CN1166788C - Optimal dissolving method of preparing rare earth fluorochloride material liquid from bastnasite concentrate - Google Patents
Optimal dissolving method of preparing rare earth fluorochloride material liquid from bastnasite concentrate Download PDFInfo
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- CN1166788C CN1166788C CNB011098422A CN01109842A CN1166788C CN 1166788 C CN1166788 C CN 1166788C CN B011098422 A CNB011098422 A CN B011098422A CN 01109842 A CN01109842 A CN 01109842A CN 1166788 C CN1166788 C CN 1166788C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention belongs to the field of wet metallurgy, which particularly relates to a preferential dissolving method for preparing material liquid of low-fluorine rare earth chloride from bastnasite concentrates. The method comprises: preference is given to rare earth hydrate RE(OH)3 containing REO to be dissolved in a hydrochloric acid reagent, the pH value of a control system is smaller than 4, and gas is added to perturb the reagent to separate out rare earth fluoride from preferential solution through precipitation, and fluorine ion impurities are eliminated; after complete reaction, the solution is boiled, the temperature is maintained, and then, material liquid of low-fluorine rare earth chloride is obtained. With the advantages of favorable effect of impurity elimination, low production cost and convenient operation, the method is suitable for various bastnasite concentrates.
Description
The invention belongs to the hydrometallurgy field, particularly a kind of optimal dissolving method that from f_c_ce_la concentrate, prepares low fluorine rare earth chloride liquid.
As everyone knows, China is a profuse country of rare earth resources, and has some unique mineral, adsorbs the Sichuan Mianning bastnasite of ore deposit and discovery recently etc. as Inner Mongol white clouds pile of stones, earth or grass bastnasite, southern ionic.In rare-earth smelting industry, what starting raw material generally used is the rare earth ore concentrate of handling through ore dressing, and grade is generally between 50-70%.When preparing rare earth chloride liquid, generally be used alone or as a mixture sulfuric acid decomposition method (acid system), NaOH decomposition method (alkaline process) or Na with f_c_ce_la concentrate
2CO
3Roasting method.The alkali process of f_c_ce_la concentrate generally comprises steps such as acid bubble, alkali decomposition, washing, excellent molten, slagging-off and batching.This technology has advantages such as simple, the low for equipment requirements and production cost of operation is low, so obtained application in some Rare Earth Separation factories at home.But also there are some shortcomings in this technology, the easy dulling of feed liquid that utilizes this conventional operation to prepare, and residual fluorine impurity concentration is up to 0.01mol/L.The direct yield of rare earth is low than acid system for another example, and is muddy with relatively poor, the easy change of feed liquid mass ratio that this method is produced, and residual fluorine foreign matter content is higher.If before entering the extracting and separating operation, do not utilize abstraction and type-reverting purifying feed liquid, to remove relevant non-rare earth impurity, after then the gained feed liquid enters extraction tank, will cause in the extraction tank organic phase to be very easy to emulsification and the organic phase wastage rate also bigger, can cause the decline of rare-earth products purity in the time of seriously.On the contrary, if utilize whole extraction processs or other transition method, then, will increase considerably production cost because of needs increase a large amount of acid and alkali consumptions.So, how under the prerequisite that as far as possible seldom increases production cost, develop a kind of from f_c_ce_la concentrate the alkaline process of the low fluorine rare earth chloride liquid of preparation decompose and improve technology and just have important practice significance.
One of purpose of the present invention is to overcome existing alkaline process when decomposing the low fluorine rare earth chloride liquid of the f_c_ce_la concentrate preparation prepared easy dulling of feed liquid that comes out, defectives such as residual fluorine impurity concentration height and rare earth yield are low, utilize perturbation principle in the chemical kinetics and the precipitation carrier band impurity-removing method in the analytical chemistry, in the excellent molten operation sequence of alkali process, add an amount of certain carbonate, or supercarbonate, or their mixing salt is done fluorine Impurity removal reagent, fluorine foreign matter content in the excellent molten material is reduced by one to two more than the order of magnitude, thereby a kind of optimal dissolving method that decomposes the low fluorine rare earth chloride liquid of f_c_ce_la concentrate preparation with alkaline process is provided.
A further object of the present invention is that the method that will be provided is applied to various f_c_ce_la concentrates and is the alkaline process decomposition technique of the mixed rare earth concentrate of main component with it.
The invention provides a kind of optimal dissolving method that from f_c_ce_la concentrate, prepares low fluorine rare earth chloride liquid, its principle is in the excellent molten operation of the rare earth hydrate of the alkali process of f_c_ce_la concentrate, utilize the principle of gas perturbation chemical equilibrium, can produce the chemical reagent of carbon dioxide with some, to the absorption that produces in the excellent molten process with contain the sedimentary metastable state colloidal particle of rare earth fluoride and carry out perturbation, rare earth fluoride is precipitated from excellent solution separates out, and by excellent molten slag carrier band, thereby reach the purpose of removing fluorion impurity.
Method feature of the present invention is: with the rare earth hydrate RE (OH) of the excellent molten REO of containing of hydrochloric acid reagent
3, the pH value of the hierarchy of control is 1～4, adds gas perturbation reagent and handles, and rare earth fluoride is precipitated from excellent solution separate out, and removes fluorion impurity, boils after reacting completely, insulation promptly obtains low fluorine rare earth chloride liquid.
The employed gas perturbation of method of the present invention reagent is for producing the compound or the mixture of carbon dioxide in system, for example can be following any one inorganic salt or any mixture between them, i.e. urea, volatile salt, bicarbonate of ammonia, salt of wormwood, saleratus, yellow soda ash, sodium bicarbonate or carbonated rare earth.
During using gas perturbation reagent, the pH value of excellent solution should be controlled in the acid range, is generally below 4, preferred pH1～4.In above-mentioned acidity scope, by the throwing ore deposit amount of one ton of rare earth oxide (REO), the suitable usage quantity of gas perturbation reagent is 50～100kg, is preferably 70～85kg.The each only throwing of this method ore deposit amount is between the 1-2.5 ton.In the excellent molten process of the present invention, the weight percent concentration of used hydrochloric acid reagent is generally 10-36% greater than 10%.
The rare earth feed liquid concentration of according to said method producing is 0.8-1.8mol/L (amounting to rare earth oxide 128-288g/L), and each impurity level is respectively: F
-, 1 * 10
-3-1 * 10
-4SiO
2, 200-800 μ g/g; Fe
2O
3, 10 μ g/g; Al
2O
3,＜100 μ g/g.Residual REO content range is 30-45% in the excellent molten slag of this method gained, and excellent molten rate is 80-90%.
Limpid bright with the feed liquid that the inventive method is produced, the fluorine foreign matter content is low, and the direct yield height of rare earth can directly enter the extracting and separating operation, can not cause occurring emulsion in the extraction tank, has reduced the wastage rate of organic phase.Be characterized in: good impurity removing effect, production cost are low, easy and simple to handle, are applicable to various f_c_ce_la concentrates.
Description of drawings:
Fig. 1: former process flow is published picture;
Fig. 2: process flow sheet of the present invention.
Below in conjunction with embodiment technical scheme of the present invention is described.
Embodiment 1
With concentration 29% the excellent molten RE (OH) that contains 1.5 tons of REO of HCl
3, control final pH=4 o'clock add 100kg (NH
4)
2CO
3Handle, boil after reacting completely, be incubated one hour.Gained feed liquid middle-weight rare earths concentration is 1.52mol/L, F
-Foreign matter content is 3.37 * 10
-3Mol/L, SiO
2Foreign matter content is 450 μ g/g, Fe
2O
3Foreign matter content is less than 10 μ g/g, Al
2O
3Foreign matter content is less than 100 μ g/g.REO content is 38.67% in the excellent molten slag, excellent molten rate 85.25%.
Embodiment 2
With concentration 20% the excellent molten RE (OH) that contains 1.5 tons of REO of HCl
3, control final pH=1.5 o'clock add 75kg Na
2CO
3Handle, boil after reacting completely, be incubated one hour.Gained feed liquid middle-weight rare earths concentration is 1.60mol/L, F
-Foreign matter content is 4.28 * 10
-3Mol/L, SiO
2Foreign matter content is 580 μ g/g, Fe
2O
3Foreign matter content is less than 10 μ g/g, Al
2O
3Foreign matter content is less than 100 μ g/g.REO content is 37.18% in the excellent molten slag, excellent molten rate 86.78%.
Embodiment 3
With concentration 31% the excellent molten RE (OH) that contains 1.5 tons of REO of HCl
3, control final pH=1 o'clock adds 180kg NH
4HCO
3Handle, boil after reacting completely, be incubated one hour.Gained feed liquid middle-weight rare earths concentration is 1.63mol/L, F
-Foreign matter content is 1.07 * 10
-3Mol/L, SiO
2Foreign matter content is 340 μ g/g, Fe
2O
3Foreign matter content is less than 10 μ g/g, Al
2O
3Foreign matter content is less than 100 μ g/g.REO content is 40.09% in the excellent molten slag, excellent molten rate 83.13%.
Embodiment 4
With concentration 15% the excellent molten RE (OH) that contains 1.5 tons of REO of HCl
3, control final pH=1.5 o'clock add 160kg KHCO
3Handle, boil after reacting completely, be incubated one hour.Gained feed liquid middle-weight rare earths concentration is 1.59mol/L, F
-Foreign matter content is 9.2 * 10
-4Mol/L, SiO
2Foreign matter content is 600 μ g/g, Fe
2O
3Foreign matter content is less than 10 μ g/g, Al
2O
3Foreign matter content is less than 100 μ g/g.REO content is 39.2% in the excellent molten slag, excellent molten rate 82.85%.
Embodiment 5
With concentration 36% the excellent molten RE (OH) that contains 1.5 tons of REO of HCl
3, control final pH=1～4 o'clock add the 90kg carbonated rare earth and handle, and boil after reacting completely, and are incubated one hour.Gained feed liquid middle-weight rare earths concentration is 1.65mol/L, F
-Foreign matter content is 6.7 * 10
-4Mol/L, SiO
2Foreign matter content is 420 μ g/g, Fe
2O
3Foreign matter content is less than 10 μ g/g, Al
2O
3Foreign matter content is less than 100 μ g/g, and REO content is 37.50% in the excellent molten slag, excellent molten rate 84.72%.
Embodiment 6
With concentration 29% the excellent molten RE (OH) that contains 1.5 tons of REO of HCl
3, control final pH=1～4 o'clock add 30kg carbonated rare earth and 100kg NH
4HCO
3Handle, boil after reacting completely, be incubated one hour.Gained feed liquid middle-weight rare earths concentration is 1.55mol/L, F
-Foreign matter content is 4.2 * 10
-3Mol/L, SiO
2Foreign matter content is 360 μ g/g, Fe
2O
3Foreign matter content is less than 10 μ g/g, Al
2O
3Foreign matter content is less than 100 μ g/g.REO content is 38.92% in the excellent molten slag, excellent molten rate 83.44%.
Claims (6)
1. the optimal dissolving method of the low fluorine rare earth chloride liquid of preparation from f_c_ce_la concentrate is characterized in that: with the rare earth hydrate RE (OH) of the excellent molten REO of containing of hydrochloric acid reagent
3, the pH value of the hierarchy of control adds gas perturbation reagent and handles less than 4, boils after reacting completely, and insulation promptly obtains low fluorine rare earth chloride liquid.Described gas perturbation reagent is for producing the compound or the mixture of carbon dioxide in system.The add-on of gas perturbation reagent is: in the throwing ore deposit amount of rare earth oxide per ton (REO), consumption is 50～100kg.
2. the optimal dissolving method of claim 1 record is characterized in that described gas perturbation reagent is urea, volatile salt, bicarbonate of ammonia, salt of wormwood, saleratus, yellow soda ash, sodium bicarbonate, carbonated rare earth or any mixture between them.
3. the optimal dissolving method of claim 1 record, the pH value that it is characterized in that reaction system is 1～4.
4. the optimal dissolving method of claim 1 record, it is characterized in that the add-on of described gas perturbation reagent is: in the throwing ore deposit amount of rare earth oxide per ton (REO), consumption is 70～85kg.
5. the optimal dissolving method of claim 1 record, the weight percent concentration that it is characterized in that used hydrochloric acid reagent is greater than 10%.
6. the optimal dissolving method of claim 1 record, the weight percent concentration that it is characterized in that used hydrochloric acid reagent is 10-36%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011098422A CN1166788C (en) | 2001-03-20 | 2001-03-20 | Optimal dissolving method of preparing rare earth fluorochloride material liquid from bastnasite concentrate |
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|---|---|---|---|
| CNB011098422A CN1166788C (en) | 2001-03-20 | 2001-03-20 | Optimal dissolving method of preparing rare earth fluorochloride material liquid from bastnasite concentrate |
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| CN1323908A CN1323908A (en) | 2001-11-28 |
| CN1166788C true CN1166788C (en) | 2004-09-15 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298871C (en) * | 2004-07-07 | 2007-02-07 | 冕宁县飞天实业有限责任公司 | Method for producing mischmetal using Mianning rare earth ore as raw material |
| CN102605198B (en) * | 2012-01-13 | 2013-09-25 | 东北大学 | Decomposition method of bastnaesite |
| CN102936656A (en) * | 2012-11-20 | 2013-02-20 | 东北大学 | Method for removing fluorine in bastnaesite sulfuric acid leaching liquid by aluminiferous adsorbing agent |
| CN103792269B (en) * | 2014-01-23 | 2016-04-20 | 包头华美稀土高科有限公司 | Fluoride ion electrode method directly measures the analytical approach of content of fluoride ion in carbonated rare earth |
| CN103952554B (en) * | 2014-05-19 | 2016-06-22 | 淄博包钢灵芝稀土高科技股份有限公司 | Precipitate the carbothiolic acid dissolubility method containing cerium carbonated rare earth |
| CN111636002B (en) * | 2020-05-28 | 2022-04-19 | 四川省冕宁县方兴稀土有限公司 | Method for removing fluorine from rare earth chloride mixed solution obtained by acid-base combination treatment |
| CN114182114A (en) * | 2021-12-14 | 2022-03-15 | 上海理工大学 | Green and clean fluorine removal method for fluorine-containing mixed rare earth chloride solution |
| CN114182113A (en) * | 2021-12-14 | 2022-03-15 | 上海理工大学 | Method for efficiently removing fluorine from fluorine-containing mixed rare earth chloride solution |
| CN115893466A (en) * | 2022-12-30 | 2023-04-04 | 中稀(广西)金源稀土新材料有限公司 | Preparation method of low-fluorine rare earth oxide |
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