eliminate the interference of fluorine to back extraction cerium, has certain using value, but fails thoroughly to solve the problem of defluorination and rare earth loss in solution.If fluorine is removed from sulphuric leachate before extraction, make fluorine/Rare Earth Separation, then the separation and acquisition that carries out rare earth from, can eliminate the impact of fluorine on subsequent treatment process.In current defluorination method, absorption method is because technique is simple, invests lowly, and " defluorination " efficiency is high, is the defluorination method of widespread use the most.In numerous sorbing materials, zirconium-containing compound has very high selectivity to fluorine, and it is large to have surface-area, adsorptivity is high, be not subject to other ion interference, water-fast feature, in the time that lower pH uses, defluorination effect is fine, can be used for underground water and trade effluent defluorination, the zirconium sorbent material after Adsorption of fluoride has again the attached regenerative power of good desorption simultaneously.
summary of the invention
Smelt for existing hamartite the wasting of resources and the problem of environmental pollution that isolation technique produces due to the existence of fluorine, the invention provides a kind of use and remove the method for fluorine in hamartite sulphuric leachate containing zirconium sorbent material, object be adopt prepare by the precipitator method containing zirconium de-fluoridation adsorbent, the fluorine sorbent material of the sulphuric leachate obtaining as hamartite oxidizing roasting-sulfuric acid leaching carries out defluorination, make fluorine and Rare Earth Separation, thereby eliminate the impact of fluorine on subsequent treatment process, greatly alleviated the pollution of flow process to environment.And the zirconium sorbent material after absorption is carried out to desorption and regeneration, thereby reduce costs.
Realizing the technical scheme of the object of the invention carries out according to following steps:
(1) by the 0.05 ~ 0.5molL that is mixed with soluble in water zirconates
-1solution, add while stirring 0.05 ~ 0.5molL
-1alkaline solution as precipitation agent, regulate pH to 9 ~ 13, generate after white precipitate, in 65 ~ 100 ℃ of stir-activating 1 ~ 4h, carry out afterwards suction filtration, the solid product obtaining is washed till neutrality with distilled water, dries 1 ~ 4h in 100 ~ 110 ℃, obtains containing zirconium sorbent material hydrous zirconium oxide;
(2) by hamartite in 400 ~ 800 ℃ of oxidizing roasting 1-4h, be 0.5 ~ 6.0molL to adding concentration in the hamartite after oxidizing roasting
-1sulfuric acid, in 50 ~ 100 ℃ leach 0.5-4h, the solvent and solute weight ratio of sulfuric acid and hamartite is (10 ~ 1): 1, obtain hamartite sulphuric leachate;
(3) by 10 ~ 100 times of hamartite sulphuric leachate thin ups, wherein Ce
4+concentration is (1 ~ 5) × 10
-3molL
-1, F
-concentration is (1 ~ 10) × 10
-3molL
-1, RE
3+concentration is (1 ~ 10) × 10
-3molL
-1, adjusting acidity is 0.1 ~ 1.0molL
-1, add preparation containing zirconium sorbent material 0.2 ~ 1.0g/50ml, vibration 10 ~ 40min, then carries out solid-liquid separation, obtain load fluorine containing zirconium adsorbent solids and defluorinate sulphuric leachate.
The reaction that absorption occurs is :-Zr-OH+3[CeF
2]
2++ 2H
+h
2[ZrF
6]+3Ce
4++ OH
-.
Add 0.01 ~ 0.2molL to containing in zirconium adsorbent solids of described load fluorine
-1naOH solution stirring 4 ~ 12h, containing zirconium sorbent material defluorinate regeneration, recycle, the add-on of NaOH solution is 25 ~ 100ml/g.
Described defluorinate sulphuric leachate can further carry out extracting and separating Rare Earth Elements Determination.
Wherein, the zirconates described in step (1) is inorganic zirconates ZrOCl
2, ZrO (NO
3)
2, ZrCl
4or Zr (NO
3)
4.
Alkaline solution described in step (1) is NaOH or ammonia soln.
Compared with prior art, feature 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, in leach liquor, add containing zirconium sorbent material, due to Zr
4+and F
-there is stronger coordination binding ability, can form stable [ZrF
6]
2-coordination ion, thus make fluorine generation Coordination Adsorption, Ce
4+with free ion form, with RE
3+jointly be present in water, then pass through solid-liquid separation, reach the object 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, the sulphuric leachate before extraction is carried out to defluorination simultaneously, can eliminate fluorine to the extraction of follow-up rare earth and the impact separating.Zirconium sorbent material after absorption can carry out regeneration, greatly reduces cost.
accompanying drawing explanation
Fig. 1 be preparation containing zirconium fluorine sorbent material of the present invention and in hamartite sulphuric leachate the schema of defluorination method;
Fig. 2 is the EDS collection of illustrative plates containing zirconium sorbent material of load fluorine in the embodiment of the present invention 1.
Embodiment
In technological process of the present invention, acidity is with EDTA-Ca complex rare-earth, use 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, Trisodium Citrate complexing aluminium for fluorine, with ion-selective electrode method;
The instrument model that the present invention adopts is PXSJ-216 ionometer, PF-1 fluoride ion electrode.
The adsorption rate of fluorine
ηbe defined as follows:
In formula:
c o,
c ebefore and after-absorption, treat the concentration (mol/l) of measured ion.
The hamartite adopting originates from Mianning, sichuan Province.
Embodiment 1
(1) by ZrOCl
2the 0.1molL that is mixed with soluble in water
-1solution, add while stirring 0.1molL
-1naOH solution as precipitation agent, regulate pH to 9, generate after white precipitate, in 65 ℃ of stir-activating 4h, carry out afterwards suction filtration, the solid product obtaining is washed till neutrality with distilled water, dries 4h in 100 ℃, obtains containing zirconium sorbent material hydrous zirconium oxide;
(2) by hamartite in 400 ℃ of oxidizing roasting 4h, be 0.5molL to adding concentration in the hamartite after oxidizing roasting
-1sulfuric acid, in 50 ℃ leach 4h, the solvent and solute weight ratio of sulfuric acid and hamartite is 5:1, obtains hamartite sulphuric leachate;
(3) by 10 times of hamartite sulphuric leachate thin ups, wherein F
-concentration is 4.3 × 10
-3molL
-1, Ce
4+concentration is 2.6 × 10
-3molL
-1, RE
3+concentration is 3.5 × 10
-3molL
-1, adjusting acidity is 0.1molL
-1, add preparation containing zirconium sorbent material 0.4g/50ml, vibration 20min, then carries out solid-liquid separation, obtain load fluorine containing zirconium adsorbent solids and defluorinate sulphuric leachate.
After solid-liquid separation, record in defluorinate sulphuric leachate: F
-concentration is 0.66 × 10
-3molL
-1, Ce
4+concentration is 2.5 × 10
-3molL
-1, RE
3+concentration is 3.3 × 10
-3molL
-1,
ηbe 84.65%, load fluorine containing the EDS collection of illustrative plates of zirconium sorbent material as shown in Figure 2, in figure, the appearance of fluorine element shows that Coordination Adsorption has occurred for fluorine and zirconium white, and does not occur rare earth element, illustrates that hydrous zirconium oxide can realize separating of fluorine and rare earth.
Add 0.01molL to containing in zirconium adsorbent solids of described load fluorine
-1naOH solution stirring 12h, containing zirconium sorbent material defluorinate regeneration, recycle, the add-on of NaOH solution is 100ml/g.
(1) by ZrO (NO
3)
2the 0.05molL that is mixed with soluble in water
-1solution, add while stirring 0.05molL
-1naOH solution as precipitation agent, regulate pH to 10, generate after white precipitate, in 75 ℃ of stir-activating 2h, carry out afterwards suction filtration, the solid product obtaining is washed till neutrality with distilled water, dries 1h in 110 ℃, obtains containing zirconium sorbent material hydrous zirconium oxide;
(2) by hamartite in 500 ℃ of oxidizing roasting 3h, be 2.0molL to adding concentration in the hamartite after oxidizing roasting
-1sulfuric acid, in 65 ℃ leach 2h, the solvent and solute weight ratio of sulfuric acid and hamartite is 10:1, obtains hamartite sulphuric leachate;
(3) by 30 times of hamartite sulphuric leachate thin ups, wherein F
-concentration is 7.23 × 10
-3molL
-1, Ce
4+concentration is 4.96 × 10
-3molL
-1, RE
3+concentration is 7.4 × 10
-3molL
-1, adjusting acidity is 1molL
-1, add preparation containing zirconium sorbent material 1.0g/50ml, vibration 10min, then carries out solid-liquid separation, obtain load fluorine containing zirconium adsorbent solids and defluorinate sulphuric leachate.
After solid-liquid separation, record in defluorinate sulphuric leachate: F
-concentration is 1.5 × 10
-3molL
-1, Ce
4+concentration is 4.62 × 10
-3molL
-1, RE
3+concentration is 6.96 × 10
-3molL
-1,
ηbe 79.25%.
Add 0.1molL to containing in zirconium adsorbent solids of described load fluorine
-1naOH solution stirring 12h, containing zirconium sorbent material defluorinate regeneration, recycle, the add-on of NaOH solution is 50ml/g.
Embodiment 3
(1) by ZrCl
4the 0.5molL that is mixed with soluble in water
-1solution, add while stirring 0.5molL
-1ammonia soln as precipitation agent, regulate pH to 10, generate after white precipitate, in 100 ℃ of stir-activating 1h, carry out afterwards suction filtration, the solid product obtaining is washed till neutrality with distilled water, dries 2h in 105 ℃, obtains containing zirconium sorbent material hydrous zirconium oxide;
(2) by hamartite in 800 ℃ of oxidizing roasting 1h, be 6.0molL to adding concentration in the hamartite after oxidizing roasting
-1sulfuric acid, in 100 ℃ leach 0.5h, the solvent and solute weight ratio of sulfuric acid and hamartite is 1:1, obtains hamartite sulphuric leachate;
(3) by 100 times of hamartite sulphuric leachate thin ups, wherein F
-concentration is 5.2 × 10
-3molL
-1, Ce
4+concentration is 2.89 × 10
-3molL
-1, RE
3+concentration is 5.02 × 10
-3molL
-1, adjusting acidity is 1molL
-1, add preparation containing zirconium sorbent material 0.4g/50ml, vibration 40min, then carries out solid-liquid separation, obtain load fluorine containing zirconium adsorbent solids and defluorinate sulphuric leachate.
After solid-liquid separation, record in defluorinate sulphuric leachate: F
-concentration is 0.89 × 10
-3molL
-1, Ce
4+concentration is 2.86 × 10
-3molL
-1, RE
3+concentration is 4.95 × 10
-3molL
-1,
ηbe 82.88%.
Add 0.15molL to containing in zirconium adsorbent solids of described load fluorine
-1naOH solution stirring 8h, containing zirconium sorbent material defluorinate regeneration, recycle, the add-on of NaOH solution is 50ml/g.
Embodiment 4
(1) by Zr (NO
3)
4the 0.2molL that is mixed with soluble in water
-1solution, add while stirring 0.2molL
-1ammonia soln as precipitation agent, regulate pH to 13, generate after white precipitate, in 75 ℃ of stir-activating 2h, carry out afterwards suction filtration, the solid product obtaining is washed till neutrality with distilled water, dries 1h in 110 ℃, obtains containing zirconium sorbent material hydrous zirconium oxide;
(2) by hamartite in 500 ℃ of oxidizing roasting 3h, be 2.0molL to adding concentration in the hamartite after oxidizing roasting
-1sulfuric acid, in 85 ℃ leach 2h, the solvent and solute weight ratio of sulfuric acid and hamartite is 10:1, obtains hamartite sulphuric leachate;
(3) by 50 times of hamartite sulphuric leachate thin ups, wherein F
-concentration is 8.4 × 10
-3molL
-1, Ce
4+concentration is 5.0 × 10
-3molL
-1, RE
3+concentration is 7.96 × 10
-3molL
-1, adjusting acidity is 1molL
-1, add preparation containing zirconium sorbent material 0.2g/50ml, vibration 10min, then carries out solid-liquid separation, obtain load fluorine containing zirconium adsorbent solids and defluorinate sulphuric leachate.
After solid-liquid separation, record in defluorinate sulphuric leachate: F
-concentration is 1.3 × 10
-3molL
-1, Ce
4+concentration is 4.98 × 10
-3molL
-1, RE
3+concentration is 7.9 × 10
-3molL
-1,
ηbe 84.52%.
Add 0.2molL to containing in zirconium adsorbent solids of described load fluorine
-1naOH solution stirring 4h, containing zirconium sorbent material defluorinate regeneration, recycle, the add-on of NaOH solution is 25ml/g.
Claims (4)
1. a method for fluorine in hamartite sulphuric leachate is removed in use containing zirconium sorbent material, in 400~800 ℃ of oxidizing roasting 1-4h, is 0.5~6.0molL to adding concentration in the hamartite after oxidizing roasting by hamartite
-1sulfuric acid, in 50~100 ℃ leach 0.5-4h, the solvent and solute weight ratio of sulfuric acid and hamartite is (10~1): 1, obtain hamartite sulphuric leachate;
It is characterized in that:
(1) by the 0.05~0.5molL that is mixed with soluble in water zirconates
-1solution, adding while stirring concentration is 0.05~0.5molL
-1alkaline solution as precipitation agent, regulate pH to 9~13, generate after white precipitate, in 65~100 ℃ of stir-activating 1~4h, carry out afterwards suction filtration, the solid product obtaining is washed till neutrality with distilled water, in 100~110 ℃ of baking 1~4h, obtain containing zirconium sorbent material hydrous zirconium oxide;
(2) by 10~100 times of hamartite sulphuric leachate thin ups, wherein Ce
4+concentration is (1~5) × 10
-3molL
-1, F
-concentration is (1~10) × 10
-3molL
-1, RE
3+concentration is (1~10) × 10
-3molL
-1, adjusting acidity is 0.1~1.0molL
-1, add preparation containing zirconium sorbent material 0.2~1.0g/50ml, vibration 10~40min, then carries out solid-liquid separation, obtain load fluorine containing zirconium adsorbent solids and defluorinate sulphuric leachate.
2. the method for fluorine in hamartite sulphuric leachate is removed in a kind of use according to claim 1 containing zirconium sorbent material, it is characterized in that the zirconates described in step (1) is inorganic zirconates ZrOCl
2, ZrO (NO
3)
2, ZrCl
4or Zr (NO
3)
4.
3. the method for fluorine in hamartite sulphuric leachate is removed in a kind of use according to claim 1 containing zirconium sorbent material, it is characterized in that the alkaline solution described in step (1) is NaOH or ammonia soln.
4. the method for fluorine in hamartite sulphuric leachate is removed in a kind of use according to claim 1 containing zirconium sorbent material, it is characterized in that adding 0.01~0.2molL to containing in zirconium adsorbent solids of described load fluorine
-1naOH solution stirring 4~12h, make containing zirconium sorbent material defluorinate regeneration, recycle, the add-on of NaOH solution is 25~100ml/g.
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